United States Office Of Air Quality EPA-454/R-00-038d
Environmental Protection Planning And Standards September 2000
Agency Research Triangle Park, NC 27711
Air
EPA
Source Characterization For
Sewage Sludge Incinerators
Final Emissions Report
Volume III of III
Appendix K - Appendix P
Metropolitan Sewer District (MSD)
Mill Creek Wastewater Treatment Plant
Cincinnati, Ohio
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EP A-454/R-00-03 8d
SOURCE CHARACTERIZATION FOR SEWAGE SLUDGE INCINERATORS
FINAL EMISSIONS REPORT, VOLUME III OF III, APPENDIX K - APPENDIX P
METROPOLITAN SEWER DISTRICT (MSD)
MILL CREEK WASTERWATER TREATMENT PLANT
CINCINNATI, OHIO
Prepared for:
Clyde E. Riley (MD-19)
Emissions, Monitoring and Analysis Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Air and Radiation
Office of Air Quality Planning and Standards
Research Triangle Park, North Carolina 27711
September 2000
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TABLE OF CONTENTS
Page
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
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TABLE OF CONTENTS
(Continued)
Page
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, 02, and C02 5-5
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 5-20
5.2.1 Scrubber Water Sampling 5-20
5.2.2 Scrubber Water Analysis 5-23
5.2.2.1 PCB Analysis 5-23
5.2.2.2 D/F Analysis 5-24
5.2.2.3 Chlorine Analysis , 5-25
5.2.2.4 pH/Temperature Determination 5-25
5.3 Process Sludge Feed 5-25
5.3.1 Sludge Feed Sampling 5-25
5.3.2 Sludge Feed Analysis 5-30
5.3.2.1 PCB Analysis 5-30
v
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TABLE OF CONTENTS
(Continued)
Page
5.3.2.2 D/F Analysis 5-30
5.3.2.3 Chlorine Analysis . . 5-33
5.3.2.4 Percent Solids Analysis 5-34
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 . . . 6-1
6.1.1.2 Continuous Emission Monitoring 6-3
6.1.2 Sample Handling 6-7
6.1.3 Laboratory Analysis 6-7
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 OA 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 PitotTube 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
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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 Chaln-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
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
vii
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TABLE OF CONTENTS
(Continued)
F-2 D/F tab 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
6-1 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
I-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
Appendix L • Continuous Emissions Monitoring (CEM) Data
L-1 CEM Test Data Summary
L-2 1-Min Data Printouts
viii
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TABLE OF CONTENTS
(Continued)
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 COj and 02 Protocols (40 CFR 60, Appendix A, Method 3A)
N-10 Composite Sampling
Appendix 0 - List of Project Participants with Titles
0-1
MSD
0-2
USEPA
0-3
Battelle
0-4
ETS
0-5
Pacific Environmental
0-6
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 OA Officer Site Visit Checklist
ix
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LIST OF TABLES
Page
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% Oj) 2-9
Table 2-3. Toxic PCB Results - WHO Toxic Equivalent Stack Gas
Concentrations (ng/dscm, adjusted to 7% 02) 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% 02i 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. Bias and Instrument Drift Check Data 6-5
Table 6-4. Response Time Check 6-4
Table 6-5. Sample Transfer Schedule 6-7
x
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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-Sa. 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
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LIST OF TABLES
(Continued)
Page
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 6-53
Table 6-25. Summary of PCB Results and Standard Recoveries for Scrubber
Water Outlet Samples 6-54
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 6-87
xii
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LIST OF FIGURES
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 5-26
Figure 5-8. Flow Diagram for Preparation and Extraction of Scrubber
4 Water Samples for D/F Analysis 5-27
Figure 5-9. Flow Chart for Sludge Feed Sampling 5-29
Figure 5-10. Flow Diagram for Sample Preparation and Extraction of Sludge
Feed Samples for PCB Analysis 5-31
Figure 5-11. Flow Diagram for Preparation and Extraction of Sludge Feed
Samples for D/F Analysis 5-32
xiii
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APPENDIX K
Equations and Guidelines Used for Calculating
M. . . . - M - i/i. , ¦ L%.. ; Vr ... ...... - .... *-*.
-.iSs'yc- 1 * 'Sr-.;: u a,v- ^-'i^-ar*
Resultsj
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K-l
Stack Sampling Reference Methods 2-5
Example Calculations
K-1
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APPENDIX K-1
STACK SAMPLING REFERENCE METHODS
EPA METHODS 2-5 EXAMPLE CALCULATIONS (English Units)
Metered Gas Sample Volume at Standard Conditions
AH
y xyx-^L. x
m 29.92
13.6
+ 460
2. Gas Volume of Water Vapor Collected in Impinger Liquid
W» = <- *0*0.04707
3. Gas Volume of Water Vapor Collected in Silica Gel
= <*, - 0.04715
4. Moisture Volume Fraction in Flue Gas
V + ^
fi _ we(sM) vwsg(st$
m v + V + V
rtrae(stt5 *m{sW5
5.' Moisture Volume Percentage in Flue Gas
%H20 = Bm* 100
6. Absolute Pressure of Flue Gas
p = p +
s s 13.6
7. Nitrogen Content of Flue Gas
%N2 = 100 - (%C02 + %02 * %CO)
8. Dry Molecular Weight of Flue Gas
Md = 0.44 x%C02 + 0.32 *%02 + 0.28 x (%A/2 + %CO)
9. Wet Molecular Weight of Flue Gas
- SJ + 18-e^
K-2
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10.
EPA METHODS 2-5 EXAMPLE CALCULATIONS - continued
Concentration at 7% 02
C7 =C^x
20.9-7.0
20.9-%0,
11, Average Gas Velocity, ft/sec
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NOMENCLATURE FOR EPA METHODS 2-5 EXAMPLE CALCS
As
= _ Stack area, ft2
An
= Cross-sectional area of nozzle, ft2
Bws
= Moisture volume fraction
Cp
= Pitot tube coefficient (=0,84)
C, '
= Stack gas concentration, as measured, in ng/dscm
C7
= Stack gas concentration, adjusted to 7% oxygen, in ng/dscm
Ds
= Stack diameter, inches
AH
= Average meter orifice pressure, in.W.C,
AP
= Pitot tube differential pressure, in.W.C.
Fc
= Combustion factor
Y
= Meter calibration factor, gamma
%!
= Isokinetic Variation, percentage
L
= Length of rectangular stack or duct, inches
md
Dry molecular weight, Ib/lb-mole
Ms
= Wet molecular weight, Ib/lb-mole
Pb
= Barometric pressure, in.Hg
Ps
= Absolute stack pressure, in.Hg
P
¦ italic
= Average static pressure, in.W.C.
Qa
= Actual gas flow rate, acfm
Qs
= Standard gas flow rate, scfm
QsJ
= Dry standard gas flow rate, dscfm
Tm
= Average meter temperature, °F
Ts
= Average stack temperature, °F
vf
= Final impinger volume, ml
V,
= Initial impinger volume, ml
vm
= Uncorrected metered gas volume, dcf
^m(std)
= Corrected gas volume, dscf
= Average gas velocity, ft/sec
^wc(std)
= Gas volume of water caught in impingers, scf
^wsg(std)
= Gas volume of water caught in silica gel, scf
w
= Width of rectangular stack or duct, inches
w,
= Final silica gel mass, grams
w,
= Initial silica gel mass, grams
%Oj
= Dry volumetric concentration of 02, %dv
%co2
= Dry volumetric concentration of C02, %dv
%co
= Dry volumetric concentration of CO, %dv
%n2
= Dry volumetric concentration of N2, %dv
%EA
= Percent excess air
e
= Total sampling time, minutes
K-4
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K FACTOR FOR ISOKINETIC SAMPLING
K = 846.72xDn4*AH4xCp*<1-BJ2*
Md*(Tm^ 460) * P.
MS*(T~ 460}*P
m
NOMENCLATURE
Nozzle Diameter, inches
Orifice Meter Coefficient, in. W,C.
Pitot tube coefficient (=0.84)
Moisture volume fraction
Dry molecular weight, Ib/lb-mole
Average meter temperature, °F
Wet molecular weight, Ib/lb-mole
Absolute stack pressure, in.Hg
Wet molecular weight, Ib/lb-mole
Average stack temperature, °F
Meter Absolute Pressure, in.Hg
(Assume Pm = PB, the barometric pressure)
K-5
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K-2
Example Calculations for PCB Analysis
K-6
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APPENDIX K-2
EXAMPLE CALCULATIONS FOR PCB ANALYSIS
1. Concentration of the PCB compounds in the air sample.
c = Aj^Qh
* Ab x RF„ x Ws
where:
Cx
concentration of unlabeled PCB congeners in the front half or back
half extract (pg/dscm),
Ax
sum of the integrated ion abundances of the quantitation ions for
unlabeled PCBs, •
sum of the integrated ion abundances of the quantitation ions for the
labeled internal standards,
a,
quantity, in pg, of the internal standard added to the sample before
extraction,
RF„
calculated mean relative response factor for the analyte,
W,
volume of air sampled (dscm).
2. Concentration of a native PCB analytc in an emission sample is computed by summing
the concentration of the front half and the back half, as follows:
Concentration in emission sample (pg/dscm) =
where:
= Concentration of the compound in the front half (pg/dscm), calculated per Equation J.
- Concentration of the compound in the back half (pg/dscm), calculated per Equation I,
3. Concentration of the PCB compounds in the sludge extract
c = A x Qts
x Ak x RFn x Ws
where;
C, = concentration of unlabeled PCB congeners in the sample (pg/g, dry
weight),
A, = sum of the integrated ion abundances of the quantitation Ions for
unlabeled PCBs,
Au - sum of the integrated ion abundances of the quantitation ions for the
labeled internal standards,
Q„ = quantity, in pg, of the internal standard added to the sample before
extraction,
RF„ ¦ calculated mean relative response factor for the analyte,
= weight of sample extracted (g, dry weight),
K-7
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4. Concentration of the PCB compounds in the scrubber water extract
c
* Ais x RF„x Vs
where:
Cx = concentration of unlabeled PCB congeners in the sample (pg/L),
A, = sum of the integrated ion abundances of the quantitation ions for
unlabeled PCBs,
Aa = sum of the integrated ion abundances of the quantitation ions for the
labeled internal standards,
Qb - quantity, in pg, of the internal standard added to the sample before
extraction,
RF„ = calculated mean relative response factor for the analyte,
Vt *= volume of sample extracted (L).
5. Calculate the percent recovery of the internal standards measured in the sample extract,
using the formula:
At *
Percent recovery = ==*— * J 00
Qa* A„x RF t
where:
Aa = sum of the integrated ion abundances of the quantitation ions for the
labeled internal standard,
An = sum of the integrated ion abundances of the quantitation ions for the
labeled recovery standard,
Qu - quantity, in pg, of the internal standard added to the sample before
extraction,
Q„ = quantity, in pg, of the recovery standard added to the cleaned-up
sample residue before HRGC/HRMS analysis, and
RFa * calculated mean relative response factorfor the labeled internal
standard relative to the appropriate recovery standard.
Calculate the percent recovery of the cleanup standard similarly.
6. Accuracy
Accuracy is defined as the agreement between a measurement and the actual (i.e., true) value.
Accuracy is expressed as the percent recovery of an analyte that has been used to fortify an
investigative sample (XAD resin) or a standard matrix (e.g., analyte free water) at a known
concentration prior to analysis, and is expressed by the following formula:
K-8
-------
Accuracy = % Recovery
¦r
where:
A, =
A0 =
Af
Total amount found in fortified sample or standard
Amount found in unfortified sample
Amount added to sample.
Laboratory accuracy will be assessed through the analysis of matrix spikes and surrogate spikes
and the determination of percent recoveries.
7. Precision
Precision is defined in EPA Requirements for Quality Assurance Project Plans for Environ-
mental Data Operations, U.S. EPA QA/R-5, as the measure of mutual agreement among
individual measurements of the same property, usually under prescribed similar conditions
expressed generally in terms of analysis of samples relative to the average of those results for a
given analyte using the formula:
8. Completeness
Completeness is a measure of the relative number of analytical data points that meet all of the
acceptance criteria for accuracy, precision, and any other criteria required by the specific
analytical methods used. The level of completeness can also be affected by loss or breakage of
samples during transport, as well as external problems that prohibit collection of the sample.
%RSD- -^-xlOO
X
where:
X
%RSD
o
Relative standard deviation
Standard deviation of the triplicate sample results
Average of the triplicate results.
K-9
-------
K-3
Relative Standard Deviation Calculation Worksheet
K-10
-------
51
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K-11
-------
wrm
MSO Sewaga SfcidQa tnctoaniKy T«sl Program
Dndmctt. OH
WA1435
Drift Test Report
mm
WWarOut
SfudQO
aMai
W0R3
VVOR4
Moan
SO
%*SD
3R2
SR3
SR4
. W«n
50
ttRSD
4 165
1.83?
2.52
2.64?
1J0774
42.417
40 669
41096
45 366
42.460
2.935616
M72
am
0«42
0654
0 814
0.196697
19.192
7015
7.369
7.289
7,231
0.193629
2.678
0 157
0.074
0.124
0.116
0041769
35 315
0691
0674
0 736
0.701
0033151
4.726
ijw
1.272
1.621
1.923
0.21010$
14.366
1225
13.497
12.656
12 868
0623582
4.646
0.006
0.022
005
0.0S3
0.032063
14111
0231
0276
0241
0.249
0023629
• 477
0.135
0046
0 098
0.093
0.04471
46.675
1 116
1.214
1.479
1 270
0.160977
14.719
0.240
0.116
0236
0.200
0.073323
36.661
1.772
1.863
1.676
1.644
0.062164
3.372
0.1 If
0.033
0.063
0.078
0.04319
55136
0.472
0565
0.536
0 524
0047565
• 075
0.159
0.06
0 125
0.114
0049663
43.412
0.878
09EB
0,959
0935
0.049568
8.361
0.113
0.046
0096
0.066
0034034
36.422
0.453
0601
0.656
0 570
0.10499
16.416
0.264
0.143
0296
0.23S
0.06M68
J4.M7
2.5?8
2.572
2.778
2 625
0.133061
5.676
0688
0366
0 653
0.566
0.176001
30.968
6 002
676
6711
6 498
0.430644
6.628
0 03
0014
0.044
0.029
0.015011
51.174
0.161
0.196
OJ218
0 199
001852
6.307
KB CongaiMr
3,3^,4Metrac$*3«&iprtflny1 (TC8) (PCB-7?)
2.3,?,4,4'-p«ntacftorQbtpheny< (PbCB) (PC0-1OS)
2.3.4,4',5-f5®ol«cNoa3ttph<»nv< (PeCB) (PCB-H4)
2.3'.4,4,,5-pofit»chlocofc»pheoyl (PeCB) (PCB-116)
2,.3.4.4,.5-pe«lachloroNptienyt (PeCB) JPCB-123)
S.J^^'.S-peoUcWorobltrfwiyl {P«CB| (PC0-126)
2.3,3\4.4\S4>ex»chtarob»pha»»tf (H*CB) (PCIM56)#
2,3,?,4,4'.5,'*ie)i»cMorobl|)h«ny4 (HxCB) (PCB-157*
2,TA4\SStmMf*xi*iH*wnt HpCOF
0.017
0029 10 03$)
fVALUEf
0.006
•VALUE!
0339
0264
0.377
0300
0.070
23.459
Total HpCOF
0006
10 396
0008
3.470
5996
172 656
0.313
034
0441
0365
0.087
18.5Q2
OctaCDF
1.121
1 733
1 416
1424
0306
21.482
0 756
0.932
1-272
0.997
0.262
26.565
Total CDF
¦1.619
2.778
1963
2.193
0 512
23341
3923
4.381
5.605
4.703
0981
20.669
Total COO * CDF
-------
K-4
Gas Concentration Correction to
7% 02 Worksheet
K-13
-------
9/3/99 Air Corn • 7% Oxygen
Dloxln/Furan Results
MSD Incinerator Tost
Cincinnati, OH
Uncorrected Concentration ng/dscm Corrected Concentration ng/dscm
Analyta
Run 2
Run 3
Run 4
Run 2
Run 3
Run 4
Dloxtns
2,3,7,8-TCDD#
0.107
0.067
0.034
0.209
0.118
0.063
Total TCDD
3.025
3.534
0.719
5.922
6.218
1.333
1,2,3,7,8-PCDD
0.017
0.013
0.005
0,033
0.023
0.009
Total PCDD
0.706
0.658
0.188
1.382
1.158
0.348
1,2,3,4,7,8-HxCDD
0.015
0.015
0.006
0.029
0,026
0.011
1,2,3,6,7,8-HxCDD
0.038
0.039
0.013
0.074
0.069
0.024
1,2,3,7,8.9-HxCDD
0.039
0.035
0.015
0.076
0,062
0.030
Total HxCDD
0.806
0.583
0.324
1.188
1.026
0.600
1,2,3.4,6,7,8-HpCOD
0.204
0.203
0.093
0.399
0.357
0.172
Total HpCDD
0.459
1.453
0.237
0.899
2.557
0.439
OctaCOO
0.317
0.241
0.14
0.621
0.424
0.259
Total CDD
5.113
6.469
1.608
10.010
11.382
2.980
Furans
2.3,7,8-TCDF #
1.583
1.236
0.533
3.099
2.175
0.988
Total TCDF
5.607
4.879
2,571
10.977
8.585
4.765
1,2,3,7,8-PCDF
0.195
0.15
0.067
0.382
0.264
0.124
2,3,4,7,8-PCDF
0.389
0.282
0.123
0.782
0.496
0.228
Total PCDF
4,933
3.666
1.536
9.658
6.450
2.847
1,2,3,4,7,8-HxCDF
0.226
0.178
0.091
0.442
0.313
0.169
1,2,3.6,7,8-HxCDF
0.081
0.066
0.035
0.159
0.118
0.065
2,3,4,8,7, B-HxCDF
0.128
0.097
0.051
0.247
0.171
0.095
1,2,3,7,8,9-HxCDF
NO
NO
ND
ND
ND
ND
Total HxCDF
1.126
0.879
0.41
2.204
1.547
0.760
1,2,3,4,6.7.8-HpCDF
0.223
0.184
0.102
0,437
0.324
0.189
1,2,3,4,7.8,9-HpCDF
0.022
0.017
0.009
0.043
0.030
0.017
Total HpCDF
0,328
0.261
0.136
0.642
0.459
0.252
OctaCDF
0.09
0.083
0042
0.176
0.146
0.078
Total CDF
12.084
9.768
4.697
23.657
17.187
8.705
Total CDD ~ CDF
17.197
16.237
6.305
33.667
28.569
11.685
WA1-05
Draft Test Report
Oj Concentration
Correction Fqn.
R2 Formula:
R3 Formula:
R4 Formula:
Uncorrected * 13.9/7.1
Uncorrected * 13.9/7.9
Uncorrected* 13.9/7.5
-------
9/24/99 Air Correction , 'xygen
PCB Results
MSD Incinerator Test
Cincinnati, OH
7% O,
Uncorrected Concentration ng/dscm Corrected Concentration ng/dscm
Analyte
Run 2
Run 3
Run 4
Run 2
Run 3
Run 4
PCB-77
15.623
10.681
4.275
30.586
18.793
7.923
PCB-105
2.689
2.455
0.945
5.225
4.320
1.75-:
PCB-114
0.389
0.340
0.137
0.762
0.598
0.254
PCB-118
5.722
5.268
2.211
11.202
9.269
4.098
PCB-123
0.121
0.111
0.038
0.237
0.195
0.070
PCB-126
0.700
0.584
0.210
1.370
1.028
0.389
PCB-156
0.645
0.565
0.213
1.263
0.994
0.395
PCB-157
0.221
0.179
0.079
0.433
0.315
0.146
PCB-167
0.380
0.337
0.138
0.760
0.593
0.252
PCB-169
0.559
0.487
0.141 '
1.094
0.822
0.261
PCB-170
1.080
0.968
0.437
2.114
1.700
0.810
PCB-180
2.689
2.374
0.858
.5.264
4.177
1.586
PCB-189
0.095
0.078
0.044
0.186
0.134
0.082
02 Concentration R2 Formula: Uncorrected * 13.9/7,1
Correction Eqn. R3 Formula: Uncorrected * 13.9/7,9
R4 Formula: Uncorrected * 13.9/7.5
WA 1-05
Revised Draft Test Report
WHO Toxic Equivalent
TEFs Corrected Concentration ng/dscm
Run 2 Run 3 Run 4
1.00E-04
3.06E-03
1.88E-03
7.92E-04
1.00E-04
5.23E-04
4.32E-04
1.75E-04
5.00E-04
3.81 E-04
2.99E-04
1.27E-04
1.00E-04
1.12E-03
9.27E-04
4.10E-04
1.00E-04
2.37E-05
1-95E-05
7.04E-0S
0.1
1.37E-01
1.03E-01
3.89E-02
5.00E-04
6.31E-04
4.97E-04
1.97E-04
5.00E-04
2.16E-04
1.57E-04
7.32E-05
1.00E-05
7.B0E-06
5.93E-06
2.52E-06
0.01
1.09E-02
8.22E-03
2.61 E-03
1.00E-04
2.11 E-04
1.70E-04
8.10E-05
1.00E-05
5.26E-05
4.18E-05
1.59E-05
1.00E-04
1.86E-05
1.34E-05
8.15E-06
Corrected * TEF = TEQ Concentration
Concentration
-------
0/24J99 Concentration Correction to SUi' Volume and 7* Oxygon WA1-05
PAH Aii ik»u,. Revised DraB Test Report
1 MSD Incinerator Test
Cincinnati. OH Resulti
MSD Incinerate* Test
Cincinnati, OH
Lab Concentration (ngftample) Sampled Votume (dscm) Uncorrected Concentration Ccwraded Concentration
Anatyts
bju4
Run 2 Run 3
Run 4 Run 2
Run 3
Run 4
Run 2
Run 3
Run 4
Run 2
Run 3
Run 4
Acanapft^han®
160
130
28
1482
1.555
1.675
109.4391
83.80129
15 52239
214.2541
147.0959
28.78818
Acanafrthytone
1700
2000
280
1.482
1555
1875
1182.791
1286.174
155,2235
2276.449
2263.014
287.8816
AnSvBoanB
210
82
93.
1 462
1 555
1 875
143.8388
52.73312
55 52239
281 2088
9278359
102:9015
Benm(a)aRthraoene
138
390
821
1 482
1.555
1.875
93.02328
250.8039
48.95522
182116
441.2878
90.73035
Bemofbyiuoranthene
1210
1030
268
1 482
1 555
1.875
827.8334
862.3794
158.806
1620.298
1185.452
294.3204
OanasOQIIuorarithefw
1110
882
157
1 482
1.555
1.675
759 2339
381.4148
93 73134
1488 388
635907
173 7154
8«nio(g.h.l)ooryana
110
S3
0
1.482
1.555
1.875
75.2394
34.0838
0
147.2997
59.96988
0
Berajtfejpyrene
8200
10340
270
1 482
1.555
1.875
6292.75
8849.518
181.194
12319 61
11699 76
298.7463
Clvyaana
3500
2077
483
1 482
1.555
1.875
2393.981
1335.691
288 3582
4886.808
2350 14
534.4239
DtMnn
-------
Continuous EMssionsMomtoring
-------
L-l
CEM Test Data Summary
L-1
-------
Table L-1. CEM pally Results
CO', ppmov 1380 1170 I 1130 1230
THC\ ppm,jv 70.6 I 54.2 j 37.5 I 54.1
COj", % v 5.16 j 5.50 I 5.07 j 5.24
0-,', %v 13.7 j 13.0 j 13.4 | 13.4
* CO, C02, and O, 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.
L-2
-------
L-l-1
CEM Daily Results
L-3
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR
LINEARITY CHECK
JULY 19, 1999
Starting
07-19-99
02
C02
CO
%dv
%dv
ppmdv
Time
v"
12:21
4.07
4.82
-3.32
12:22
0.11
0.78
-3.32
12:23
0.06
0.57
-1.63
12:24
0.092
0.16Z
O.OOZ
12:25
21.06H
17.90H
0.00
12:26
15.01
13.58
0.00
12:27
11.71M
10 .-93H
0.00
12:28
0.06
0.17
2129.00
12:29
0.02
0.13
3042.00
12:30
0.01
0.12
3005.OOH
12:31
0.03
0.14
2953.00
12:32
0.01
0.13
1376.00
12:33
0.02
0.13
911.00L
12:34
0.15
0.22
1060.00
12:35
-0.00
0.11
1742.00
12:36
0.00
0.11
1819.00M
12:37
0.05
0.11
1820.00
12:38
0.15
0.12
1815.00
12:39
4.00
0.14
1815.00
12:40
5.97
0.15
1814.00
L-4
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR
LINEARITY CHECK
JULY 20, 1999
Starting
07-20-99
02.
C02
CO
%dv
%dv
ppmdv
Tine
07
56
0.00
0.10
3971.00
07
57
O.OOZ
0.10Z
254.00
07
58
3.25
2.20
6.07Z
07
59
21.06H
18.05H
5.73
08
00
18.96
16.35
-4.86
08
01
11.80M
10.96M
0.39
08
02
19.61
17.27
-5.65
08
03
11.98
10.98
-5.37
08
04
12.66
11.48
2.18
08
05
14.76
2.13
659.20
08
0&
18.82
13.68
2568.00
08
07
21.31
17.40
126.50
08
08
11.68
11.00
-4.25
08
09
11.32
10.94
-5.03
08
10
0.32
0.52
2592.00
08
11
0.05
0.11
5890.00
08
12
0.03
0.10
4771.00
08
13
0.08
0.14
1933.00
08
14
0.03
0.10
1897.00
08
15
0.04
0.12
2097.00
08
16
0.01
0.10
3075.00
08
17
0.01
0.10
4231.00
08
18
0.01
0.10
5009.00
08
19
0.00
0.10
5799.00
08
20
0.00
0.10
5922.00H
08
21
0.00
0.09
5909.00
08
22
0.00
0.10
4343.00
08
23
0.00
0.09
1806.00
08
24
0.04
0.12
1878.00L
08
25
0.02
0.10
1756.00
08
26
0.02
0.09
2027.00
08
27
0.00
0.09
3016.00
08
28
0.26
0.15
3105.00M
08
29
7.09
0.14
2922.00
08
30
8.39
0.14
1183.00
1-5
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR
LINEARITY CHECK
JULY 21, 1999
Starting
07-21-99
02
C02
CO
%dv
%dv
ppmdv
Time
09:01
8.26
0.57
1550.00
09:02
8.05
0.57
1550.00
09:03
7.20
0.56
1539.00
09:04
1.08
0.19
619.50
09:05
O.OOZ
0.112
-0.45Z
09:06
6.23
5.23
-2.29
09:07
10.72
8.76
4.59
09:08
20.99H
18.46H
-6.60
09:09
16.69
14.45
-6.43
09:10
11.75M
11.12M
82.60
09:11
0.07
0.15
5532.00
09:12
0.08
0.13
5676.00H
09:13
0.06
0.11
2986.00
09:14
0.00
0.09
1878.00L
09:15
0.05
0.10
1808.00
09:16
-0.00
0.09
2957.00
09:17
0.00
0.09
4689.00
09:18
-0.01
0.09
5881.00
09:19
-0.01
0.09
3975.00
09:20
-0.01
0.08
1908.00
09:21
-0.01
0.08
2724.00
09:22
-0.01
0.08
3106.00M
09:23
0.06
0.10
3100.00
09:24
1.24
0.25
3040.00
09:25
0.22
0.11
1343.00
1-6
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR
LINEARITY CHECK
JULY 22, 1999
Starting
07-22-99
02
C02
CO
%dv
%dv
ppmdv
Time
06:41
9.26
0.57
1571.00
06:42
1.48
0.18
870.00.
06:43
0.00
0.10
75.60
06:44
0.002
0.11Z
3.632
06:45
15.16
8.26
7.16
06:46
20.81H
17.96H
1.01
06:4?
20.10
17,28
-6.32
06:48
11.53L
10.91L
-5.65
06:49
6.80
6.79
105.70
06:50
0.03
0.13
4458.00
06:51
0.01
0.10
5925.00H
06:52
0.02
0.09
5894.00
06:53
0.16
0.11
3896.00
06:54
-0.00
0.09
1898.00
06:55
-0.00
-0.09
1852.00L
06:56
0.11
0.09
2273.00
06:57
-0.00
0.09
3045.00M
06:58
0.06
0.09
2008.00
06:59
-0.07
0.08
474.10
07:00
8.38
3.31
394.40
L-7
-------
Marker Description Display Average
A Data was Absent from original raw data file. /
C CYLINDER GAS AUDIT /
D DELAY FOR SAMPLING TRAIN TROUBLESHOOTING /
H HIGH CALIBRATION GAS /
L LOW CALIBRATION GAS /
M MID CALIBRATION GAS /
P SAMPLING POINT / /
R RESPONSE TIME *' /
Z ZERO CALIBRATION GAS /
Data was not used in calculated parameter averages.
1-8
-------
Lr2
One Minute Data Printouts
L-9
-------
L-2-1
Daily Data
L-10
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2A
JULY 20, 1999
Starting
07-20-99
Time
02
- % dv
CO 2
%dv
CO
ppmdv
15
01
14.25
4 .85
1407.00
15
02
14 .25
4 . 85
1395.00
15
03
14.18
4.89
1389.00
15
04
14 .23
4 .87
1391.00
15
05
14 .18
4.90
1353.00
15
06
14.18
4.89
1399.00
15
07
14.17
4.92
1403.00
15
08
14.12
4.96
1380.00
15
09
14.18
4 . 92
1392.00
15
10
14 .23
4.89
1413.00
15
11
14 .24
4.89
1438.00
15
12
14.28
4.87
1436.00
15
13
14 .23
4.89
1425.00
15
14
14.24
4 .88
1395.00
15
15
14 .16
4 .94 •••
1408.00
15
16
14.13
4.97
1445.00
15
17
14.09
5.00
1429.00
15
18
14.04
5.04
1416.00
15
19
14 .11
4.99
1419.00
15
20
14.14
4.96
1444.00
15
21
14.09
4.99
1435.00
15
22
14.01
5.06 -
1400.00
15
23
14 . 04
5.05
1404.00
15
24
13 .98
5.10
1411.00
15
25
14 . 04
5 . 05
1378.00
15
26
13.97
5.10
1362.00
15
27
13.99
5.08
1377.00
15
28
13 . 94
5.11
• 1353.00
15
29
13.90
5.15
1370.00
15
30
13 . 90
5.16
1375.00
15
31
13.84
5.22
1370.00
15
32
13 . 88
5.17
1368.00
15
33
13.83
5.20
1364.00
15
34
13 .86
5.18
1377.00
15
35
13 .86
5.18
1397.00
15
36
13.89
5.15
1390.00
15
37
13.89
5.15
1425.00
15
38
13.90
5.14
1426.00
15
39
13.89
5.14
1434.00
15
40
13 . 87
5 .17
1447.00
15
41
13 .83
5.19
1461.00
15
42
13 .94
5.10
1465.00
15
43
14.00
5.03
1471.00
15
44
13.99
5.05
1463.00
15
45
13.99
5.03
1444.00
L-11
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2A
JULY 20, 1999
Starting
07-20-99
02
C02
CO
• % dv
%dv
ppmdv
Time
15 :46
13.97
5.05
1447.00
15:47
14.06
4.98
1447.00
15:48
14.10
4.94
1462.00
15:49
14 .01
5.01
1466.00
15:50
13.99
5.02
1446.00
15:51
13 .97
5.04
1425.00
15:52
14.03
4.98
1470.00
15:53
14.09
4.95
1494.00
15:54
14.19
4 .86
1476.00
15:55
14.10
4.93
1449.00
15:56
14,09
4.94
1403.00
15:57
13.99
5.02
1422,00
15:58
13 .78
5.14
1405.00
15:59
13.66
5.23
1387.00
1-6:00
13.55
5.32
1407.00
16:01
13.39
5.45
1387.00
16:02
13.33
5.49
1398.00
16:03
13.30
5.50
1398,00
16:04
13.27
5.53
1426.00
16:05
13.16
5.62
• 1429.00
16:06
13.15
5.65
1422.00
16:07
13.22
5.60
1407.00
16:08
13.25
5 .59
1371,00
16:09
13 .36
5.50
1353.00
16 :10
13.35
5.51
1379,00
16 :11
13 .36
5.50
1387.00
16 :12
13 .29
5.57
1403.00
16:13
13 .24
5.62
1416.00
16 :14
13.18
5.66
1444.00
16 :15
13 .29
5.58
1455.00
16:16 -
13.36
5.51
1456.00
16 :17
13.29
5.57
1462.00
16:18
13.40
5.48
1462.00
16:19
13.36
5.53
1459.00
16:20
13.37
5.52
1465.00
16:21
13.37
5.53
1449.00
16:22
13.47
5.45
1469.00
16:23
13 .43
5.48
1465.00
16:24
13 .44
5.46
1453.00
16:25
13 .47
5.43
1430.00
16:26
13.57
5.37
1419.00
16:27
13.61
5.33
1398.00
16:28
13.63
5.30
1394.00
16:29
13.58
5.32
1415.00
16:30
13.56
5.34
1393.00
L-12
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2A
JULY 20, 1999
Starting
07-20-99
02
CO 2
CO
" % dv
%dv
ppmdv
Time
"
16:31
13 .56
5 .35
1376.00
16:32
13 .41
5.47
1353.00
16 :33
13 .45
5.43
1377.00
16:34
13.50
5.41
1396.00
16:35
13.58
5.35
1398.00
16:36
13 .46
5.45
1384.00
16:37
13.51
5.40
1381.00
16:38
13.67
5.27
1392.00
16:39
13.65
5.27
1397.00
16 :40
13.68
5.24
1428.00
16:41
13.7-7
5.16
1457.00
16:42
13.77
5 .16
1457.00
16 :43
13 .76
5.18
1487.00
16:44
13 .77
5.16
1503.00
16:45
13.76
5.17
1507.00
16 :46
13.79D
5.15D
1537.OOD
16 :47
13.7ID
5.22D
1546.00D
16 :48
13.68D
5.23D
1543.OOD
16 :49
13.69D
5.23D
1536.OOD
16:50
13.7ID
5.22D
1522.OOD
16:51
13.61D
5.31D
1500.OOD
16:52
13.64D
5.29D
1496.OOD
16:53
13.72D
5.20D
1476.OOD
16:54
13 .63D
5.28D
1446.OOD
16:55
13 .54D
5.36D
1437.OOD
16:56
13 .44D
5.44D
1426.OOD
16:57
13.55D
5.34D
1429.OOD
16 :58
13.4 ID
5.44D
1415.OOD
16 :59—
13.42D
5 .44D
1394.OOD
17:00
13.29D
5.55D
1398.OOD
17:01
13.23
5.61
1373.00
17:02
13 .18
5 .65
1355.00
17:03
13 .13
.5.69
1337.00
17 :04
13 .21
5.62
1352.00
17:05
13.18
5.67
1341.00
17 :06
13 .21
5.64
1337.00
17:07
13 .35
5'. 54
1334.00
17:08
13 .46
5.44
1346.00
17:09
13.48
5.44
1337.00
17:10
13.60
5.34
1339.00
17:11
13 .68
5.28
1377.00
17:12
13.74
5.23
1344.00
17:13
13 .76
5.21
1360.00
17:14
13.83
5 .16
1358.00
17:15
13.85
5.15
1333.00
1-13
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2A
JULY 20, 1999
Starting
07-20-99
.02
C02
CO
• % dv
%dv
ppmdv
Time
17:16
13.90
5.10
1309.00
17:17
13.96
5.06
1297.00
17:18
13.96
5.05
1286.00
17:19
14.05
4 .97
1269.00
17:20
14 .12
4.90
1269.00
17:21
14.16
4.87
1248.00
17:22
14 .14
4 . 87
1267.00
17:23
14 .18
4 .83
1288.00
17:24
14.17
4.85
1299.00
17:25
14 .15
4.87
1308.00
17:26
14 .20
4 .82
1317.00
17:27
14 .26
4.76
1313.00
17:28
14.25
4.75
1334.00
17:29
14 .21
4.79
1347.00
17:30
14.28
4.73
1370.00
17:31
14.27
4 .73
1377.00
17:32
14.29
4.71
1378.00
17:33
14.23
4.74
1412.00
17:34
14 .39
4 .60
1443.00
17:35
14.37
4.62
1457.00
17:36
14.33
4.65
1486.00
17:37
14.23
4.73 '
1477.00
17; 3B
14.22
4.73
1474.00
17:39
14 ,12
4 .81
1469.00
17:40
14 . 09
4.84
1469.00
17:41
14.04
4.87
1457.00
17:42
14 . 09
4 .85
1471.00
17:43
14 .03
4 ,89
1450.00
17 :44
13 .99
4.92
1471.00
17:45
14.06
4 .86
1459.00
17:46
14.00
4.90
1449.00
17:47
13.85
5.02
1449.00
17:48
13.87
5.02
1413.00
17:49
13 .71
5.15
1416.00
17:50
13.65
5.20
1428.00
17:51
13.52
5.30
1425.00
17:52
13.49
5.34
1441.00
17:53
13.48
5.33
1444.00
17:54
13.50
5.31
1453.00
17:55
13.48
5.35
1442.00
17:56
13.42
5.39
1461.00
17:57
13.39
5.40
1465.00
17:58
13.30
5.48
1449.00
17:59
13.27
5.52
1478.00
18:00
13 .24
5 .54
1475.00
L-14
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2A
JULY 20, 1999
Starting
07-20-99
Time
.02
" % dv
C02
%dv
CO
pptndv
18
01
13 .32
5.50
1465.00
18
02
13 .40
5.42 '
1478.00
18
03
13.42
5 .41
1467.00
18
04
13 .46
5.39
1460.00
18
05
13 .36
5 .45
1463.00
18
06
13 .43
5.39
1470.00
18
07
13 .47
5.37
1482.00
18
08
13.44
5.41
1513.00
18
09
13 .52
5.35
1543.00
18
10
13.55
5.33
1551.00
18
11
13.58
5.28
1564.00
18
12
13 .54
5.33
1607.00
18
13
13 .55
5.32
1599.00
IB
14
13 .52
5.34
1563.00
18
15
13.53
5.35
1570.00
195 MinAvg
13 .77
5.18
1416.02
Data Corrected for Calibrations
195 MinAvg 13.57 5.13 1392.23
L-15
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2A
JULY 20, 1999
Calibrations:
[C02 ] Span Value = 20
LOW Calibration Gas = 0.00 HIGH Calibration Gas = 11.01
INITIAL CALIBRATION TIME --> 1424
LOW Cal. Response = 0.12 HIGH Cal. Response = 10.9S
FINAL CALIBRATION TIME > 1823
LOW Cal. Response = 0.15 HIGH Cal. Response = 10.93
LOW System Drift = 0.13 % HIGH System Drift = -0.34 %
[CO ] Span Value =6000
LOW Calibration Gas =- 0.00 HIGH Calibration Gas = 1809.00
INITIAL CALIBRATION TIME --> 1424
LOW Cal. Response = 4.13 HIGH Cal. Response « 1847.30
FINAL CALIBRATION TIME > 1823
LOW Cal. Response = 0.00 HIGH Cal. Response = 1831.3 0
LOW System Drift « -0.07 % HIGH System Drift = -0.27 %
[02 ] Span Value = 25
LOW Calibration Gas = 0.00 HIGH Calibration Gas •= 11.5"
INITIAL CALIBRATION TIME --.> 1424
LOW Cal. Response = 0.17
FINAL CALIBRATION TIME > 1823
LOW Cal. Response = 0.11
LOW System Drift =
HIGH Cal. Response = 11.80
HIGH Cal. Response = 11.59
-0.83 %
-0.21 % HIGH System Drift =
L-16
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2b
JULY 20, 1999
Starting
07-20-99
,02
C02
CO
- % dv
%dv
ppmdv
Time
18
31
13,37
5.74
1422.00
18
32
13.45
5.69
1439.00
18
33
13 .44
5.70
1430.00
18
34
13.38
5.76
1419.00
18
35
13 .47
5 .67
1421.00
18
36
13.58
5.58
1430.00
18
37
13.56
5.59
1415.00
18
38
13.57
5.59
1406.00
18
39
13.64
5 .53
1378.00
18
40
13 .68
5.50
1387,00
18
41
13.69
5.49
. 1389.00
18
42
13.70
5.50
1375.00
18
43
13 .76
5.45
1373.00
18
44
13 .81
5.40
1389.00
18
45
13 .92
5.32
1397.00
18
46
13 .88
5.34
1412.00
18
47
13 .84
5.36
1415.00
18
48
13.90
5.30
1426.00
18
49
13 .91
5.31
1440.00
18
50
13.91
5.31
1441.00
18
51
13.93
5.28
1434 .00
18
52
13.94
5.26
1435.00
18
53
13.93
5.27
1433.00 -
18
54
13 . 94
5.26
1426.00
18
55
14 . 01
5.22
1410.00
18
56
14 .10
5 .14
1375.00
18
57
13 . 99
5.23
1356.00
18
58
14 . 02
5.23
1353.00
18
59
- 14.12
5.14
1341.00
19
00
14.11
5.14
1354.00
19
01
14 .10
5.15
1374.00
19
02
14.08
5.16
1374.00
19
03
14 .11
5.'14
1382.00
19
04
14.10
5.15
1379.00
19
05
14.14
5.12
1387.00
19
06
14 .14
5.13
1389.00
19
07
14 .13
5.12
1418.00
19
08
14.24
5.03
1449.00
19
09
14.26
5.03
1453.00
19
10
14 .26
5 .00
1453.00
19
11
14.29
4 .99
1446.00
19
12
14.33
4 . 97
1428.00
19
13
14.35
4 .95
1426.00
19
14
14.34
4.95
1394.00
19
15
14.32
4 .97
1386.00
L-17
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2b
JULY 20, 1999
Starting
07-20-99
02
CO 2
CO
¦ % dv
%dv
ppmdv
Time
19
16
14.36
4.93
1398.00
19
17
14 .39
4 .92
1402.00
19
18
14.46
4.85
1390.00
19
19
14.45
4.86
1404.00
19
20
14 .40
4 .89
1405.00
19
21
14.39
4.91
1395.00
19
22
14.34
4.96
1402.00
19
23
14.29
5.00
1397.00
19
24
14 .25
5.03
1397.00
19
25
14.24
5.03
1423.00
- 19
26
14.28
5.01
1435.00
19
27
14.31
4.98
1445.00
19
28
14.29
5.00
1438.00
19
29
14.31
4.97
1424.00
19
30
14 .15
5.11
1416.00
19
31
14.08
5.16
1442.00
19
32
14 .03
5.22
1442.00
19
33
13 .98
5.27
1414.00
19
34
13.91
5.33
1390.00
19
35
13.94
5.31
1383.00
19
36
13 .92
5.33
1381.00
19
37
13.80
5.43
1370.00
19
38
13.67
5.55
1365.00
19
39
13 .60
5.63
1360.00
19
40
13.60
5.64
1350.00
19
41
13 .59
5.65
1376.00
19
42
13.65
5 .60
1395.00
19
43
13 .62
5.61
1431.00
19
44
13.46
5.74
1450.00
19
45
13 .50
5.73
1482.00
19
46
13 .48
5.75
1483.00
19
47
13.54
5.71
1456.00
19
48
13.62
5.61
1450.00
19
49
13.60
5.63
1479.00
19
50
¦ 13.59
5.65
1502.00
19
51
13.52
5.72
1510.00
19
52
13.48
5.74
1505.00
19
53
13.55
5.68
1502.00
19
54
13.58
5.67
1475.00
19
5 5
13.60
5.67
1453.00
19
56
13.56
5.70
1429.00
19
57 •
13.62
5.66
1423.00
19
58
13.64
5.64
1394.00
19
59
13 .63
5.65
1383.00
20
00
13.59
5.68
1384.00
L-18
-------
METROPOLITAN SE^ER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2b
JULY 20, 1999
Starting
07-20-99
•°2
C02
CO
• % dv
%dv
ppradv
Time
20
01
13,61
5.69
1374.00
20
02
13 .56
5.70
1381.00
20
03
13.59
5.69
1373.00
20
04
13 .63
5.64
1348.00
20
05
13.62
5.66
1358.00
20
06
13 .69
5 .61
1356.00
20
07
13.69
,
5.61
1343.00
20
08
13.87
5.46
1359.00
20
09
13 . 94
5.42
1370.00
20
10
13.93
5.43
1382.00
20
11
13.89
5.48
1396.00
20
12
13.99
5.42
1432.00
20
13
14.15
5.28
1418.00
20
14
14 .20
5.25
1397.00
20
15
14 .16
5.27
1421.00
20
16
14.24
5.22
1409.00
20
17
14 .34
5.14
13 83.00
20
18
14.40
5.09
1370.00
20
19
14 .39
5.08
1358.00
20
20
14 .39
5.08
1374.00
20
21
14 .45
5.01
1374.00
20
22
14 .37
5.08
1343.00
20
23
14 .39
5.06
1312.00
20
24
14 .37
5.06
1307.00
20
25
14 .45
4 . 98
1303.00
20
26
14 .49
4.94
1302.00
20
27
14 .46
4 .96
1295 .00
20
28
14 .36
5.02
1300.00
20
29
14 .29
5.10
1321.00
20
30
14 .38
5.01
1335.00
20
31
14 .36
5.02
1308.00
20
32
14 .33
5.03
1305.00
20
33
14 .36
5.00
1318.00
20
34
14.43
4.95
1340.00
20
35
14 .36
5 .00
1343.00
20
36
14.35
5 .01
1356.00
20
37
14 .31
5.03
1340.00
20
38
14 .29
5.04
1333.00
20
39
14 .32
5.01
1332.00
20
40
14.31
5.02
1341.00
20
41
14.34
4.99
1360.00
20
42
14 .26
5.05
1374.00
20
43
14 .33
4.99
1374.00
20
44
14.27
5.06
1375.00
20
45
14.31
5.01
1373.00
L-19
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2b
JULY 20, 1999
Starting
07-20-99
02
C02
CO
' -"% dv
%dv
ppmdv
Time
20:46
14 .24
5.04
1381.00
20:47
14 .26
5.04
1403.00
20:48
14.30
5.01
1425.00
20:49
14.33
4.97
1440.00
20:50
14.33
4.97
1450.00
20:51
14.32
5.00
1462.00
20:52
14.30
5.00
1449.00
20:53
14.29
5.02
1446.00
20:54
14 .26
5.03
1456.00
20:55
14 .13
5.14
1443.00
20:56
14.18
5.10
1428.00
20:57
14.11
5.15
1421.00
20:58
14.08
5.19
1419.00
20:59
14.01
5.25
1396.00
21:00
14 -.-04
5.22
1401.00
21:01
13.91
5.33
1373.00
21:02
13.89
5 .35
1375.00
21:03
13.88
5.35
1382.00
21:04
13.89
5.34
1371.00
21:05
13.84
5.39
1372.00
21:06
13.74
5.48
1356.00
21:07
13 .75
5.49
1385.00
21:08
13 .72
5.51
1389.00
21:09
13 .69
5.53
1368.00
21:10
13.71
5 .52
1353.00
21:11
13 .78
5 .47
1363.00
21:12
13.83
5.43
1348.00
21:13
13.93
5.35
1340.00
21:14
13.86
5.39
1332.00
21:15
13.91
5.36
1298.00
21:16
13.96
5.31
1268.00
21:17
14.01
5.29
1276.00
21:18
14.09
5.22
1264.00
21:19
14.11
5.22
1249.00
21:20
14.19
5.16
1253.00
21:21
14.26
5.12
1268.00
21:22
14.31
5.08
1263.00
21:23
14.34
5.06
1265.00
21:24
14.44
5.00
1258.00
21:25
14.50
4.96
1258.00
21:26
14.57
4.91
1270.00
21:27
14.59
4.89
1272.00
21:28
14.60
4 .89
1256.00
21:29
14 .62
4.87
1266.00
21:30
14.71
4.80
1266.00
1-20
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2b
JULY 20, 1999
Starting
07-20-99
Time
< 02 CO2
•' % dv %dv
CO
ppmdv
180 MinAvg
14.03 5.26
1383.51
Data Corrected for Calibrations
180 MinAvg 13.92 • 5.19 1366.72
L-21
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 2b
JULY 20, 1999
Calibrations:
i
[C02 ] Span Value = -20
LOW Calibration Gas = 0.00 HIGH Calibration Gas — 11.01
INITIAL CALIBRATION TIME --> 1823
LOW Cal. Response = 0.15 HIGH Cal. Response = 10.93
FINAL CALIBRATION TIME. > 2138
LOW Cal. Response = 0.14 HIGH Cal. Response = 11.05
LOW System Drift = -0.07 %
HIGft
System Drift =
0.63 %
[CO ] Span Value = 6000
LOW Calibration Gas = 0-00
HIGH
Calibration Gas
'= 1809.00
INITIAL CALIBRATION TIME 1823
LOW Cal. Response = 0.00
HIGH
Cal. Response =
1831.30
FINAL CALIBRATION TIME > 2138
LOW Cal. Response = 0.77.
HIGH
Cal. Response =
1830.90
LOW System Drift = 0.01 % HIGH System Drift = -0.01 %
(
I
[02 ] Span Value = 25
LOW-Calibration Gas = 0.00
INITIAL CALIBRATION TIME 1823
LOW Cal. Response = 0.11
FINAL CALIBRATION TIME > 2138
LOW Cal. Response = 0.07
LOW System Drift =
HIGH Calibration Gas = 11.50
HIGH Cal. Response = 11.59
HIGH Cal. Response = 11.62
0.13 %
-0.19 % HIGH System Drift *
1-22
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3A
JULY 21, 1999
Starting
07-21-99
Time
02
% dv
C02
%dv
CO
ppmdv
10:16
14.86
4.49
1598.00
10:17
14.93
4.43
1628.00
10:18
14.81
4.53
1617.00
10:19
14.72
4.60
1594.00
10:20
14.68
4.64
1570.00
10:21
14.65
4.67
1560.00
10:22
14.63
4.68
1568.00
10:23
14.65
4.64
1592.00
10:24
14.65
4.64
1587.00
10:25
14.65
4.63
1589.00
10:26
14.66
4.63
.1572.00
10:27
14.78
4.53
1582.00
10:28
14.94
4.39
1635.00
10:29
15.05
4.30
1691.00
10:30
15.14
4.22
1732.00
10:31
15.17
4.20
1766.00
10:32
15.03
4.28
1746.00
10:33
15.02
4.31
1721.00
10:34
14.96
4.37
1706.00
10:35
15.00
4.34
1692.00
10:36
14.94
4.37
1685.00
10:37
14.98
4.34
1693.00
10:38
15.09
4.26
1706.00
10:39
15.13
4.24
1684.00
10:40
15.13
4.22
1678.00
10:41
15.04
4.27
1669.00
10:42
14.98
4.33
1636.00
10:43
14.98
4.33
1627.00
10:44
14.79
4.46
1633.00
10:45
14.72
4.46
1637.00
10:46
14.16
4.83
1472.00
10:47
13.76
5.07
1281.00
10:48
13.41
5.28
1181.00
10:49
13.22
5.38
1070.00
10:50
13.21
5.38
1061.00
10:51
13.25
5.30
1060.00
10:52
13.17
5.34
1062.00
10:53
13.09
5.37
1079.00
10:54
12.88
5.51
1061.00
10:55
12.65
5.68
1033.00
10:56
12.39
5.89
1013.00
10:57
12.12
6.11
996.00
10:58
11.92
6.27
989.00
10:59
11.75
6.41
995.00
11:00
11.58
6.52
979.00
1-23
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RON 3A
JULY 21, 1999
Starting
07-21-99
02
C02
CO
.%- dv
%dv
ppmdv
Time
11:01
11.40
6.69
987.00
11:02
11.50
6.68
1016.00
11:03
11.90
6.49
1041.00
11:04
12.92
5.91
1114.00
11:05
13.28
5.64
1232.00
11:06
13.53
5.43
1251.00
11:07
13.72
5.28
1279.00
11:08
13.91
5.13
1292.00
11:09
14.02
5.04
1320.00
11:10
13.70
5.19
1320.00
11:11
13.61
5.24
1190.00
11:12
13.62
5.25
1160.00
11:13
13.64
5.23
1148.00
11:14
13.71
5.17
1160.00
11:15
13.81
5.09
1185.00
11:16
13.83
5.-08
1212.00
11:17
13.75
5.14
1213.00
11:18
13.72
5.17
1227.00
11:19
13.77
5.11
1220.00
11:20
13.78
5.11
1233.00
11:21
13.68
5.21
1225.00
11:22
13.82
5.11
1215.00
11:23
13.98
4.97
1253.00
11:24
14.16
4.82
1336.00
11:25
14.18
4.82
1357.00
11:26
14.12
4.85
1342.00
11:27
14.12
4.83
1336.00
11:28
14 • 01
4.91
1341.00
11:29
13.99
4.92
1346.00
11:30
14.12
4.82
1349.00
11:31
14.21
4.75
1376.00
11:32
14.20
4.75
1405.00
11:33
14.32
4.66
1427.00
11:34
14.35
4.62
1439.00
11:35
14.31
4.65
1442.00
11:36
14.27
4.67
1462.00
11:37
14.28
4.65
1456.00
11:38
14.30
4.64
1478.00
11:39
14.37
4.56
1508.00
11:40
14.34
4.59
1505.00
11:41
14.37
4.57
1508.00
11:42
14.30
4.64
1504.00
11:43
14.24
4.67
1516.00
11:44
14.16
4.73
1519.00
11:45
14.04
4.84
1497.00
L-24
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3A
JULY 21, 1999
Starting
07-21-99
02
C02
CO
%. dv
%dv
ppmdv
Time
-¦
11:46
14.02
4.85
1502.00
11:47
13.95
4.90
1494.00
11:48
13.99
4.86
1502.00
11:49
13.98
4.88
1508.00
11:50
13.99
4.87
1521.00
11:51
14.01
4.83
1531.00
11:52
13.93
4.90
1502.00
11:53
13.93
4.87
1511.00
11:54
13.64
5.01
1549.00
11:55
13.09
5.38
1366.00
11:55
12.78
5.61
1296.00
11:57
12.44
5.86
1245.00
11:58
12.13
6.11
1248.00
11:59
11.78
6.36
1246.00
12:00
11.40
6.66
1257.00
- 12:01
10.95
7.00
1306.00
12:02
10.46
7.41
1362.00
- 12:03
9.92
7.85
1539.00
12:04
9.60
8.18
1749.00
12:05
9.86
8.14
2137.00
12:06
10.24
7.98
1886.00
12:07
11.21
7.30
1727.00
12:08
12.03
6.64
1506.00
12:09
12.78
6.06
1321.00
12:10
13.37
5.57
1262.00
12:11
13.70
5.28
1222.00
12:12
13.90
5.10
1218.00
12:13
13.86
5.13
1225.00
12:14
13.34
5.44
1198.00
12:15
12.02
6.38
- 1159.00
12:16
11.75
6.63
1162.00
12:17
11.83
6.63
1170.00
12:18
12.12
6.44
1173.00
12:19
12.43
6.20
1151.00
12:20
12.65
6.05
1154.00
12:21
12.89
5.86
1153,00
12:22
13.04
5.75
1136.00
12:23
13.19
5.63
1111.00
12:24
13.21
5.61
1124.00
12:25
13.22
5.59
1130.00
12:26
13.18
5.60
1103.00
12:27
13.16
5.62
1094.00
12:28
13.20
5.56
1102.00
12:29
13.22
5.55
1134.00
12:30
13.17
5.59
1117.00
L-25
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3A
JULY 21, 1999
Starting
07-21-99
02
C02
CO
,% . dv
%dv
ppmdv
Time
12:31
13.17
5.57
1118.00
12:32
13.26
5.50
1141.00
12:33
13.27
5.49
1147.00
12:34
13.34
5.43
1136.00
12:35
13.29
5.46
1144.00
12:36
13.39
5.35
1144.00
12:37
13.33
5.40
1108.00
12:38
13.20
5.48
1094.00
12:39
13.04
5.58
1093.00
12:40
13.00
5.59
1079.00
12:41
12.84
5.71
1053.00
12:42
12.76
5.74
1022.00
12:43
12.70
5.79
1012.00
12:44
12.83
5.72
1022.00
12:45
12.89
5.72
1040.00
12:46
13.05
5.65
1042.00
12:47
13.03
5.65
1021.00
12:48
13.04
5.65
1025.00
12:49
13.00
5.65
1024.00
12:50
12.93
5.70
1026.00
12:51
13.05
5.60
1043.00
12:52
13.09
5.60
1026.00
12:53
13.03
5.63
1040.00
12:54
13.01
5.63
1051.00
12:55
13.05
5.60
1044.00
12:56
13.08
5.60
1030.00
12:57
13.18
5.53
1016.00
12:58
13.19
5.52
1022.00
12:59
13.22
5.49
1019.00
13T00
13.18
5.51
1013.00
13:01
13.24
5.46
1011.00
13:02
13.30
5.40
980.00
13:03
13.29
5.42
970.00
13:04
13.31
5.37
957.00
13:05
13.28
5.41
960.00
13:06
13.29
5.40
980.00
13:07
13.27
5.39
978.00
13:08
13.27
5.39
974.00
13:09
13.31
5.38
966.00
13:10
13.27
5.41
947.00
13:11
13.30
5.37
965.00
13:12
13.31
5.37
965.00
13:13
13.35
5.32
947.00
13:14
13.29
5.38
944.00
13:15
13.30
5.37
927.00
L-26
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3A
JULY 21, 1999
Starting
07-21-99
02
C02
CO
% dv
%dv
ppmdv
Time
-
-
180 MinAvg
13.45
5.34
1283.57
Data Corrected for Calibrations
180 MinAvg 13.32 5.35 1244.74
L-27
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3B
JULY 21, 1999
Starting
07-21-99
02
CO 2
CO
%¦ dv
%dv
ppmdv
Time
-
13:36
13.13
4.96
918.00
13:37
13.11
4.94
946.00
13:38
13.09
4.97
946.00
13:39
13.10
4.95
955.00
13:40 .
13.12
4.95
949.00
13:41
13.12
4.93
946.00
13:42
13.10
4.95
946.00
13:43
13.28
4.93
947.00
13:44
13.58
5.02
969.00
13:45
13.54
5.08
953.00
13:46
13.54
5.06
966.00
13:47
13.54
5.07
991.00
13:48
13.45
5.14
1022.00
13:49
13.45
5.14
1039.00
13:50
13.47
5.12
1024.00
13:51
13.44
5.16
1035.00
13:52
13.37
5.18
1040.00
13:53
12.96
5.45
1*055.00
13:54
12.76
5.62
1067.00
13:55
12.78
5.61
1084.00
13:56
12.71
5.66
1078.00
13:57
12.70
5.69
1064.00
13:58
12.60
5.75
1067.00
13:59
12.49
5.84
1072.00
14:00
12.42
5.91
1097.00
14:01
12.42
5.94
1144.00
14:02
12.44
5.94
1153.00
14:03
12.45
5.95
1139.00
14:04
12.45
5.94
1137.00
14:05
12.43
5.96
1177.00
14:06
12.29
6.08
1177.00
14:07
12.28
6.10
1175.00
14:08
12.12
6.22
1176.00
14:09
12.05
6.29
1180.00
14:10
11.85
6.46
1194.00
14:11
11.69
6.57
1221.00
14:12
11.58
6.65
1210.00
14:13
11.50
6.73
1211.00
14:14
11.42
6.79
1203.00
14:15
11.34
6.90
1222.00
14:16
11.32
6.90
1210.00
14:17
11.33
6.91
1190.00
14:18
11.32
6.89
1187.00
14:19
11.32
6.91
1187.00
14:20
11.35
6.89
1183.00
L-28
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3B
JULY 21, 1999
Starting
07-21-99
02
CO 2
CO
.%, dv
%dv
ppmdv
Time
14:21
11.36
6.91
1195.00
14122
11.45
6.81
1188.00
14:23
11.46
6.81
1183.00
14:24
11.55
6.77
1173.00
14:25
11.68
6.67
1161.00
14:26
11.76
6.62
1157.00
14:27
11.77
6.60
1163.00
14:28
12.00
6.46
1159.00
14:29
13.09
5.73
1190.00
14:30
13.33
5.55
1265.00
14:31
13.42
5.47
1263.00
14:32
13.46
5.42
1276.00
14:33
13.50
5.37
1298.00
14:34
13.55
5.32
1293.00
14:35
13.48
5.36
1290.00
14:36 ~
13.53
5.32
1296.00
14:37
13.55
5.30
1267.00
14:38
13.53
5.30
1253.00
14:39
13.46
5.36
1237.00
14:40
13.51
5.32
1233.00
14:41
13.49
5.32
1241.00
14:42
13.49
5.32
1262.00
14:43
13.51
5.30
1258.00
14:44
13.55
5.26
1243.00
14:45
13.58
5.24
1250.00
14:46
13.53
5.26
1251.00
14:47
13.57
5.23
1249.00
14:48
13.61
5.18
1246.00
14:49
13.58
5.21
1259.00
14:50
13.61
5.19
1241.00
14:51
13.52
5.26
1244.00
14:52
13.48
5.28
1249.00
14:53
13.49
5.27
1222.00
14:54
13.55
-
5.22
1230.00
14:55
13.52
5.25
1216.00
14:56
13.51
5.26
1194.00
14:57
13.49
5.29
1180.00
14:58
13.50
5.29
1164.00
14:59
13.48
5.29
1144.00
15:00
13.54
5.25
1133.00
15:01
13.56
5.22
1132.00
15:02
13.56
5.22
1145.00
15:03
13.58
5.19
1136.00
15:04
13.56
5.22
1119.00
15:05
13.59
5.20
1100.00
1-29
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3B
JULY 21, 1999
Starting
07-21-99
02
C02
CO
.,%¦ dv
%dv
ppmdv
Time
-
15:06
13.66
5.13
1106.00
15:07
13,57
5.17
1115.00
15:08
12.55
5.87
1097.00
15:09
12.48
5.95
1061.00
15:10
12.49
5.95
1043.00
15:11
12.44
5.99
1026.00
15:12
12.54
5.92
1041.00
15:13
12.51
5.94
1038.00
15:14
12.56
5.91
1041.00
15:15
12.60
5.88
1053.00
15:16
12.63
5.86
1052.00
15:17
12.69
--
5.83
1065.00
15:18
12.75
5.77
1067.00
15:19
12.85
5.66
1076.00
15:20
12.82
5.70
1069.00
15:21
12.89
5.64
1068.00
15:22
12.95
5.59
1074.00
15:23
13.06
5.49
1067.00
15:24
13.06
5.50
1059.00
15:25
13.09
5.47
1075.00
15:26
13.16
5.41
1071.00
15:27
13.18
5.38
1067.00
15:28
13.13
5.41
1067.00
15:29
13.14
5.40
1064.00
15:30
13.21
5.36
1049.00
15:31
13.17
5.38
1036.00
15:32
13.16
5.38
1051.00
15:33
13.24
5.30
1033.00
15:34
13.24
5.29
1039.00
15:35
13.17
5.34
1032.00
15:36
13.14
5.36
1029.00
15:37
13.14
5.35
1030.00
15:38
13.04
5.43
1011.00
15:39
13.06
5.4i
1012.00
15:40
13.14
5.36
1007.00
15:41
13.19
5.30
986.00
15:42
13.08
5.38
989.00
15:43
13.06
5.39
987.00
15:44
13.07
5.37
1007.00
15:45
13.13
5.32
1022.00
15:46
13.07
5.39
1019.00
15:4,7
13.09
5.35
1024.00
15:48
13.10
5.33
1035.00
15:49
13.16
5.29
1044.00
15:50
13.15
5.30
1043.00
L-30
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - ION 3B
JULY 21, 1999
Starting
07-21-99
02
C02
CO
„ % dv
%dv
ppmdv
Time
15:51 ~
13.11
5.31
1056.00
15:52
13.09
5.32
1078.00
15:53
13.05
5.34
1075.00
15:54
13.06
5.33
1067.00
15:55
13.09
5.32
1067.00
15:56
13.13
5.29
1067.00
15:57
13.04
5.36
1062.00
15:58
13.05
5.33
1072.00
15:59
13.01
5.35
1098.00
16:00
12.96
5.39
1105.00
16:01
12.90
5.44
1111.00
16:02
12.90
5.45
1120.00
16:03
12.78
5.53
1117.00
16:04
12.71
5.59
1117.00
16:05
12.62
5.65
1107.00
16:06
12.62
5.66
1120.00
16:07
12.59
5.68
1119.00
16:08
12.48
5.77
1144.00
16:09
12.34
5.88
1139.00
16:10
12.27
5.94
1150.00
16:11
12.28
5.92
1153.00
16:12
12.13
6.05
1157.00
16:13
12.11
6.07
1139.00
16:14
12.03
6.12
1140.00
16:15
11.99
6.18
1135.00
16:16
11.93
6,22
1127.00
16:17
11.85
6.28
1136.00
16:18
11.85
6.28
1127.00
16:19
11.74
6.37
1124.00
16:20
11.71
6.40
1119.00
16:21
11.65
6.44
1099.00
16:22
11.57
6.51
1090.00
16:23
11.57
6.51
1089.00
16:24
11.70
6.43
1081.00
16:25
11.51
6.60
1067.00
16:26
11.57
6.55
1051.00
16:27
12.09
6.24
1053.00
16:28
12.87
5.67
1151.00
16:29
12.95
5.62
1186.00
16:30
12.99
5.59
1184.00
16:31
13.00
5.58
1178.00
16:32
12.99
5.57
1181.00
16:33
13.03
5.55
1167.00
16:34
13.07
5.51
1178.00
16:35
13.12
5.46
1190.00
L-31
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3B
JULY 21, 1999
Starting
07-21-99
Time
02
%• dv
C02
%dv
CO
ppmdv
180 MinAvg
12.80
5.66
1115.78
Data Corrected for Calibrations
180 MinAvg 12.74 5.66 1095.76
L-32
-------
TROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 3B
JULY 21, 1999
Calibrations;
[C02 ] Span Value = 20
LOW Calibration Gas = 0.00
INITIAL CALIBRATION TIME —> 1326
LOW Cal. Response = 0.15
FINAL CALIBRATION TIME > 1643
LOW Cal. Response = 0.14
LOW System Drift =
HIGH Calibration Gas = 11.01
HIGH Cal. Response = 10.88
HIGH Cal. Response = 10.89
0.06 %
-0.04 % HIGH System Drift =
[CO ] Span Value s 6000
LOW Calibration Gas = 0.00 HIGH Calibration Gas = 1809.00
JITIAL CALIBRATION TIME —> 1326
LOW Cal. Response = - 2.06 HIGH Cal. Response = 1851.50
FINAL CALIBRATION TIME > 1643
LOW Cal. Response = 0.26 HIGH Cal. Response = 1831.10
LOW System Drift = -0.03 %
HIGH
System Drift =
-0.34 %
[02 ] Span Value = 25
LOW Calibration Gas = 0.00
HIGH
Calibration Gas
= 11.50
INITIAL CALIBRATION TIME —> 1326
.
LOW Cal. Response = 0.11
HIGH
Cal. Response =
11.70
FINAL CALIBRATION TIME > 1643
LOW Cal. Response = 0.12
HIGH
Cal-. Response =
11.44
LOW System Drift = 0.07 % HIGH System Drift = -1.03 %
L-33
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 4A
JULY 22, 1999
Starting
07-22-99
Time
02
, %. dv
€02
%dv
CO
ppmdv
08
16
12.98
5.43
1372.00
08
17
12.93
5.48
1351.00
08
18
12.97
5.46
1351.00
08
19
12.91
5.51
1332.00
08
20
12.91
5.50
1313.00
08
21
12.88
5.51
1311.00
08
22
12.91
5.52
1316.00
08
23
12.95
5.47
1309.00
08
24
13.01
5.45
1289.00
08
25
12.97
5.47
1281.00
08
26
12.98
5.48
1263.00
08
27
12.98
5.49-
1258.00
08
28
13.05
5.45
1257.00
08
29
13.04
5.43
1258.00
08
30
13.13
5.38
1253.00
08
31
13.12
5.38
1230.00
08
32
13.10
5.39
1216.00
08
33
13.13
5.36
1211.00
08
34
13.12
5.39
1184.00
08
35
13.02
5.47
1146.00
08
36
12.99
5.50
1115.00
08
37
13.00
5.47
1119.00
08
38
12.95
5.51
1117.00
08
39
12.91
5.55
1116.00
08
40
12.98
5.51
1097.00
08
41
13.33
5.51
1097.00
08
42
13.72
5.43
1100.00
08
43
13.79
5.38
1102.00
08
44
13.98
5.22
1096.00
08
45
14^-07
5.16
1106.00
08
46
14.14
5.11
1096.00
08
47
14.27
5.02
1096.00
08
48
14.40
4.93
1082.00
08
49
14.47
4.86
1067.00
08
50
14.53
4.80
1062.00
08
51
14.49
4.81
1067.00
08
52
14.41
4.84
1055.00
08
53
14.38
4.87
1065.00
08
54
14.40
4.88
1084.00
08
55
14.33
4.90
1086.00
08
56
14.25
4.96
1084.00
08
57
14.18
4.99
1075.00
08
58
14.16
4.99
1078.00
08
59
14.10
5.02
1082.00
09
00
14.05
5.05
1058.00
L-34
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 4A
JULY 22, 1999
Starting
07-22-99
Time
02
,.%.dv
C02
%dv
CO
ppmdv
09:01
14.09
5.01
1043.00
09:02
14.10
5.02
1056.00
09:03
14.14
4.97
1066.00
09:04
14.16
4.94
1089.00
09:05
14.24
4.89
1097.00
09:06
14.27
4.85
1110.00
09:07
14.27
4.85
1096.00
09:08
14.35
4,78
1114.00
09:09
14.42
4.76
1125.00
09:10
14.46
4.72
1129.00
09:11
14.55
4.65
1133.00
09rl2
14.60
4.62
1131.00
09:13
14.57
4.65
1138.00
09:14
14.60
4.61
1132.00
09:15
14.59
4.63
1143.00
09:16
14.60
4.63
1176.00
09:17
14.63
4.60
1182.00
09:18
14.64
4.59
1204.00
09:19
14.67
4.56
1224.00
09:20
14.65
4.58
1249.00
09:21
14.58
4.63
1226.00
09:22
14.55
4.67
1202.00
09:23
14.57
4.64
1184.00
09:24
14.57
4.64
1172.00
09:25
14.56
4.64
1172.00
09:26
14.51
4.69
1156.00
09:27
14.48
4.70
1145.00
09:28
14.39
4.78
1143.00
09:29
14.38
4.80
1136.00
09:30
14.35
4.80
1134.00
09:31
14.36
4.82
1136.00
09:32
14.32
4.85
1139.00
09:33
14.23
4.90
1130.00
09:34
14.28
4.87
1160.00
09:35
14.31
4.86
1181.00
09:36
14.36
4.80
1179.00
09:37
14.31
4.84
1182.00
09:38
14.36
4.81
1180.00
09:39
14.32
4.83
1213.00
09:40
14.34
4.81
1216.00
09:41
14.25
4.88
1202.00
09:42
14.19
4.92
1185.00
09:43
14.12
4.97
1192.00
09:44
14.07
5.00
1185.00
09:45
13.99
5.05
1183.00
1-35
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RON 4A
JULY 22, 1999
Starting
07-22-99
Time
02
C02
%dv
CO
ppmdv
180 MinAvg
13.95
5.05
1152.38
Data Corrected for Calibrations
180 MinAvg 13.87 5.05 1136.17
L-36
-------
fTROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 4A
JULY 22, 1999
Calibrations:
[C02 3 Span Value = 20
LOW Calibration Gas = 0.00 HIGH Calibration Gas = 11.01
INITIAL CALIBRATION TIME —> 707
LOW Cal. Response = 0.11 HIGH Cal. Response = 10.85
FINAL CALIBRATION TIME > 1123
LOW Cal. Response = 0.13 HIGH Cal. Response = 10.91
LOW System Drift = 0.11
%
HIGH
System Drift a
0.29 %
[CO ] Span Value =
6000
LOW Calibration Gas = 0.00
HIGH
Calibration Gas
= 1809.00
INITIAL CALIBRATION TIME —>
707
LOW Cal. Response = 5.42
HIGH
Cal. Response =
1831.90
FINAL CALIBRATION TIME > :
1123
LOW Cal. Response = 5.42
HIGH
Cal. Response =
1831.30
LOW System Drift = -0.00 % HIGH System Drift = -0.01 %
[02 ] Span Value = 25
LOW Calibration Gas = 0.00
INITIAL CALIBRATION TIME —> 707
LOW Cal. Response = 0.06
FINAL CALIBRATION TIME > 1123
LOW Cal. Response = 0.11
HIGH Calibration Gas = 11.50
HIGH Cal. Response = 11.43
HIGH Cal. Response s 11.73
LOW System Drift = 0.20 % HIGH System Drift = 1.22 %
L-37
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 4B
JULY 22, 1999
Starting
07-22-99
02
C02
CO
' -'% dv
%dv
ppmdv
Time
11:36
12.36
5.03
1146.00
11:37
12.88
5.08
1157.00
11:38
12.78
5.14
1146.00
11:39
12.83
5.15
1146.00
" 11:40
12.86
5.10
1154.00
11:41
12.85
5 .12
1154.00
11:42
12.77
.5.18
1154.00
11:43
12.74
5.24
1131.00
11:44
12.83
5.16
1131.00
11:45
12.84
5.16
1142.00
11:46
12.90
5.10
1166.00
11:47
12.94
5.07
1192.00
11:48
12.92
5.10
1200.00
11:49
12.93
5.08
1208.00
11:50
12.92
5.09
1220.00
11:51
12.94
5.06
1224.00
11:52
12.90
5.10
1235.00
11:53
12.95
5.03
1237.00
11:54
12.91
5.06
1234.00
11:55
12 . 90
5.06
1227.00
11:56
12,82
5.12
1212.00
11:57
12 .82
5.12
1187.00
11:58
12.81
5.13
1192.00
11:59
12.83
5.11
1212.00
12:00
12 . 80
5.13
1238.00
12 :01
12 .76
5.17
1248.00
12:02
12.78
5.14
1254.00
12:03
12 .80
5.14
1247.00
12:04
12.76
— 5.16
1257.00
12:05
12.76
5.15
1283.00
12:06
12.71
5.19
1294.00
12:07
12.79
5.15
1309.00
12:08 _
12.73
5.18
1297.00
12:09
12.67
5.22
1279.00
12:10
12.64
5.26
1269.00
12:11
12.65
5.28
1266.00
12:12
12.68
5 .24 '
1283.00
12:13
12.67
5.24
1294.00
12:14
12.73
5.20
1294.00
12:15
12.62
5.31
1284.00
12:16
12.62
5.31
1264.00
12:17
12.58
5.34
1254.00
12:18
12.60
5.33
1248.00'
12:19
12.50
5.41
1234.00
12:20
12 .49
L-%843
1234.00
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 4B
JULY 22, 1999
Starting
07-22-99
02
CO 2
CO
-*% dv
%dv
ppmdv
Time
12:21
12.51
5.41
1220.00
12:22
12.50
5.42
1185.00
12:23
12 .41
5.47
1182.00
12 :24
12 .37
5.51
1180.00
12 :25
12.44
5.45
1187.00
12 :26
12 .46
5.47
1185.00
12:27
12.62
5.32
1170.00
12 :2 8
12.52
5.39
1127.00
12:29
12.62
5.34
1124.00
12:30
12.60
5.35
1134.00
12:31
12.97
5.42
1130.00
12 :32
13.00
5.41
1116.00
12:33
13 .05
5.37
1106.00
12 : 34
13 .01
5.41
1103.00
12 :35
13 .00
5.41
1093.00
12:36
13.13
5.31
1076.00
12 :3 7
13.12
5.32
1067.00
12:38
13.16
5.28
1062.00
12 :39
13 .19
5.27
1057.00
12 :40
13.25
5.22
1060.00
12 :41
13 .34
5.15
1066.00
12 :42
13 .39
5.09
1083.00
12 :43
13 .38
5.09
1110.00
12:44 '
13 .40
5.07
1122.00
12:45
13 . 44
5.04
1145.00
12 : 4 6
13 .39'
5.07
1136.00
12 :47
13 .41
5.06
1137.00
12 :48
13 .42
5.04
1116.00
12 :49
13 .45
5.02
1128.00
12 :50
13 .46
5.00
1129.00
12 :51
13.49
4 . 97
1132.00
12 :52
13 .50
4.96
1119.00
12 :53
13.45
5.01
1111.00
12:54
13 .51
4.95
1096.00
12 :55
13.47
5.01
1093.00
12:56
13.49
5.00
1109.00
12 :57
13 .53
4.97
1093.00
12:58
13 .61
4.90
1072.00
12 : 59
13 .65
4.89
1062.00
13 :00
13 .64
4.90
1055.00
13 : 01
13.75
4.81
1053.00
13:02
13.72
4.84
1053.00
13:03 '
13 .72
4.83
1064.00
13:04
13.76
4.82
1062.00
13:05
13.74
4.82
1067.00
1-39
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 4B
JULY 22, 1999
Starting
07-22-99
02
C02
CO
' -'% dv
%dv
ppmdv
Time
13:06
13.80
4.78
1076.00
13:07
13 .76
4.81
1089.00
13:08
13.75
4.83
1109.00
13:09
13 .69
4.86
1097.00
13 :10
13 .79
4.80
1113.00
13 :11
13.72
4.85
1125.00
13 :12
13.74
4.83
1142.00
13:13
13.69
4 .88
1128.00
13:14
13.69
4 .87
1117.00
13 :15
13 .69
4.89
1114.00
13:16
13.66
4.89
1116.00
13:17
13.70
4.89
1132.00
13:18
13.76
4.82
1126.00
13 :19
13.81
4 .79
1122.00
13 :2Q
13 .80
4 .80
1117.00
13 :21
13.79
4.82
1113.00
13:22
13.79
4 .83
1111.00
13:23
13.72
4 .87
1106.00
13:24
13.75
4.86
1098.00
13:25
13 .75
4 . 87
1122.00
13:26
13.73
4.87
1120.00
13 :27
13.69
4 .92
1100.00
13 :28
13 .76
4 .87
1114.00
13 :29
13.71
4 .89
1130.00
13:30
13.74
4.88
1123.00
13 :31
13 .67
4 . 93
1123.00
13 :32
13.62
4.98
1114.00
13 :33
13.61
4 . 97
1129.00
13 :34
13.51
5.07
1114.00
13:35
13 .46
5.10
1113.00
13:36
13.50
5.08
'1131.00
13:37
13 .54
5.05
1133.00
13:38
13.49
5.09
1143.00
13 :39
13.59
5.02
1127.00
13:40
13.58
5.02
1138.00
13:41
13.47
5.10
1120.00
13:42
13.49
5.08
1132.00
13 :43
13.54
5.06
1144.00
13 :44
13 .49
5.08
1133.00
13 :45
13.48
5.09
1133.00
13:46
13 .49
5.08
1143.00
13:47
13.46
5.09
1154.00
13 :48
13.41
5.13
1151.00
13:49
13.35
5.17
1133.00
13:50
13.35
5.18
1133.00
1-40
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR - RUN 4B
JULY 22, 1999
Starting
07-22-99
02
C02
CO
' •'% dv
%dv
ppmdv
Time
13:51
13.26
5.26
1120.00
13 :52
13 .29
5.22
1142.00
13 :53
13 .35
5.18
1134.00
13 :54
13.39
5.15
1115.00
13 :55
13.37
5.15
1124.00
13 :56
13 .39
5.14
1123.00
13:57
13.35
5.15
1133.00
13 :58
13.34
5.18
1136.00
13:59
13.34
5.18
1134.00
14:00
13.34
5.19
1133.00
14 :01
13.36
5.16
¦ 1124.00
14:02
13 .33
5.19
1118.00
14 :03
13.33
5.19
1108.00
14 :04
13 .26
5.26
1071.00
14:05
13.29
5.23
1070.00
14 :06
13.30
5.24
1087.00
14:07
13 .38
5.18
1089.00
14 :08
13.33
5.22
1086.00
14 :09
13.27
5.27
1076.00
14 :10
13 .27
5.28
1080.00
14 :11
13 .24
5.31
1084.00
14 :12
13 .26
5.28
1082.00
14 :13
13 .23
5.33
1079.00
14 :14
13 .30
5.24
1086.00
14 :15
13 . 06
5.44
1081.00
14 :16
13 .13
5.37
1067.00
14 :17
13 . 03
5.46
1071.00
14 : 18
13 .04
5.46
1082.00
14 :19
13 . 05
5.43
1056.00
14 :20
13.07
5.43
1070.00
14 :21
13.04
5.46
1080.00
14 :22
13.06
5.45
1061.00
14 :23
13.12
5,40
1033.00
14 :24
13 .20
5.34
1027.00
14 :25
13.27
5.28
1023.00
14 :26
13 .34
5.24
1044.00
14 :27
13.41
5.19
1058.00
14 :28
13.74
4.96
1093.00
14 :29
14 . 02
4.76
1154.00
14:30
14.08
4 .72
1163.00
14 :31
14.23
4.61
¦1175.00
14 :32
14.31
4.56
1184.00
14:33
14.38
4 .51
1172.00
14 :34
14 .44
4.46
1164.00
14 :35
14 .54
4 .37
1179.00
L-41
-------
METROPOLITAN SEWER DISTRICT
SEWAGE SLUDGE INCINERATOR
JULY 22, 1999
- RUN 4B
Calibrations:
[C02 ] Span Value = 20
LOW Calibration Gas = 0.00 HIGH Calibration Gas «= 11.01
INITIAL CALIBRATION TIME --> 1123
LOW Cal. Response - 0.13 HIGH Cal. Response = 10.91
FINAL CALIBRATION TIME > 1443
LOW Cal. Response = 0.13 HIGH Cal. Response = 10.85
LOW System Drift = -0.03 * HIGH System Drift = -0.32 %
[CO ] Span Value * SO00
LOW Calibration Gas <= 0.00 HIGH Calibration Gas = 1809.00
v.
INITIAL CALIBRATION TIME --> 1123
LOW Cal. Response = 5.42 HIGH Cal. Response = 1831.30
FINAL CALIBRATION TIME >1443
LOW Cal. Response = 5.71 HIGH Cal. Response = 1853.80
LOW System Drift = 0.00 % HIGH System Drift = 0.38 %
[02 ] Span Value = 25
LOW Calibration Gas = 0.00 HIGH Calibration Gas = 11.5C
INITIAL CALIBRATION TIME --> 1123
LOW Cal. Response = 0.11 HIGH Cal. Response = 11.73
FINAL CALIBRATION TIME > 1443
LOW Cal. Response = 0.12 HIGH Cal. Response = 11.80
LOW System Drift = 0.03 % HIGH System Drift = 0.27 %
L-42
-------
L-3
jnfim mr *¦"% m* T\ a • » *
CEM Response Time Determination
L-43
-------
RESPONSE TIME DETERMINATION
FACILITY, £' /) C /\s~% A /hi D
HATE
ANALYZER TYPE_
SPAN GAS CONCENTRATION 3 <>CZ
ANALYZER REPSONSE Xlt 1
UPSCALE RESPONSE TIME
1 /JT SECONDS
2 / 5"V SECONDS
3 I ^ $ SECONDS
AVG. /57.3 SECONDS
"NTS:
0
T.-ul 3 ^ U*.
faunctd' uf t*
fltoru^" £ ^-Wo *i
^z' s*%0"\-h*'•"*> St
DOWNSCALE RESPONSE TIME
1 /W SECONDS
2
3
/yt SECONDS
/V2 SECONDS
AVG, /VM SECONDS
L-44
-------
RESPONSE TIME DETERMINATION
FACILITY f.'^c /hi/)
[date
ANALYZER TYPE_
(Os
|SPAN GAS CONCENTRATION_ if. 0 % ^
ANALYZER REPSONSE
I
UPSCALE RESPONSE TIME
1 hH SECONDS
? UH SECONDS
i
/ SECONDS
AVG. /J.Q. >> SECONDS
COMMENTS;
DOWNSCALE RESPONSE TIME.
1 / H SECONDS
2 />(!L SECONDS
3
I ( 9 SECONDS
AVG. />2 ¦7 SECONDS
L-45
-------
RESPONSE TIME DETERMINATION
FACILITY /h\0
DATE
ANALYZER TYPE
SPAN GAS CONCENTRATION ^
ANALYZER REPSONSE J-&.7 W-
UPSCALE RESPONSE TIME
1 SECONDS
2 117 SECONDS
3 SECONDS
*
AVG- M,-0 SECONDS
ITS:
DOWNSCALE RESPONSE TIME
1 //i SECONDS
2 tlf SECONDS
3 !° ? SECONDS
AVG. //y.? SECONDS
L-46
-------
L-4
CEM Calibration Records
L-47
-------
EPA METHOD 20
INTERFERENCE RESPONSE TABLE
Date:
Analyzer Type:
Serial Number-
Span Value:
04/19/93
Carbon Dioxide #5
91-20-15
20 %
[lest Gas Type
Concentration
(ppmdv)
Analyzer
Output
% of Span
Ico
488
0.101
0.00511
02
21.9
0,203
0.01021
S02
231
-0.021
0,0011
NOx
232
-0.007
0.00041
Total
0.01661
% of Span = (Analyzer output response/Instrument span) x 100
The sum of the (% of Span) values should not exceed 2%.
L-48
-------
METHOD 20
INTERFERENCE RESPONSE TABLE
DATE: 5 "
ANALYZER TYPE: ^ 0 jL-
SERIAL NUMBER: ¥tf~ ' ZZ*Z—
TEST GAS TYPE
CONCENTRATION
(ppmdv)
ANALYZER
OUTPUT
% OF SPAN
0^ m Oi 1 Vrf
zi-l z
O'OtO
,00$
COi Hnozwri
to. if %
-ao36~
SO% $Lr\ ovs/fo
zzt
o-o
o.o
Ax AAL W/
-0.HO
D.&IZ
TOTAL
- O'OOff
. % OE. SPAN._=_4ANALY2LEB- O.OTBUT. RESEONSE/INSTRTTMKNT SPAN), Z-1Q0
The sum of the (% of Span) values should not exceed 2%.
L-49
-------
REFERENCE METIIOl ALTERATION DAT1V
aGE ( OF/
ANALYZER id
UI1ITS:
>((?*&)
SPAN * ftQOO
SOUBCE dj^Jj
LOCATION
TECHNICIAN;
! £T5 jk/> -T-ffg-
nATB(S)i
r / 2f / 11
ANALYZER CALIBRATION
RANGE
GAS
CYLINDER ID
GAS
VALUE
ANALYZER
RESPONSE
ERROR
% SPAN
TIM!
ZERO
jhl axzhi*
0
0' 001
0 0 O)
LOW
CO hlA otftU
2f€'l
3 o o > o
-------
METHOD 20
INTERFERENCE RESPONSE TABLE
DATE: 1
ANALYZER TYPE: Ot '
SERIAL NUMBER: ^2.4(^9
TEST GAS TYPE
CONCENTRATION
(ppm&v)
ANALYZER
OUTPUT
% OP SPAN
SO*. cyl.*-ZM£ISl
72A
O.OZ
^0* tA,l.*/UMicnxs/
ZZh
O.tn
5.D
c-vl- W.t.
44 T~
0. D\
tc^
X e vU*AlSlt2/ig /9
I&4 %
&. oo
O.b
TOTAL
0,1
—% OF SPAN « (ANALYZER OUTPUT RESPONSE/INSTRUMENT SPAN) X 100
The sum of the (% of Span) values should not exceed 2%.
L-51
-------
REFERENCE METHOt .ALTERATION DATA
ANALYZER ID! q
/ozy^i
UNITSs %
SPAN,
SOURCE IDI
LOCATION! £j2
TECHNICIAN!
DATE(S) 5 pi /
03
1 AL/t*tSiy*>
?.? 9
?.9«5
0. \ '
HIGH
X'/tLrtoW/L?
z\.n
at. no
D
laws'
OTHER
.•SYSTEM BIAS AND'DRIFT
SYSTEM BIAS
SYSTEM DRIFT
UN ID
RANGE
ANALYZER
RESPONSE
SYSTEM
RESPONSE
ABSOLUTE
ERROR
ERROR
* SPAN
TIME
SYSTEM
RESPONSE
ABSOLUTE
ERROR
ERROR
% SPAN
TIME
ZERO
UPSCALE
ZERO
UPSfcALE
•
ZERO
UPSCALE
ZERO
UPSCALE
ZERO
UPSCALE
ZERO
1
UPSCALE
t mriAnl
• ii \ rtmn r»r»n
-------
L-5
CEM Calibration Gas Certification Records
L-53
-------
SPECTRA GASES
A7//
277 Coit St • Irvinglon, NJ 07111 USA Tel.: (973) 372-2060 * (800) 932-0624 • Fax (973) 372-8551
Shipped From: 80 Industrial Drive * Alpha, N.J. 08865
I
CERTIFICATE OF ANALYSIS
CUSTOMER:
SGI ORDER # :
ITEM#:
P.O.#:
ETS, INC
132640
3
6732
CERTIFICATION DATE: 4/22/98
EXPIRATION DATE: 4/22/2001
EPA PROTOCOL MIXTURE
PROCEDURE #: G1
CYLINDER #: CC90980
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 350
1
I
I
I
CERTIFICATION HISTORY
COMPONENT
DATE OF
ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Propane
4/22/98
86.6 ppm
86.6 ppm
~/-1%
\
;
BALANCE
REFERENCE STANDARDS
Nitrogen
COMPONENT
SRM/NTRM#
CYLINDER#
CONCENTRATION
Propane
SRM-2643a
SX20148
99.1 ppm
INSTRUMENTATION
COMPONENT
MAKE/MODEL
SERIAL#
DETECTOR
CALIBRATION
DATE(S)
Propane
H. Packard 6890
US00001434
GC-FID
3/25/98
tr-
I
I
I
I
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE TMS STANDARD THE CYLINDER PRESSURE IS LESS THAN 160 PSIG.
ANALYST:
DATE:
TED NEEME
4/22/98
I -Kd
I
-------
5G
SPECTBR GHSES INC.
//»3
3434 Route 22 West • Branchburo, NJ 08876 USA Tel.: (908) 252-9300 • (800) 932-0624 ~ Fax: (908) 252-0811
Shipped From; 80 Industrial Drive * Alpha, NJ 08865
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE it: 61
CUSTOMER:
SGI ORDER #:
ITEM#:
P.O.#;
ETS, INC
136421
3
6933
CYLINDER #: CC94773
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 350
CERTIFICATION DATE: 10/5/98
EXPIRATION DATE: 10/5/2001
CERTIFICATION HISTORY
COMPONENT
DATE OF
ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Propane
10/5/98
124.6 ppm
•124.6 ppm
+/-1%
BALANCE Nitrogen
PREVIOUS CERTIFICATION DATES: None
REFERENCE STANDARDS
COMPONENT
SRM/NTRM#
CYLINDER#
CONCENTRATION
Propane
GMIS-1
CC53375
1004 ppm
INSTRUMENTATION
COMPONENT
MAKE/MODEL
SERIAL*
DETECTOR
CALIBRATION
DATEIS)
Propane
H. Packard 6890
US00Q01434
GC-RID
10/1/88
"WIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES. -vr
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 160 PSIG.
ANALYST:" fj\k- DATE: 10/5/98
TED NEEME
/
k
Tgr
-------
— ^6/
SPECTBH BHSES INC.
3434 Route 22 West • Branctiburg, NJ 0887S USA Tel.: (908) 252-9300 • (800) 932-0624 • Fax: (908) 252-0811
Shipped From: 80 Industrial Drive • Alpha, NJ 08865
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE#: G1
CUSTOMER:
SGI ORDER#:
ITEM#:
P.O.#:
ETS, INC
142592
8
7212
CYLINDER #: CC84936
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 590
CERTIFICATION DATE: 5/14/99
EXPIRATION DATE: 5/14/2002
CERTIFICATION HISTORY
COMPONENT
DATE OF
ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Cartoon Dioxide
5/14/99
18.00%
18.00%
+/-1%
Oxygen
5/14/99
21J %
21.0%
+/-1%
<
BALANCE NHrogen
PREVIOUS CERTIFICATION DATES: None
REFERENCE STANDARDS
COMPONENT
SRM/NTRM#
CYLINDER#
CONCENTRATION
Carbon Dioxide
NTRM-82745x
CC79944
20.00%
Oxygen
NTRM-82659X
CC83900
22.80 %
INSTRUMENTATION
COMPONENT
MAKE/MODEL
SERIAL#
DETECTOR
CALIBRATION
DATE(S)
Carbon Dioxide
Horiba V1A-510
571417045
NDIR
5/3/99
Oxygen
Horiba MPA-510
570694081
PM
mm
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 150 PSIG.
<2#
ANALYST: SC ' DATE: 5/14/99
FRED PIKULA
-------
SPECTRA GRSES INC.
3434 Route 22 West • Branchburg, NJ 08876 USA Tel: (908) 252-9300 • (800) 932-0624 ~ Fax; (908) 252-0811
Shipped From; 80 Industrial Drtw • Alpha, NJ 08865
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE #: G1
CUSTOMER:
SGI ORDER#:
ITEM#:
P.O.#:
ETS, INC
139104
9
7305
CYLINDER #: CC88474
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 590
CERTIFICATION DATE: 1/22/99
EXPIRATION DATE: 1/22/2002
CERTIFICATION HISTORY
COMPONENT
DATE OF
" ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Oxygen
1/22/99
11.50%
11.50%
+/-1%
Carbon Dioxide
' 1/22/99
11.01 %
11.01 %
+/-1%
BALANCE Nitrogen
PREVIOUS CERTIFICATION DATES: None
REFERENCE STANDARDS
COMPONENT
SRM/NTRM#
CYLINDER#
CONCENTRATION
Oxygen
NTRM-82659X
CC8390C
22.80%
Carbon Dioxide
NTRM-82745X
CC79944
20.00%
INSTRUMENTATION
COMPONENT
MAKE/MODEL
SERIAL#
DETECTOR
CALIBRATION
DATE(S)
Oxygen
Horiba MPA-510
570694081
PM
12/30/98
Carbon Dioxide
Horiba VlA-510
571417045
NDIR
1/20/99
L
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 150 PSIG.
ANALYST:
DATE: 1/22/99
FRED P1KULA
L-57
-------
¦50
SPECTRH GRSES INC.
SfoJ-
3M4 Routt 22 Wtst • Branaitairs. KJ 08676 USA Tel.: (903) 252-S3X) • (&Mj 332462< • fw. (90E| 252-0311
Shipped from: 80 Industrial Drive • Alpha, NJ 08865
I
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE #: <31
CUSTOMER:
SGI ORDER M:
ITEM# :
P.O.#:
ETS, INC
135096
1
6873
CYLINDER #: CC79858
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 350
CERTIFICATION DATE: 8/18/98
EXPIRATION DATE: 8/16/2001
COMPONENT
DATE OF
ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Carbon Monoxide
a/ii/98
8/18/38
614.0 ppm
915,3 ppm
915 ppm
+/-1% -
*
BALANCE Nitrogen
PREVIOUS CERTIFICATION DATES: None
REFERENCE STANDARDS
COMPONENT
SRM/NTRM#
CYLINDER#
CONCENTRATION
Carbon Monoxide
NTRM-81681
CC55773
894 ppm
-
INSTRUMENTATION
COMPONENT
MAKE/MODEL
SERIAL#
DETECTOR
CALIBRATION
DATE(S)
Cartoon Monoxide
Horiba VIA-510
570423011
NDIR
7/30/98
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE TWS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 1S0 PSK5.
>V_.'
ANALYST:
FRED PIKULA
DATE:
8/18/98
Me
-------
5b
SPECTRH GRSES INC
7 of
3434 Route 22 West • Branchbuis, NJ 08876 USA Tel; (908) 252-9300 «(800) 932-0624 • Fax: (908) 252-0811
Shipped From: 80 Industrial Drive * Alpha, NJ 08865
CERTIFICATE OF ANALYSIS
CUSTOMER:
SGI ORDER#:
ITEM#:
P.O.#:
ETS, INC
135096
3
6873
EPA PROTOCOL MIXTURE
PROCEDURE #: G2
CYLINDER #: CC75430
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 350
CERTIFICATION DATE: 8/18/98
EXPIRATION DATE: 8/18/2001
CERTIFICATION HISTORY
COMPONENT
DATE OF
ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Carbon Monoxide
8/11/98
8/18/98
5962 ppm
5979 ppm
5971 ppm
~/-1%
BALANCE Nitrogen
PREVIOUS CERTIFICATION DATES: None
REFERENCE STANDARDS
COMPONENT
SRM/NTRM#
cylinder#
CONCENTRATION
Carbon Monoxide
NTRM-81681
CC55773
994 ppm
-
INSTRUMENTATION
COMPONENT
MAKOMODEL
SERIAL#
DETECTOR
CALIBRATION
DATE(S)
Carbon Monoxide
Horiba VIA-510
570423011
NDIR
7/30/98
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 160 PSIG.
ANALYST: DATE: 8/18/98
FRED PIKULA
-------
5b
SPECTRR GRSES INC.
S?o3
3434 Route 22 West • Branchburg, NJ 08876 USA Tel.: (908) 252-9300 • (800) 932-0624 • Fax; (908) 252-0811
Shipped From: 80 Industrial Drive • Alpha. NJ 08865
I
CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE #: G2
CUSTOMER:
SGI ORDER #:
ITEM#:
P.O.#:
ETS, INC
135096
2
6873
CYLINDER #: CC53292
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 350
CERTIFICATION DATE: 8/18/98
EXPIRATION DATE: 8/18/2001
CERTIFICATION HISTORY
COMPONENT
DATE OF
ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Carbon Monoxide
8/11/98
8/18/98
2999 ppm
3011 ppm
3005 ppm
+/-1%
I
BALANCE Nitrogen
PREVIOUS CERTIFICATION DATES: None
REFERENCE STANDARDS
COMPONENT
SRM/NTRM#
CYLINDER#
CONCENTRATION
Carbon Monoxide
NTRM-81681
CC55773
994 ppm
-
INSTRUMENTATION
COMPONENT
MAKE/MODEL
SERIAL#
DETECTOR
CALIBRATION
DATE(Sy
Carbon Monoxide
Horiba VlA-510
570423011
NDIR
7/30/98
5
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 150 PSK3.
ANALYST: . DATE: B/18/9B
FRED PIKULA
J
-------
¦nn
5G
SPECTRA GASES INC
3434 Route 22 West • Branchburg. NJ 08876 USA Tel.: (908) 252-9300 • (800) 932-0624 • Fax; (908) 252-0811
Shipped From: 80 Industrial Drive > Alpha, NJ 08865
r
i
i
i
i
i
i
i
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CERTIFICATE OF ANALYSIS
EPA PROTOCOL MIXTURE
PROCEDURE#: G2
CUSTOMER;
SGI ORDER #:
ITEM#:
P.O.#:
ETS, INC
144039
1
7275
CYLINDER #: CC109915
CYLINDER PRES: 2000 PSIG
CGA OUTLET: 350
CERTIFICATION DATE: 7/6/99
EXPIRATION DATE: 7/6/2002
CERTIFICATION HISTORY
COMPONENT
DATE OF
ASSAY
MEAN
CONCENTRATION
CERTIFIED
CONCENTRATION
ANALYTICAL
ACCURACY
Carbon Monoxide
6/29/99
7/6/99
1813 ppm
1804 ppm
1809 ppm
+/-1%
• —
BALANCE Nitrogen
PREVIOUS CERTIFICATION DATES: None
REFERENCE STANDARDS
COMPONENT
SRM/NTRM#
CYUNDER#
CONCENTRATION
Carbon Monoxide
NTRM-81681
CC55773
994 ppm
,
INSTRUMENTATION
COMPONENT
MAKE/MODEL
SERIAL#
DETECTOR
CALIBRATION
DATE(S)
Carbon Monoxide
Horiba VlA-510
570423011
NDIR
6/28/99
THIS STANDARD WAS CERTIFIED ACCORDING TO THE EPA PROTOCOL PROCEDURES.
DO NOT USE THIS STANDARD IF THE CYLINDER PRESSURE IS LESS THAN 150 PSIG.
ANALYST:
i/v •
DATE:
7/6/99
FRED PIKULA
3a;
-------
Scott Specialty Gases
i2§i> C0M6£RMEft£ STREET, fkdr. Ml 48083
(810)589-2950 FAX:(810) 589-2134
CERTIFICATE OF ANALYSIS: EPA PROTOCOL GAS
Customer
Assay Laboratory
CLEAN AIR ENGINEERING
Scott Specialty Gases, Inc
Purchase Order:
18566-71-65000
ATTN DON ALLEN
1290 Combermere
Scott Project M:
543076
500 W WOOD STREET
Troy. MI 48083
PALATINE, IL 60067
ANALYTICAL INFORMATION
Calibration Standards; Procedure GI; September, 1993.
Cylinder Nnmbcr: AAL9476
.Cylinder Pressure + : 1900 psig
Certificate Date: 4/7/99
Previous Certificate Date :
None
Expiration Date : 4/7/2002
i
I
I
I
I
I
. .ANALYZED CYLINDER
Cnmnonenta
Carbon Dioxide
Oxygen
Certified Concentration
6.13 V.
14.2 %
Analytical-Uncertainty*
*1% NIST Directly Traceable
±1% NIST Directly Traceable
Balance Gas: Nitrogen
. +Do*ot«>e when cylinder [umiuie it bdow ISt) p«
Expiration Date
Cylinder Number
Concentration
.;-NTRM 18000
4/12/2001
ALM047394
17.95 % Carbon Dioxide in Nitrogen
";r NTRM2659
12/1/2001
ALM065379
20.92 % Oxygen in Nitrogen
¦ • iJjSTRTIMF.NTATION
.
Instroment/Model/Serial #
Last Date Calibrated
Analytical Principle
C02: Horiba/OPE-13 5
4/7/99
Non-dipersive Infrared
. Horiba
4/7/99
Paramagnetic
ANALYZER READINGS (Z-2>n>Gaj
R-Refertnee Cu T-TestGas
r~Correlation Coefficient)
• Components
Carbon Dioxide
Oxygen
First Triad Analysis
DMK«7«S
RMponM Unas mv
Z1K3.00
l»1"«L20
T1M&20
RMO20
H«C00
T2MU0
S>0l00
TV4120
*3-9020
Aoo.Conc.cfCuH.Cyt. (.13%
OMK4/7/BB
Rupon
m Uhftr mv
21-O.X
R1 «120l00
T14U0
R2-12Q.00
12-000
T24U0
ZK.00
TMMO
R>12000
Avg.Cane.aTCiat.Cyl WJ%
Second Triad Analysis
Calibration Curve
r»l 40000
NTRM18000
Com—:
A*-0004990676
B-0.115273700
c-aooocsrrst
(MLOOOOtOSM
Cow»tmfaMA iP1
r*1j00000
KTRM26S6
Cmantr
AMI 021996850
*0213390000
C*A 000236055
tx.oooooin2
(¦0.000000000
Special Notes
Cyfedcr
Analyst
L-62
-------
Scott Specialty Gases
1290 CQM8ERMERE STREET, TROY, MI 41083 Phone : {241) 588-2950 Fix: (248) 589-2134
CERTIFICATE OF ANALYSIS: EPA PROTOCOL GAS
Customer
CLEAN AIR ENGINEERING- /
ATTN DON ALLEN
500 W WOOD STREET
PALATINE, IL 60067
Assay Laboratory
Scott Specialty Gases, Inc
1290 ComberTnere
Troy, MI 48083
Purchase Order:
Scott Project #:
18373-75-65000
539848
ANALYTICAL INFORMATION
•
Calibration Standards; Procedure Gl; September, 1993.
Cylinder Number: ALM008858
Cylinder Pressure + : 1900 psig
Certificate Date: 2/8/99
Previous Certificate Date: None
Expiration Date: 2/8/2002
¦ANAT.V7.Rn CVT.TVDrB
Components
Carbon Monoxide
Certified Concentration
467.0 ppm
Analytical Uncertainty*
±1% NIST Directly Traceable
Balance Gas: Nitrogen
~Do sol a* wfcot cylinder prcssswe ts below ISO pag.
~Aftilyticil iccttticy U iftdttiivc of ami known cmor sources which tt least include prccUiop of the measurement processe*.
REFERENCE STANT>ART)
Type Expiration Date
NTRM 1681 8/1/2002
Cylinder Number
ALM024833
Concentration
966.1 ppm Carbon Monoxide in Nitrogen
INSTRUMENTATION
Instrument/Model/Serial #
CO: Horiba/OPE-135/565607092
Last Date Calibrated
2/8/99
Analytical Principle
Non-dispcrsive Infrared
ANALYZER READINGS (Z-Zero Gas R-Refereact Gas T-Tcst Gas r-Corrrf»tioo Coefficient)
'.Components First Triad Analysis'
Carbon Monoxide
Oat«2rU89 PtMpcrw
Unfcs: tm
Z1-O.0Q K1>100.00
Tl«5®40
R2-100.00 23-OJX
T2-MW
2J-0.00 T>ML40
po-ioaoo
Avg. Cane. a> Cut Cyt «7Jppm
Second Triad Analysis
omrnwam
flMparacU
TteflW
Zl'O.OO
«1-100,00
T1««.40
rcMoaoo
23-aoo
TO-S8.40
2M00
1MMQ
ro-ioaao
Avq. Cone, af Cutt. Cyt 484.7
ppm
Calibration Curve
CMc«Mra004aA«Cs*Cx *0* «£x
r*1JOQQG
CfcntfantK
0"0000»HW
NTfUM1M1
A»04112«$000
OOi00337X)tr7
. E-OiOOOOOOOOO
Special Notes
Mai! . . , .
Analyst
L-63
-------
* »• * • - - -ay»wiw«tr- -.
Process Field Data Sheets,
-------
M-l
Process Data Summary Tables
M-1
-------
Table M-l
THC, 02, Moisture, and Feed Rate Process Data
MSD Emission Test Program
No Runs
July 19,1999
Total Hydrocarbons (ppm)
1
1
Hour
Uncorrected
Corrected (7% 02, dry)
Oxygen
h2c
Sludge Feed
Hourly
Hourly
Rolling
(%)
(%)
(dry tons/hr) 1
Average
Average
Average
1
0:00
45.8
81.5
89.3
12.8
3.1
1.80
1:00
40.7
72.3
76.2
12.8
3.0
1.79
2:00
43.3
68.6
74.1
11.5
3.0
1.78
3:00
43.4
72.6
71.2
12.4
3.0
1.78
4:00
38.2
66.3
69.2
12.6
3.0
1.78
5:00
41.2
72.9
70.6
12.8
3.0
1.78
6:00
46.4
84.8
74.7
13.1
2.9
1.80
7:00
46.1
80.2
79.3
12.7
2.9
1.79
8:00
52.6
92.7
85.9
12.8
2.9
1.78
9:00
45.8
83.1
85.3
12.7
2.9
1.78
10:00
37.0
57.8
77.9
11.7
3.1
1.79
11:00
28.2
45.9
62.3
12.1
2.9
1.43
12:00
21.7
40.6
48.1
13.3
3.1
1.16
13:00
22.0
46.7
44.4
14.2
3.2
1.58
14:00
36.8
65.8
51.1
12.9
3.0
1.78
15:00
49.9
90.9
67.8
13.0
3.0
1.78
16:00
55.5
97.7
84.8
12.8
3.0
1.79
17:00
35.2
53.4
80.7
11.5
3.1
1.59
18:00
44.2
60.9
70.7
9.6
3.3
1.27
19:00
14.4
26.9
47.1
13.3
3.1
1.55
20:00
28.8
53.0
47,0
12.9
3.0
1.80
21:00
48.2
89.1
56.3
13.2
3.0
1.87
22:00
52.8
78.4
73.5
11.7
3.1
1.87
23:00
43.5
72.4
79.9
12.2
3.1
1.76
Average
40.1
68.9
12.5
1 «
| 1.70
Set up day 110 tests
M-2
-------
Table M-l
THC, 02, Moisture, and Feed Rate Process Data
MSB Emission Test Program
Runs land 2
July 20,1999
Total Hydrocarbons (ppm)
Hour
Uncorrected
Corrected (7% 02, dry)
Oxygen
H20
Sludge Feed
Hourly
Average
Hourly
Average
Rolling
Average
(%)
(%)
(dry tons/hr)
0:00
23,6
38.1
62.9
12.0
3.1
' 1.72
1:00
22.6
48.3
52.9
14.3
3.1
1.72
2:00
26.5
40.6
42.3
10.8
3.1
1.72
3:00
21.0
38.6
42.5
13.1
3.1
1.72
4:00
35.2
63.9
47.7
13.0
3.1
1.72
5:00
39.4
69.4
57.3
12.8
3.0
1.72
6:00
39.7
67.7
67.0
12.5
3.0
1.72
7:00
38.3
63.3
66.8
12.3
3.0
1.72
8:00
40.1
69.0
66.7
12.6
3.0
1.72
9:00
39.1
64.6
65.7
12.3
3.0
1.72
10:00
37.7
66.7
66.8
12.8
3.0
1.72
11:00
34.1
54.1
61.8
11.8
3.1
1.72
12:00
28.6
46.4
55.7
12.0
3.1
1.72
13:00
26.5
44.7
48.4
12.4
3.1
1.72
14:00
30.0
49.4
46.8
12.2
3.1
1.72
15:00
37.4
66.8
53.6
12.9
3.1
1.72
16:00
42.0
71.4
62.5
12.5
3.1
1.72
17:00
38.5
67.7
68.6
12.7
3.1 "
1.72
18:00
41.6
63.2
67.4
10.8
3.1
1.72
19:00
41.9
75.5
68.8
13.0
3.1
1.72
20:00
42.8
74.8
71.1 -
12.7
3.1
1.72
21:00
43.4
78.2
76.2
13.0
3.1
1.74
22:00
40.3
67.5
73.5
12.3
3.1
1.81
23:00
39.9
63.8
69.9
12.0
3.1
1.81
Run 1 Average
57.9
12.2
3.1
1.72
1 o Average
70.6
12.5
3.1
1.74
Shaded cells include test run data
M-3
-------
Table M-l
THC, 02, Moisture, and Feed Rate Process Data
MSD Emission Test Program
Run 3
July 21,1999
Total Hydrocarbons (ppra)
Hour
Uncorrected
Corrected (7% 02, dry)
Oxygen
H20
Sludge Feed
Hourly
Average
Hourly
Average
Rolling
Average
(%)
(%)
(dry tons/hr)
0:00
34.7
57.9
63.1
12.3
3.1
1.45
1:00
45.3
77.6
66.4
12.6
3.0
1.45
2:00
43.6
67.5
67.7
11.3
3.0
1.45
3:00
35.5
58.1
67.7
12.2
3.0
1.45
4:00
40.9
70.5
65.4
12.6
3.0
1.45
5:00
44.8
77.8
68.8
12.7
3.0
1.45
6:00
45.6
78.7
75.7
12.6
3.0
1.45
7:00
39.2
63.6
73.4
12.1
3.0
1.45
8:00
36.3
61.7
68.0
12.5
3.0
1.44
9:00
42.7
84.5
69.9
13.7
3.0
1.45
10:00
45.1
94.8
80.3
14.1
3.1
1.45
11:00
41.6
73.3
84.2
12.8
3.2 -
1.45
12:00
47.9
72.6
80.2
11.6
3.2
1.45
13:00
27.2
44.7
63.5
12.2
3.2
1.45
[ 14:00
27.1
41.3
52.9
11.4
3.3
1.45
15:00
22.6
36.8
41.0
12.1
3.2
1.45
16:00
20.4
31.3
36.5
11.5
3.3
1.45
17:00
22.7
38.8
35.7
12.5
3.2
1.45
18:00
18.2
24.9
31.7
9.4
3.3
1.44
1 19:00-
15.8
24.1
29.3
11.5
3.3
1.41
| 20:00
16.7
29.2
26.1
12.7
3.2
1.39
1 21:00
22.4
38.9
30.7
12.6
3.2
1.39
1 22:00
18.4
32.4
33.5
12.7
32
1.39
23:00
25.9
45.8
39.0
12.8
3.2
1.39
I Run 3 Average
54.2
12.3
3.2
1.45
Shaded cells include test run data
M-4
-------
Table M-l
THC, 02, Moisture, and Feed Rate Process Data
MSB Emission Test Program
Run4
July 22,1999
Total Hydrocarbons (ppm)
Hour
Uncorrected
Corrected (7% 02, dry)
Oxygen
H20
Sludge Feed
Hourly
Hourly
Rolling
(%)
(%)
(dry tons/hr)
Average
Average
Average
0:00
21.0
37.7
38.6
12.9
3.2
1.55
1:00
28.0
48.7
44.1
12.6
3.2
1.53
2:00
21.0
34.4
40.3
10.9
3.2
1.53
3:00
29.7
51.6
44.9
12.6
3.2
1.53
4:00
20.6
35.8
40.6
12.7
3.1
1.53
5:00
18.8
31.7
39.7
12.4
3.1
1.53
6:00
21.6
42.5
36.6
13.7
3.1
1.53
7:00
37.7
80.1
51.4
14.2
3.2
1.53
8:00
32.5
57.3
60.0
12.7
3.2
1.53
9:00
20.4
37.8
58.4
13.2
3.2
1.53
10:00
20.1
34.6
43.2
12.6
3.2
1.53
11:00
20.8
.36.3
36.2
12.7
3.3
1.53
12:00
18.5
31.4 •
34.1
12.5
3.3
1.53
13:00
19.2
33.3
33.7
12.7
3.3
1.53
14:00
18.2
30.6
31.8
12.4
3.3
1.53
15:00
22.6
38.8
34.2
12.6
3.3
1.53
16:00
24.7
39.4
36.3
11.9
3.3
1.53
17:00
18.9
31.4
36.5
12.3
3.3
1.53
18:00
23.7
33.1
34.6
9.8
3.4
1.53
19:00
18.6
31.6
32.0
12.5
3.3
1.51
20:00
23.4
39.6
34.7
12.4
3.3
1-52
21:00
23.3
37.1
36.1
11.9
3.3
1.54
22:00
22.9
39.2
38.6
12.6
3.3
1.57
23:00
28.1
48.4
41.6
12.6
3.2
1.58
Pun 4 Average
37.5
12.6
3.3
1.53
Shaded cells include test run data
M-5
-------
M-2
MSD Daily Data Reports
ki «
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
1 of £
Mill Creek Waste Water Treatment Plant
7/19/1999
Incinerator #6 "Daily
* Report
"*
-
Uncorr.
CEM
Moist
C«r.
Rolling
Sludge
Sludge
Aocum,
LOWEST
HIGHEST
Report
THC
Oxygen
H20
THC
C. THC
Fa«d
Feed
Sludge
STATUS
STATUS
Event
Hour
(ppm)
(%)
(*)
(ppm)
(ppm)
I
I
(dry Ib/hr)
(dry tons)
0:00
45.8
12.81
3.09
81.51
89.29
15426
3604
1.60
BURN
BURN
NO
1:00
40.7
12.85
3.02
72.30
76.18
15345
3585
3.59
BURN
BURN
NO
2:00
43.3
11.46
2.98
88.61
74.14
15245
3561
537
BURN
BURN
NO
3:00
43.4
12.38
3.00
72.63
71.18
15245
3561
7.16
BURN
BURN
NO
4:00
38.2
12.65
Z97
66.26
69.17
15245
3561
8.94
_ BURN
BURN
NO
5:00
41.2
12.83
2.95
72.93
70.60
15245
3561
10.72
BURN
BURN
NO
6:00
46.4
13.10
2.92
64.81
74.67
15384
3594
12.51
BURN
BURN
NO
7:00
46.1
12.70
2.92
80.21
79.32
15366
3589
14.31
BURN
BURN
NO
8:00
52.6
12.76
2.89
92.71
85.91
15245
3561
16.09
BURN
BURN
NO
8:00
45.8
12.68
Z91
83.09
85.34
15245
3561
17.87
BURN
BURN
NO
10:00
" 37,3
11.73
3.05
87.84
77.68
15329
3581
19.66
BURN
BURN
NO
11:00
28.2
12.13
2.93
48.85
62^6
12211
2852
21.09
BURN
BURN
NO
12:00
21.7
13.34
3.09
40.60
48.10
9891
2311
22L24
BURN
BURN
NO
13:00
22.0
14.22
3.20
46.75
44.40
13506
3155
23.82
BURN
BURN
NO
14:00
36.8
12.93
3.01
65.84
S1.06
15245
3561
25.60
BURN
BURN
NO
15:00
49.9
13.02
3.04
90.93
67,84
15245
3561
27.38
BURN
BURN
NO
16:00
55.5
12.80
3.02 '
97.74
84.64
15314
3577
29.17
BURN
BURN
NO
17:00
35,2
11.49
3.05
53.41
80.69.
13645
3187
30.76
BURN
BURN
NO
18:00
44.2
9.59
3.28
60.95
70.70
10666
2539
32.03
BURN
BURN
NO
19:00
14,4
13.30
3.13
26.94
47.10
13268
3104
33.58
BURN
BURN
NO
20:00
28.8
12.94
3.02
52.98
46.96
15408
3599
35.36
BURN
BURN
NO
21:00
46.2
13.19
3.02
89.06
96.33
15971
3731
37.25
BURN
BURN
NO
22.-00
52.8
11.70
3.12
78.39
73.48
15971
3731
39.11
BURN
BURN
NO
23:00
43.5
12.24
3.12
72.37
79.94
15079
1*99
40.88
BURN
BURN
NO
40.1
12.54
3.03
66.95
69,47
14562
3406
40.88
0
0.234
•NOTE: FOR-YES* REPORT EVENT
02 - HIGH OXYGEN VIOLATION DP - LOW SCRUBBER DP VIOLATION
SQ - LOW SCRUBBER FLOW VIOLATION OP ¦ HIGH OPACITY VIOLATION
j
Print Data: 8/24/99
Print Tlm« 10:52 AM
M-7
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 2 of 5
Mill Creek Waste Water Treatment Plant
Date of Report
'
7/19/1999
Incinerator #6 "Dally" Report
_
Fuel
Acatm.
Fuel
Aeoim.
Fuel
Accum.
Furnace
Scrubtur
FKia
Breach
Scrub Q
inc. Bum
N. Gas
N. Gas
Digester
Digester
Oil
Fuel DO
Pressure
D.P,
Opadty
02
GPM
Hours
Hour
(tcfh)
«*>
(scftn)
(Bpm)
(sal)
(ln.H20)
(InJ-CO)
(*)
{%>
(hr)
0:00
2S03
2903
0
0
-0.51
28.45
4.0
5.3
1225
1
1:00
2732
jg35
6
6
-0.50
28.13
3.0
4.2
1224
1
2:00
1960
7825
1030
1036
-051
28.15
3.0
4.0
1226
1
3:00
1437
9062
2615
3651
-0.50
28.05
3.0
3.7
1226
1
4:00
1201
10263
2340 .
5991
-0.50
26.18
3.0
4.1
1227
5:00
184
10447
6
5997
-0.50
28.08
3.0
45
1228
1
6:00
0
10447
12
6009
-0.50
28.00
3.0
5.6
1227
1
7:00
36
10483
30
6039
-0.50
28.03
3.0
3.8
1226
1
8:00
166
10649
0
6039
-0.50
28.05
3.0
5.1
1297
9:00
3756
14405
0
6039
•0.50
2B2B
2.9
5.4
1352
1
10:00
2521
16926
S
6045
•0.50
28.50
3.5
2.8
1355
1
11:00
0
16926
6
6051
-0.50
28,13
2.7
5.7
1351
12:00
1756
18682
12
6063
-0.49
28.18
2.0
8.9
1347
13:00
3695
22377
1937
8000
•0.2(9
27.70
2.7
6.1
1338
1
14:00
271
22646
2548
10548
¦0.30
27.08
3.0
5.2
1335
1
15:00
2
22650
876
11224
-0.31
26.85
2.6
5.5
1332
1
16:00
1665
24315
15
11239
-0.30
26.95
4.3
4.9
1332
1
17:00
3233
27548
406
11645
•0.30
27.30
3.0
3.4
1332
1
18:00
1468
29016
577
12222
-0.30
28.28
3.1
6.1
1331
19:00
4599
33615
17
12239
•0.31
27.33
3.0
5.1
1328
1
20:00
602
34217
0
12239
-0,30
27.08
3.0
4,8
1327
1
21:00
3556""
37773
614
12853
-039
Z7JS3
3.7
4.2
1327
1
22:00
3695
41468
1797
14650
•0.34
28.40
3.9
4.4
1325
1
23:00
3476
44944
1871
16521
-0.35
28.35
3.8
4.5
1323
1
1873
44944
688
16521
•042
27JT7
3.1
4.9
12S6
24
™ N.LB.
Incinerator was not In bum mode.***
PROCESS OXYGEN DAILY (MANUAL) CALIBRATION APROX TIME:
09£7
BY:
KG
Cattration Results of THC and 02Anatyiers
Tlma of Catoration
Bottle conc.
Cylinder
Zere
Span
(pom)
10*
(ppm)
(ppm)
8:
15
1 DW
1(0
•*•34161
0.0
1", b.O
02
19.9
130
0.1
20.10
Print Date: 8/24/89
Print Time: 10S2 AM
M-R
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County Pay* 3 o;
Mill Creek Waste Water Treatment Plant
V
7/19/1899
Incinerator #6 "Daily" Report
Afterb.
Breech
Hrth. 1
Hrth.2
Hrth.3
Hrtti. 4
Hrtfi.5
Hrtti. 6
Hrth.7
Hrth. 8
Hrtti, 9
Temp.
Temp.
Tamp.
Temp.
Temp.
Tamp.
Temp,
Temp.
Temp.
Temp,
Temp.
Hour
(F)
(F)
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Mill Creek Waste Water Treatment Plant
Incinerator #6 "Daily" Report
Page 4 of 5
Date of Report
7/19/1999
Mnute*>
Hour
RANGE LIMIT =
0
26.0
15
Scrubber
inches H20
30
45
HrAvg
#
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County p2ge 5 ef 5
Mill Creek Waste Water Treatment Plant
Date of R»"so*
Incinerator #8 "Daily" Report
--
7/19/1999
Minute=» 0
Hour
6
12
18
HtM Gas Opacity
(%)
24 30 36
42
48
54
HrAvg
#>20
#>60
0:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
1:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
2:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
3:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
4:00
3
3
3
3
3
3
3
-3
3
3
3.0
0
0
5:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
8:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
7:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
8:00
3
3 —
3
3
3
3
3
3
3
3
3.0
0
0
9:00
3
3
3
3
3
3
3
3
3
2
2.9
0
0
10:00
3
5
5
4
3
3
3
3
3
3
3.5
0
0
11:00
3
3
3
3
3
3
3
2
2
2
2.7
0
0
12:00
2
2
2
2
2
2
2
2
2
2
.2.0
0
0
13:00
2
2
2
3
3
3
3
3
3
3
2.7
0
0
14:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
15:00
3
3
3
3
3
2
2
2
2
3
2.5
0
0
16:00
• 3
3
3
2
17
. 3
3
3
3
3
4.3
0
0
17:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
18:00
3
4
3
3
3
3
3
3
3
3
3.1
0
0
19:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
20:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
21.-00
4
4
3
4
4
4
4
4 '
3
3
3.7
0
0
22:00
3
4
3
3
4 ¦
4
4
4
4
4
3.9
0
0
23:00
4
4
3
3
4
4
4
4
4
4
3.8
0
0
3.1
3.2 3.0 3.0 3.7 3.1 3.1 3.0
OPACITY DAILY AUTOMATIC CALIBRATION AT TIME 18:27
3.0
3.0
3.1
0
0
Print Data: 8/24/99
Print Tim*: 10:52 AM
M-11
1
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 1 of 5
Mill Creek Waste Water Treatment Plant
Date of Report
•* /,
7/20/1999
Incinerator #6 "Da!
ly" Report
-
Unoofr,
CEM
Moist
Corr.
Rolling
Sludge
Sludge
Aecum.
LOWEST
HIGHEST
Report
THC
Oxygen
H20
THC
C. THC
Peed
Peed
Sludge
STATUS
STATUS
Event
Hour
(ppm)
(%)
(*)
(ppm)
(ppm)
(wet tb/hr) (dry Ib/hr)
(dry tons)
0:00
23.6
12.02
3.09
38.08
62.95
14156
3446
1.72
BURN
BURN
NO
1:00
22.6
14.28
3.12
48.29
52.91
14156
3448
3.45
BURN
BURN
NO
2:00
26.5
10.76
3.07
40.64
42.34
14156
3448
5.17
BURN
BURN
NO
£00
21.0
13.06
3.06
38.56
42J0
14156
3448
6.90
BURN
BURN
NO
4:00
35.2
13.03
3.08
83J6
47.69
14156
3448
8.62
BURN
BURN
NO
5:00
39.4
12.79
3.02
89.39
ST 27
14156
3448
10.35
BURN
BURN
NO
6:00
38,7
12.52
3.03
87.69
86.98
14156
3448
12.07
BURN
BURN
NO
7:00
38.3
12.26
3.03
83J5
86.81
14156
3448
13.79
BURN
BURN
NO
8:00
40.1
12-62
3.02
69.03
66.69
14156
3448
15.52
BURN
BURN
NO
9:00
v39.1
1Z25
3.05
64.63
65.67
14156
3448
17.24
BURN
BURN
NO
10:00
,37.7
12.84
3.03
66.70
66.79
14156
3448
18.97
BURN
BURN
NO
11:00
34.1
11.83
3.10
54.08
61.61
14156
3448
20.69
BURN
BURN
NO
12:00
'28.6
12.05
3,08
46.37
55.72
14156
3448
22.41
BURN
BURN
NO
13:00
26.5
12.37
3.08
44.69
48.36
14156
3448
24.14
BURN
BURN
NO
14:00
30.0
12^3
3.12
49.36
46.81
14156
3446
25.86
BURN
BURN
NO
15:00
37.4
12.92
3.12
66.81
53.62
14156
3448
27JS
BURN
BURN
NO
16:00
42.0
12.49
3.14
71.43
6233
14156
3448
29.31
BURN
BURN
NO
17:00
38.5
12.74
3.12
67.69
68.64
14156
3448
31.04
BURN
BURN
NO
18:00
41.6
10.78
3.13
63.18
87.43
14156
3448
32.76
BURN
BURN
NO
19:00
41.9
12.99
3.13
75.48
68.78
14156
3448
34.46
BURN
BURN
NO
20:00
42.8
12.73
3.12
74.78
71.15
14156
3448
36.21
BURN
BURN
NO
21:00
43.4
12.97
3.12
78.24
76.17
14277
3478
37 JS
BURN
BURN
NO
2230
40.3
1Z35
3.1S
87.85
73.52
14682
3825
39.76
BURN
BURN
NO
23:00
39.9
11.97
3.14
_£iZL_
69J6
14882
362S
41.57
BURN
BURN
NO
-
35.4
12.45
3.09
60.57
60.96
14222
3484
41.57
0
SbdpeMulHpaar*
0244
•NOTE: FOR -YES- REPORT EVENT
02 « HIGH OXYGEN VIOLATION DP ¦ LOW SCRUBBER DP VIOLATION
SQ - LOW SCRUBBER ROW VIOLATION OP ¦ HIGH OPACITY VIOLATION
Prirt Date: 8/24/99
Print Time: 1031 AW
M-12
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County Fv;* 2 0* 3
Mill Creek Waste Water Treatment Plant
*
7/20/1999
Incinerator #6"
Daily" Report
Fuel
Aeeum.
Fuel
Accum.
Fuel
Accum.
Furnace
Scrubber
Flue
Breech
Scrub Q Inc. Bum
N. Gas
N. Gas
Digester
Digester
Oil
Fuel OS
Pressure
D.P.
Opacity
02
GPM
Hours
Hour
(sdh)
(if)
(scfm)
(cf)
(Opm)
(gat)
(lrvH20)
(ln.H20)
(%)
(%)
(hr)
0:00
2477
2477
2064
2064
-0.35
28.23
3.5
5
1322
1
1:00
4035
6512
2397
4461
-0.35
28.25
4.0
5.5
1320
1
2:00
4802
11314
2861
7342
-0.35
28.08
3.7
5.2
1317
1
3:00
2302
13618
299
7641
*0.35
28.08
4.0
6.2
1313
1
4:00
2549
16165
0
7641
-0.35
28.00
4.0
5.5
1311
1
5:00
1827
17792
1353
1994
-0.35
28.03
4.0
5.3
1310
1
6:00
1369
19161
2002
10996
-0.35
28.03
4.0
5.0
1310
7:00
738
19899
2491
13487
-0.35
27.93
4.0
4.6
1308
1
8:00
630
20529
2964'
16451
-0.35
28.00
4.0
4.9
1307
1
9:00
629
21158
3259
19710
-0.35
28.05
3.3
4.6
1310
1
10:00
2044
23202
3231
22941
-0.35
28.10
3.6
5.4
1308
1
11:00
5402
28604
2710
25651
-0.35
28.15
3.0
3,5
1306
1
12:00
3088
31692
2293
27944
-0.36
28.08
3.0
4.2
1303
1
13:00
3128
34820
1426
29370
-0.35
28.08
3.0
4.5
1294
1
14:00
2221
37041
0
29370
-0.35
28.03
3.2
4.2
1288
1
15:00
256
37297
19
29389
-0.35
27.98
4.0
4.5
1288
1
16:00
17S
37476
564
29953
-0.35
27.95
5.2
4.5
1289
17:00
31
37507
36
29991
.
-0.38
28.00
4.0
4.5
1290
18:00
0
37507
0
29891
-0.35
28.00
4.0
4.4
1290
1
19:00
0
37507
0
29991
•0.35
28.00
4.0
4.7
1286
1
20:00
0
37507
0
29991
-0.35
27.88
4.0
4.9
1287
1
21:00
1202
38709
658
30649
-0.36
27.95
3.9
4.6
1266
1
22:00
2350
41059
13
30662
-0.35
27.63
3.7
4.5
1289
23:00
2033
43092
15
30677
-0.35
27.85
4.0
3.9
1293
1
1796
43092
1278
30677
•0.35
28.02
3.8
4-8
1301
24
~ N.I.B.
Incinerator was not In burn mode.***
PROCESS OXYGEN DAILY (MANUAL.) CALIBRATION APROX TIME:
0825
BY:
KC
Cafibratkxi Results of THC and 02 Anatyzera
Time of CaBiration
Bottle core.
Cylinder
Zero
Span
(ppm)
10*
(ppm)
(ppm)
8
15
THC
176
sx-34161
0.0
175.6
02
19.9
130
0,1
20.05
Print Data: 8/24/99
Print Time: 10:51 AM
M-13
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 3 of 5
Mill Creek Waste Water Treatment Plant.
Date of Report
•
7/20/1999
Incinerator #6 "Dally" Report
Afterb.
Breech
Hrth. 1
Hrth. 2
Hrth. 3
Hrth. 4
Hrth. 5
Hrth. 6
Hrth. 7
Hrth. 8
Hrth. 9
Temp.
Temp.
Tamp.
Tamp.
Temp.
Temp.
Temp.
Temp.
Tamp.
Temp.
Temp.
Hour
(F)
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County Pag? * of 5
Mill Creek Waste Water Treatment Plant
Qsto r\* Oon«f»
.• 7/20/19S9
Incinerator #6 "Daily" Report
Mlnuto=>
Hour
RANGE UMIT «=
0
2S.0
15
Scrubber
Inches H20
30
45
HrAvg
#
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 5 of 5
Mill Creek Waste Water Treatment Plant
Oatt of Report
*
7/20/1999
Incinerator #6 "Daily" Report
-
Aw* Cn Opiclty
m
Mintrte=>
0
6
12
18
24
30
36
42
48
5*
KrAvg *>20
#»60
Hour
0:00
4
3
3
3
3
3
4
4
4
4
3.5
0
0
1:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
2:00
4
4
4
4
4
4
4
3
3
3.7
0
0
3:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
4m
4
4
4
4
4
4
4
4
4
4
4.0
0
0
5:00
. 4
4
4
4
4
4
4
4
4
4
4.0
0
0
6.00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
7:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
8:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
9:00
4
4
3
3
3
3
3
3
3
4
3.3
0
0
10:00
4
4
4
4
4
3
3
3
3
3.6
0
0
11:00
'3
3
3
3
3
3
3
3
3
3
3.0
0
0
12:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
13:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
14:00
3
3
3
3
3
3
3
3
4
4
3.2
0
0
15:00
4
4
4
4
4
4
4
4
4
4.0
0
0
16:00
4
4
4
3
17
4
4
4
4
4
8.2
0
0
17:00
4
4
4
4
4
4
4
4.0
0
0
18:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
19:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
20&0
4
4
4
4
4
4
4
4
4
4.0
0
0
21:00
4
4
4
4
4
4
4
4
4
3.9
0
0
22fl0
3
3
3
4
4
4
4
4
3.7
0
0
23:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
3-8
3J
3.7
3.7
4J3
X8
3.8
3.7
3.8
3.8
3.8
0
0
OPACITY DAILY AUTOMATIC CALIBRATION AT TIME 1627
Print Date: 8/24*9
Print Time: 1(hS1 AH
M-16
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Mill Creek Waste Water Treatment Plant
p-ije i o'5
' 7/21/1999
Incinerator #6 "Daily" Report
Uncorr.
GEM
Moist
Corr.
Rolling
Sludge
Sludge
Accum.
LOWEST
HIGHEST
Report
THC
Oxygen
H20
THC
C. THC
Feed
Feed
Sludge
STATUS
STATUS
Event
Hour
(PPf")
m
m
(ppm)
fcjpm)
(wettb/hf)
(dry Ib/Hr)
(dry tons)
0:00
34.7
12.27
3.07
57.88
63.07
14882
2893
1.45
BURN
BURN
NO
1:00
45.3
12.56
3.05
77.59
66.42
14882
28S3
2.89
BURN
BURN
NO
2:00
43.6
11.30
3.04
67.52
87.66
14682
2893
4.34
BURN
BURN
NO
3:00
35.5
12.18
3.04
58.12
67.75
14882
2893
5.79
BURN
B'JRN
NO
4:00
40.9
12.63
3.02
70.51
65.39
14882
28S3
7.23
BURN
BURN
NO
5:00
44.8
12.70
3.02
77.64
68.83
14882
2893
8.68
BURN
BURN
NO
6:00
45.6
12.62
3.02
78.69
75.68
14882
2893
10.13
BURN
BURN
NO
7:00
39.2
12.11
3.03
63.64
73.39
14882
2893
11.57
BURN
BURN
NO
8:00
36.3
12.51
3.01
61.72
68,02
14828
2883
13.01
BURN
BURN
NO
9:00
142.7
13.72
3.04
84.47
69.94
14882
2893
14.46
BURN
BURN
NO
10:00
,45.1
14.11
3.08
94.75
80.31
14882
2893
15.91
BURN
BURN
NO
11:00
41.6
12.75
3.15
73.28
84.16
14882
2893
17.35
BURN
BURN
NO
12:00
47.9
11.56
3.21
72.55
60.19
14882
2893
18.80
BURN
BURN
NO
13:00
272
12.20
3.21
44.73
63.52
14882
2893
20.25
BURN
BURN
NO
14:00
27.1
11.44
3.25
41.33
52.87
14882
2893
21.69
BURN
BURN
NO
15:00
22.6
12.12
3.25
36.83
40.97
14882
2893
23.14
BURN
BURN
NO
16:00
20.4
11.53
3.30
31.33
36.50
14882
2893
24.59
BURN
BURN
NO
17:00
22.7
12,52
3.25
38.80
35.66
14882
2893
26.03
BURN
BURN
NO
18:00
18.2
9,43
3.31
24,90
31.68
14792
2876
27.47
BURN
BURN
NO
19:00
15.8
11.49
3.27
24.12
29,27
14556
2830
28.88
BURN
BURN
NO
20:00
16.7
12.73
3.23
29.22
26.08
14338
2787
30-28
BURN
BURN
NO
21:00
22.4
12.83
3-23
38.89
30.74
14338
2787
31.67
BURN
BURN
NO
22:00
18.4
12.74
3.23
32.40
33.50
14338
2787
33.07
BURN
BURN
NO
23:00
25.9
12.79
3.23
45.83
39.04
14338
2787
34.46
BURN
BURN
NO
32.5
12.28
3.15
55-29
56.28
14772
2872
34.46
0
SludgeMultiplief ¦
0.194
•NOTE: FOR "YES* REPORT EVENT
02 = HIGH OXYGEN VIOLATION DP « LOW SCRUBBER DP VIOLATION
SQ = LOW SCRUBBER FLOW VIOLATION OP * HIGH OPACITY VIOLATION
Print Data: 8/24/99
Print Time; 10:50 AM
M-17
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 2 o? 5
Mill Creek Waste Water Treatment Plant
Date of Report
* _*
7/21/1999
Incinerator #6 "Daily" Report
Fuel
Aocum.
Fuel
Accum.
Fuel
Aceum.
Furnace
Scrubber
Rue
Breech
Scrub O
Inc. Bum
N. Gas
N. Gas
Digester
Digester
Oil
Fuel Oil
Pleasure
D.P.
Opacity
02
GPM
Hours
Hour
(sdh)
= Incinerator was not In bum mode.***
PROCESS OXYGEN DAILY (MANUAL) CALIBRATION APROX TIME:
10:02
BY:
KC
Calibration Results of THC and 02 Anafyzers
Time of Caibration
* Bottle cone.
Cylinder
Zero
Span
(ppm)
ID*
(PPm)
(ppm)
8 :
15
TMC
176
cx-34161
0.0
175.7
02
1S.8
130
0.1
20.07
Print Date: 8/24/99
Print Tims: 10:50 AM
M-18
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Mill Creek Waste Water Treatment Plant
Fpjr c't
< 7/21/1999
incinerator #6 "Daily" Report
Afterb.
Breech
Hrth. 1
Hrth. 2
Hrth. 3
Hrth. 4
Hrsh.5
Hrth. 6
hrth. 7
Hrth. 8
Hrth. 9
Temp.
Tamp.
Temp,
Temp.
Temp,
Temp.
Temp.
Temp.
Temp.
Temp.
Temp.
Hour
(F)
CP)
(F)
(F)
(F)
m
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 4 of 5
Mill Creek Waste Water Treatment Plant
Date of Report
. 7/21/1999
Incinerator #6
"Daily"
Report
-
Scrubber
RANGE UMfT
26.0
Inches H20
Minute**
0
15
30
45
HrAvg
#
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County ?S3p ? ^ «
Mill Creek Waste Water Treatment Plant
Incinerator #6 "Daily" Report
7/21/199S
Minute** 0
Hour
6
12
18
But Gas Opacity
{%)
24 30 36
42
48
54
HrAvg
#>20
#>60
0:00
4
4
4
4
4
4
,4
4
4
4
' 4.0
0
0
1:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
2:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
3:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
4:00
4
4
4
4
4
A
4
4
4.0
0
0
5:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
6:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
7:00
4
4
4
4
4
4
4
4
4.0
0
0
8:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
9:00
4
4
4
4
4
4
5
5
S
5
4.4
0
0
10:00
5
5
5
5
5
5
S
4
4
3
4.6
0
0
11:00
4
4
4
4
4
4
4
4
4
3
3.9
0
0
12:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
13:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
14:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
15:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
16:00
¦ 3
3
3
3
16
3
3
3
3
3
4.3
0
0
17:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
18:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
19:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
20:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
21:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
22:00
3
a
3
3
3
3
3
3
3
3
3.0
0
0
23:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
3.S
3.5 3.5 3.5 4.1 3.5 3.6 3.5
OPACITY DAILY AUTOMATIC CALIBRATION AT TIME 16:27
3.5
3.5
3.6
0
0
Print Data: 8/24/99
Prbit Time: 10:50 AM
M-21
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 1 ef 5
Mill Creek Waste Water Treatment Plant
Date of Report
7/22/199S
Incinerator #6 "Dally
" Report
v
Unoorr.
CEM
Moist
Com
RdBng
Sludge
Sludge
Accum.
LOWEST
HIGHEST
Report
THC
Oxygen
H20
THC
C.THC
Feed
Feed
Sludge
STATUS
STATUS
Event
Hour
(ppm)
{%)
<%>
(ppm)
(ppm)
(wettMir)
(dry lb/hr)
{dry tons)
0:00
21.0
12.86
3.18
37.70
38.64
14296
3095
1.55
BURN
BURN
NO
1:00
28.0
12.60
322
48.67
44.07
14156
3065
3.08
BURN
BURN
NO
200
21.0
10.87
3.16
34.39
4025
14156
3065
4.61
BURN
BURN
NO
3:00
29.7
1X59
322
51.56
*4.87
14156
3065
8.14
BURN
BURN
NO
4:00
20.6
1Z67
3.12
35.81
40.59
14156
3065
7.68
BURN
BURN
NO
8:00
18.8
12.40
3.13
31.68
39.69
14156
3065
821
BURN
BURN
NO
6:00
21.6
13.65
3.13
42.45
36.65
14156
3065
10.74
BURN
BURN
NO
7:00
37.7
14.16
3.17
60.10
51.41
14156
3065
12.27
BURN
BURN
NO
8:00
32.5
12.66
3.20
57.30
59.95
14156
3065
13.81
BURN
BURN
NO
9:00
*20.4
13.20
223
37.79
58.40
14156
3065
15.34
BURN
BURN
NO
10:00
•20.1
12.59
323
34.61
4323
14156
3065
16.87
BURN
BURN
NO
11:00
20.8
12.71
3.34
3626
3622
14156
3065
18.40
BURN
BURN
NO
12:00
18.5
12.47
3.34
31.41
34.09
14156
3065
19.94
BURN
BURN
NO
13:00
19.2
12.65
3.34
33.35
33.67
14156
3065
21.47
BURN
BURN
NO
14:00
18.2
12.35
3.34
30.59
31.78
14156
3065
23.00
BURN
BURN
NO
15:00 ¦
22.6
12.56
3.34
38.76
3423
14156
3065
24.53
BURN
BURS
NO
16:00
24.7
11.90
3.34
39.42
3626
14156
3065
26.07
BURN
BURN
NO
17:00
18.9
12.27
3.34
31.38
36.52
14156
3065
27.60
BURN
BURN
NO
18:00
23.7
9.63
3.35
33.05
34.62
14156
3065
29.13
BURN
BURN
NO
19:00
18.6
12.46
3.34
31.57
32.00
13993
3029
30.65
BURN
BURN
NO
20:00
23.4
12.42
3.32
39.57
34.73
14005
3032
32.16
BURN
BURN
NO
21:00
23.3
11.90
3.30
37.05
36.06
14223
3079
33,70
BURN
BURN
NO
22:00
22.9
12.60
3.30
3925
38.62
14519
3143
3527
BURN
BURN
NO
23:00
28.1
12.60
3.23
48.41
41.57
14595
3160
36.35
BURN
BURN
NO
23.1
12.46
3.26
40.09
39.92
14185
3071
36.65
0
SMgeMultlpller ¦
0216
•NOTE: FOR "YES- REPORT EVENT
02 * HIGH OXYUEN VIOLATION OP * LOW SCRUBBER Dk VIUuA iON
SQ • LOW SCRUBBER FLOW VIOLATION OP * HIGH OPACITY VIOLATION
Print Date: 8/24/99
Print Time: 10:4^2
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
2 of 5
Mill Creek Waste Water Treatment Plant
uale oi nepcn
7/22/1339
Incinerator #6
•Daily" Report
Fuel
Aecum.
Fuel
Accum.
Fuel
Acaim.
Furnace
Scrubber
Flue
Breech
Scrub Q Inc. Bum
N. Gas
N. Gas
Digester
Digester
Oil
Fuel Oil
Pressure
DJ=.
Opacity
02
GFM Hours
Hour
(stfh)
0*0
0:00
6009
8009
7029
7029
<.36
28.20
3.0
4.8
1303 1
1:00
5785
11794
7689
14718
-0.35
28.25
3.0
3.6
1313 1
£00
8119
17913
8270
22988
-0,35
28.28
3.9
5.1
1313 1
3:00
5610
23523
7934
30922
-0J5
28.28
4.0
3.5
1308 1
4:00
6164
29687
4463
35385
-0.35
28.30
4.0
3.5
1309 1
5:00
4184
33871
1257
36842
•0.35
28.23
4.0
3.9 -
1305 1
6:00
2983
38854
6
38648
-0.35
28.10
4.0
£.1
1312 1
7:00
1576
38430
6
36654
-0.35
28.00
4.0
5.6
1302 1
8:00
5028
43458
8
36660
-0.35
28.43
4.1
4.6
1297 1
9:00
6922
50380
105
36765
-0.35
28.50
4.0
5.0
1293 1
10:00
7788
58148
0
36765
-0.35
28.45
4.0
5.0
1296 1
11:00
7484
65632
6
36771
-0.35
28.45
4.0
5.0
1303 1
12:00
7326
72958
0
36771
-0.35
28.28
3.3
5.0
1299 1
13:00
7190
80148
0
36771
-0.35
28.28
3.0
5.2
1298 1
14:00
6035
86183
2755
39526
-0.35
28.03
3.0
5.8
1291 1
15:00
5871
92054
1874
41400
-0.35
27.83
3.0
£.5
1294 1
16:00
5567
97621
0
41400
-0.35
27.70
4.3
5_2
1288 1
17:00
7772
105393
6
41406
-0.35
27.78
3.0
4.9
1291 1
18:00
5221
110614
6
41412
-0.35
27.63
3.0
5.3
1287 1
19:00
7226
117840
6
41418
-0.36
27.75
3.0
5.6
1293 1
20:00
5775
123615
0
41418
-0.35
27.75
3.0
4.8
1285 1_
21:00
6536
130151
0
41418
-0.38
27.90
3.0
5.4
1293 1
22:00
6496
136647
25
41443
-0.35
27.78
3.0
4.6
1292 1
23:00
3750
140397
31
41474
-0.35
27.83
3.0
6,4
1288 1
5850
140397
"" 1728
41474
•0.35
28.08
_3.5
4.9
1298 24
*" N.I.B.
** Indneratorwas not In bum mode."*
PROCESS OXYGEN DAILY (MANUAL) CALIBRATION APROX TIME:
08:26
BY:
KC
Calibration Results ofTHC and 02 Analyzes
Time of Captation
Bottle conc.
Cylinder
Zero
Span
(ppm)
IO#
(ppm)
(ppm)
8: 15
THC
176
#*¦34161
0.0
175.0
02
19.9
130
0.1
20.02
Print Data: 8/24/99
Print Time: 10:46 AM
M-23
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County
Page 3 of 5
Mill Creek Waste Water Treatment Plant
Date of Report
-•*
7/22/1999
Incinerator #6 "Dally" Report
*
-
Afterfc.
. Breach
Hrth. 1
Hrth. 2
Hrth. 3
Hrth. 4
Hrth. 5
Hrth. 6
Hrth. 7
Hrth. 8
Hrth. 9
Tamp.
Tamp.
Tamp.
Tamp.
Tamp.
Temp.
Tamp.
Tamp.
Tamp.
Tamp
Temp.
Hour
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County Page 4 c f 5
Mill Creek Waste Water Treatment Plant
WOlti V i t
.' 7/22/1999
Incinerator #6 "Dally" Report
Mlnute=
Hour
RANGE LIMIT =
» 0
26.0
15
Scrubber
Inches H20
30
45
HrAvg
#
-------
Metropolitan Sewer District of Greater Cincinnati and Hamilton County page5ofs
Mill Creek Waste Water Treatment Plant
Data of Report
-• 7/22/1999
Incinerator #6 "Daily" Report
Minut»=>
Hour
0
6
12
18
24
Rum Gu Opacfty
(X)
30 36
42
48
54
HrAvg
#>20
#>€
0:00
3
3
3
3
3
3
, 3
3
3
3
3.0
0
0
1:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
2:00
3
4
4
4
4
4
4
4
4
4
3.9
0
0
3:00
4
4
4
4
4
4
4
4
4
4.0
0
0
4:00
4
4
4
4
4
4
4
4
4
4.0
0
0
5:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
6:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
7:00
4
4
4
4
4
4
4
4
' 4
4
4.0
0
0
8:00
4
S
4
4
4
4
4
4
4.1
0
0
8:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
10:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
11:00
4
4
4
4
4
4
4
4
4
4
4.0
0
0
12:00
4
4
4
3
3
3
3
3
3
3
3.3
0
0
13:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
14:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
15:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
16:00
3
3
3
3
16
3
3
3
3
3
4.3
0
0
17:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
16:00'
3
3
3
3
3
3
3
3
3
3
3.0
0
0
19:00
3
3
3
3
3
3
3
9
3
3
3.0
0
c
20:00
3
3
3
3
3
3
3
3
3
3
3.0
0
0
21:00
3
a
3
3
3
3
3
3
3
3
3.0
0
0
22:00
3
3
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OPACITY DAILY AUTOMATIC CALIBRATION AT TIME: 1837
Print Data: 8/2*99
Print Tin*: 10:48 AM
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iPPENDIXfC
Sampling and Analytical Protocols
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N-l
PCB Protocols
N-1
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N-l-1
Draft Air Emissions Method
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Proposed Analytical Method for
Determination of Toxic Polychlorinated Biphenyl
Emissions from Sewage Incinerator Stationary Sources Using Isotope Dilation
High Resolution Gas Chromatography/High Resolution Mass Spectrometry
July 20,1999
Prepared by
Marielle C. Brinkman
Study Coordinator
Jane C. Chuang
Work Assignment Leader
for
C.E. (Gene) Riley
Work Assignment Manager
Kathy Weant
Project Officer
Emissions, Monitoring, and Analysis Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Battelle
505 King Avenue
Columbus, Ohio 43201-2693
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Proposed Analytical Method for Determination of Toxic
Polychlorinated Biphenyl Emissions from Sewage Incinerator Stationary
Sources Using Isotope Dilution High Resolution Gas Chron?
Resolution Mass Spectrometry
1.0 SCOPE AND APPLICATION
1.1 This analytical method applies to the determination of toxic polychlorinated
biphenyls (PCBs) in air emissions from sewage incinerator stationary sources at
nanogram to picogram levels. The sensitivity which can ultimately be achieved
for a given sample will depend upon the types and concentrations of other
chemical compounds in the sample, as well as the original sample size and
instrument sensitivity.
1.2 The analytical method presented here is intended to determine toxic PCBs in
samples containing PCBs as single congeners or as complex mixtures. The target
analytes are listed in Table 1.
1.3 The method is restricted for use only by or under the supervision of analysts
experienced in the use of high resolution gas chromatography (HRGC)/high
resolution mass spectrometry (HRMS), and skilled in the interpretation of mass
spectra.
1.4 Because of the extreme toxicity of these compounds, the analyst must take
necessary precautions to prevent exposure to himself/herself, or to others, of
materials known or believed to contain PCBs.
2.0 SUMMARY OF METHOD
2.1 Particulate and gaseous phase PCBs are collected isokinetically from the stack
and collected on a glass fiber filter, XAD-2 resin, and in impingers using a
Modified Method i(MM5) sampling train. Procedures for MM5 sample
collection are provided in EPA Method 0010. The MM5 samples consist of the
filter, front and back half solvent rinses, the XAD-2 resin module, and impinger
water and solvent rinses. The XAD-2 resin is pre-spiked with surrogate standards
to monitor sampling efficiency during the sample collection. The preparation,
pre-certification, and pre-spiking of tile XAD-2 resin is described in Appendix A
of this method. The preparation and pre-certification of the particulate filter is
described in Appendix B of this method.
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2.2 The field samples are combined into two separate fractions for extraction and
analysis: (1) front half reagent rinses and filter, and (2) back half reagent rinses,
XAD-2 resin, and the impinger water contents and reagent rinses.
2.3 The analytical.flow diagram depicting the front and back half extraction
procedures is shown in Figure 1. The samples are extracted using Soxhlet and/or
solid phase extraction (SPE) techniques._Front and back half sample extracts are
cleaned using acid/base partitioning, and silica and carbon column
chromatography. The flow diagram depicting the cleanup procedures is shown in
Figure 2. The separate front and back half extracts are analyzed using
HRGC/HRMS.
2.3.1 Isotopically labeled internal standards are added to each fraction separately
before extraction.
2.3.2 Isotopically labeled cleanup standards are added to the front half extract
prior to sample cleanup. Isotopically labeled cleanup standards are not
added to the back half extract (See Section 7.2.4.3).
2.3.3 The PCB analytes in the processed extracts are separated with HRGC and
identified and measured with HRMS. Results are quantified using relative
response factors.
2.4 Various performance criteria are specified herein which the analytical data must
satisfy to ensure the quality of the data. These represent minimum criteria which
mast be incoiporated into any program in which toxic PCBs are determined in
emissions from stationary sources.
DEFINITIONS AND ABBREVIATIONS
3.1 Definitions and Acronyms
3.1.1 Analyte - a PCB compound measured by this method. The analytes are
listed in Table 1.
3.12 Calibration Standard (CS) - a solution prepared from a secondaiy
standard and/or stock solutions and used to calibrate the response of fee
instrument with respect to analyte concentration.
3.1.3 Calibration Verification Standard (VER) - the mid-point calibration
standard (CS3) that is used to verify calibration. See Table 4.
3.1.4 Congener - refers to a particular compound of the same chemical family.
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3.1.5 CS1, CS2, CS3, CS4, CSS - see calibration standards in Table 4,
3.1.6 HRGC - high resolution gas chromatograph or gas chromatography,
3.1.? MKiVIjs - hign resolution mass spectrometer or mass spectrometry.
3.1.8 Internal Standard (IS) - a component which is added to every sample
and is present in the same concentration in every blank, quality control
sample, and calibration solution. The IS is added to the sample before
extraction and is used to measure the concentration of the analyte and
surrogate compound. The IS recovery serves as an indicator of the overall
performance of the analysis.
3.1.9 K-D - Kudema-Danish concentrator, a device used to concentrate the
analytes in a solvent.
3.1.10 Laboratory Blank - see Laboratory Method Blank.
3.1.11 Laboratory Method Blank - an aliquot of reagent water or solvent that is
treated exactly as a sample including exposure to all laboratory glassware,
equipment, solvents, reagents, internal standards, and surrogates that are
used with samples. The laboratory method blank is used to determine if
analytes or interferences are present in the laboratory environment, the
reagents, or the apparatus.
3.1.12 Laboratory Spike Sample - a laboratory-prepared matrix blark spiked
with known quantities of analytes. The laboratory spike sample is
analyzed exactly like a sample. Its purpose is to assure that the results
produced by the laboratory remain within the limits specified in the
method for precision and recovery.
3.1.13 May - this action, activity, or procedural step is neither required nor
prohibited.
3.1.14 May Not - this action, activity, or procedural step is prohibited.
3.1.15 Must - this action, activity, or procedural step is required.
3.1.16 m/z Scale - the molecular mass to charge ratio scale.
3.1.17 PAR - precision and recovery standard; secondary standard used to
prepare laboratory spike QC samples.
3.1.18 Percent Relative Standard Deviation (%RSD) - the standard deviation
times 100 divided by the mean. Also termed "coefficient of variation."
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3.1.19 PFK - perfluorokerosene; the mixture of compounds used to calibrate the
exact mJz scale in the HRMS.
3.1.20 Primary Dilution Standard - a solution containing the specified analytes
that is purchased or prepared from stock solutions and diluted as needed to
prepare calibration solutions and other solutions.
3.1.21 QC Check Sample - a sample containing all or a subset of fee analytes at
known concentrations. The QC check sample is obtained from a source
external to the laboratory or is prepared from a source of standards
different from the source of calibration standards. It is used to check
laboratory performance with test materials prepared external to the normal
preparation process.
3.1.22 Reagent Water - water demonstrated to be free from the analytes of
interest and potentially interfering substances at the analyte estimated
detection limit; e.g., HPLC grade water.
3.1.23 Recovery Standard - a known amount of component added to the
concentrated sample extract before injection. The response of the internal
standards relative to the recovery standard is used to estimate the overall
recovery of the internal standards.
3.1.24 Relative Response Factor - the response of the mass spectrometer to a
known amount of an analyte relative to a known amount of an internal
standard.
3.1.25 RF - response factor. See Section 10.2.2.
3.1.26 RPD - relative percent difference, defined as the absolute value of the
difference between two values divided by the mean of the two values,
expressed as a percentage.
3.1.27 S/N - signal to noise ratio.
3.1.28 Should - this action, activity, or procedural step is suggested but not.
required.
3.1.29 SICP - selected ion current profile; the line described by the signal at an
exact m/z.
2.1.30 SPE - solid-phase «« e?rtr,ctint? te^hniq^e in which an analvte
is extracted from an aqueous sample by passage over or through a material
capable of reversibly adsorbing the analyte. Also termed liquid-solid
extraction.
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3.1.31 Specific Isomers - a specific isomer is designated by indicating the exact
positions (carbon atoms) where chlorines are located within the moiecuie.
For example, 2,3,3',4,4'-PeCB refers to only one of t.h* 7n<5 prp
isomers -.that isomer which is chlorinated in the 2,3,3',4,4-position of the
biphenyl ring structure,
3.1.32 Specificity - the ability to measure an analyte of interest in the presence of
interferences and other analytes of interest encountered in a sample.
3.1.33 Stock Solution - a solution containing an analyte that is prepared using a
reference material traceable to EPA, the National Institute of Science and
Technology (NIST), or a source that will attest to the purity and
authenticity of the reference material.
3.1.34 Surrogate Standard - a labeled analyte is added in a known amount to
the XAD-2 resin of the sampling train prior to sampling, and allowed to
equilibrate with the matrix before the gaseous emissions are sampled. Its
measured concentration in the extract is an indication of the sampling
efficiency and possible sample breakthrough during the sample collection.
The surrogate standard has to be a component that can be completely
• resolved, is not present in the sample, and does not have any interference
effects.
3.1.35 Toxic PCB - any or all of the toxic chlorinated biphenyl isomers shown in
Table 1.
3.1.36 VER - see Calibration Verification Standard (Section 3.1.3).
Abbreviations
3.2.1 PCB - any or all of the 209 possible polychlorinated biphenyl isomers .
3.2.2 TCB - abbreviation for tetrachlormated biphenyl.
3.2.3 PeCB - abbreviation for pentachlorinated biphenyl.
3.2.4 HxCB - abbreviation for hexachlorinated biphenyl.
3.2.5 HpCB - abbreviation for heptachlorinated biphenyl.
3.2.6 DCB - abbreviation for decachlorinated biphenyl.
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INTERFERENCES
4.1 Method interferences may be caused by contaminants in solvents, reagents,
glassware, and other sample processing hardware that lead to discrete artifacts
and/or elevated backgrounds at the ions monitored. All of these materials must be
routinely demonstrated to be free from interferences under the conditions of the
analysis by analyzing field and laboratory blanks as "described in Sections 9.1,1
and 9.2.2.
4.2 Solvents, reagents, glassware, and other sample processing hardware may yield
artifacts and/or elevated baselines causing misinterpretation of chromatograms.
Specific selection of reagents and purification of solvents by distillation in all-
glass systems may be required. Where possible, reagents are cleaned by extraction
or solvent rinsing. The toxic PCB congeners 105,114,118,123,156,157,167,
and 180 have been shown to be very difficult to completely eliminate from the
laboratory, and baking of glassware in a kiln or furnace at 450-500 °C may be
necessary to remove these and other contaminants.
4.3 Proper cleaning of glassware is extremely important because glassware may not
only contaminate the samples but may also remove the analytes of interest by
adsorption onto the glass surface.
4.3.1 Glassware should be rinsed with methanol and washed with a detergent
solution as soon after use as is practical. Sonication of glassware
containing a detergent solution for approximately 30 seconds may aid in
cleaning. Glassware with removable parts, particularly separatory funnels
with fluoropolymer stopcocks, must be disassembled prior to detergent
washing.
4.3.2 After detergent washing, glassware should be rinsed immediately; first
with methanol, then with hot tap water. The tap water rinse is followed by
distilled water, methanol, and then methylene chloride rinses.
4.3.3 Baking of glassware in kiln or other high temperature furnace (450-
500eC) may be warranted after particularly dirty samples are encountered.
However, baking should be minimized, as repeated baking of glassware
may cause active sites on the glass surface that may irreversibly adsorb
PCBs.
4.3.4 Immediately prior to use, the Soxhlet apparatus should be pre-extracted
with methylene chloride for 3 hours to remove any possible background
contamination.
4.4 The use of high purity reagents minimizes background contamination and
interference problems. Purification of solvents by distillation in all-glass systems
may be required.
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4.5 Matrix interferences may be caused by contaminants that are co-extracted from
the sample. The extent of matrix interferences may vary considerably v, ltll LiC
source being sampled. Toxic PCBs are often associated with other interfering
chlorinated compounds which are at concentrations several orders of magnitude
higher than that of the PCBs of interest. The cleanup procedures in Section 11.3
can be used to reduce many of these interferences, but unique samples may
require additional cleanup approaches.
4.6 Two high resolution capillary columns, a J&W DBXLB, 60 m x 0.25 mm x 0.25
fxm (J&W), and a 50 m x 0.23 mm x 0.25 jum HT-& (SGE), are recommended for
PCB analysis because both of these columns will resolve all 13 toxic PCBs.
Equivalent columns that sufficiently resolve the toxic PCBs may also be used.
4.7 If other gas chromatographic conditions or other techniques are used, the analyst
is required to support the data through an adequate quality assurance program.
5.0 SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this method has not been
precisely defined. Nevertheless, each chemical compound should be treated as a
potential health hazard. Therefore, exposure to these chemicals must be reduced
to the lowest possible level by whatever means available.
5.2 The laboratory is responsible for maintaining a current file of OSHA regulations
regarding the safe handling of the chemicals specified in this method. A reference
file of material safety data (MSD) sheets should also be made available to all
personnel involved in the chemical analysis.
5.3 PCBs and methylene chloride have been classified as known or suspected human
or mammalian carcinogens.
6.0 EQUIPMENT AND SUPPLIES
6.1 Balances
6.1.1 Analytical—Capable of weighing 0.1 mg.
6.1.2 Top loading—Capable of weighing 10 mg.
6.2 Extraction Apparatus
6.2.1 Solid Phase Extraction (SPE); for impinger water.
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SPE manifold, and a vacuum source capable of maintaining 25 in. Hg,
equipped with shutoff valve and vacuum gauge shall be used. SPE
columns containing octadecyl (Clg) bonded silica uniformly enmeshed in
an inert matrix—Fisher Scientific 14-378 °F (or equivalent) are used to
extract the impinger water. Equivalent extracting procedures may be used
to extract the target analytes from the impinger water.
6.2.2 Soxhlet Extraction; for XAD-2 resin and particulate filter.
The XAD-2 resin and particulate filters will be extracted using the Soxhlet
technique. The Soxhlet extractor shall be a 50-mm ID, 200-mL capacity
with 500-mL flask (Cal-Glass LG-6900, or equivalent, except substitute
500-mL round-bottom flask for 300-mL flat-bottom flask). The heating
mantle shall be hemispherical to fit 500-mL round-bottom flask (Cal-Glass
LG-8801-112, or equivalent). The heating mantle is controlled with a
variable transfonner(Powerstat, or equivalent), 110 volt, 10 amp.
6.3 Filtration Apparatus
6.3.1 Pyrex Glass Wool—heated in an oven at 450-500 *C for J hours minimum.
6.3.2 Glass Funnel—125-to 250-mL.
6.3.3 Glass Fiber or Quartz Fiber Filter Paper—Whatman GF/D (or equivalent).
6.4 Cleanup Apparatus
6.4.1 Drying Column—15- to 20-mm ID Pyrex chromatographic column
equipped with coarse-glass frit or glass-wool plug.
6.4.2 Pipets
6.4.2.1 Disposable, Pasteur, 150-mm long * 5-mm ID (Fisher Scientific
13-678-6A, or equivalent).
6.4.2.2 Disposable, serological, 25-mL (E- to 10- mm ID).
6.4.3 Glass Chromatographic Columns
6.4.3.1 150-mm long * 8-mm ID, (Kontes K-420155, or equivalent) with
coarse-glass frit or glass-wool plug and 250-mL reservoir.
6.4.3.2 200-mm long x 15-mm ID, with coarse-glass frit or glass-wool
plug and 250-mL reservoir.
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6.5.2.3 300-mm long * 22-mm ID, with coarse-glass frit, 300-mL reservoir, and
glass or fluoropolymer stopcock.
6.5.3 HPLC/GPC
6.5.3.1 HPLCwith a UV detector.
6.5.3.2 Auto sampler capable of injecting 500 to 600 of sample.
6.5.3.3 Programmable fraction collector.
6.5.3.4 Recorder or integrator capable of recording the signal from a UV
detector.
6.5.3.5 60 mL fraction collector vials/tubes.
6.5.3.6 Liquid chromatography pump capable of providing a constant flew of 5
or 10 mTVmin.
6.5.3.7 122.5 x 300 mm, 100 A pore size, Phenogel GPC/size exclusion column.
6.5.3.8 7.8 x 50 mm Phenogel precolumn.
6.5.4 Oven—-For baking and storage of adsorbents, capable of maintaining a constant
temperature (±5°C) in the range of 105-250°C.
Concentration Apparatus
6.6.1 Rotary evaporator—Buchi/Brinkman-American Scientific No. E5045-10 or
equivalent, equipped with a variable temperature water bath.
6.6.1.1 Vacuum source for rotary evaporator equipped with skutofT valve at the
evaporator and vacuum gauge.
6.6.1.2 A recirculating water pump and chiller are recommended, as use of tap
water for cooling the evaporator wastes large volumes of water and can
lead to inconsistent performance as water temperatures and pressures
vary.
6.6.1.3 Round-bottom flask—100-mL and 500-mL or larger, with ground-glass
fitting compatible with the rotary evaporator.
6.6.2 Kudema-Danish (K-D) concentrator
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6.4.3.3 300-mm long x 22-mm ID, with coarse-glass firit, 300-mL
reservoir, and glass or fluoropolymer stopcock.
6.4.3.4 Oven—For baking and storage of adsorbents, capable of
.maintaining a constant temperature (±5 °C) in the range of 105-
- 250°C.
Concentration Apparatus
6.5.1 Rotary Evaporator—Buchi/Brinkman-American Scientific No. E5045-10
or equivalent, equipped with a variable temperature water bath and
vacuum source. A recirculating water pump and chiller are recommended,
as use of tap water for cooling the evaporator wastes large volumes of
water and can lead to inconsistent performance if water temperatures and
pressures vaiy.
6.5.2 Kudema-Danish (K-D) Concentrator—Concentrator tubes (10-mL
graduated, Kontes K-570050-1025, or equivalent), ground-glass stoppers
(size 19/22 joint) to prevent evaporation of extracts, evaporation flasks (
500-mL, Kontes K-570001-0500, or equivalent), Snyder column (three-
ball macro, Kontes K-503000-0232, or equivalent) may be used.
6.5.2.1 Glass or silicon carbide boiling chips-approximately 10/40 mesh,
should be extracted with methylene chloride, and baked at 450°C
for 1 hour minimum.
6.5.2.2 Fluoropolymer chips (optional) shall be extracted with methylene
chloride prior to use. A heated water bath capable of maintaining
a temperature within ±2°C shall be used in a fume hood.
6.5.3 Nitrogen Blowdown Apparatus—Equipped with water bath controlled in
the range of 30 - 60°C (N-Evap, Organomation Associates, Inc., or
equivalent), installed in a fume hood may be used.
6.5.4 TurboVap Nitrogen Blowdown—Turbovap H, Zymark, or equivalent may
be used, equipped with concentrator tubes (Turbotubes, or equivalent).
Analytical Instrumentation
6.6.1 Gas Chromatograph—Shall have splitless or on-column injection port for
capillary column, temperature program with isothermal hold, and shall
meet all of the performance specifications in Section 10.
6.6.2 GC Columns—Each of the GC columns listed below is capable of
resolving the 13 toxic PCB congeners analyzed for in this method. Other
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GC columns may be used so long as resolution of the PCB if
concern from their most closely eluting leading and trailing congeners can
be demonstrated.
6.6.2.1' -Column #1—50 m long * 0.25±0.02-mm ID; 0.25-nm film HT-8
- (SGE, or equivalent).
6.6.2.2 Column #2—60 m long x 0.25±0.02-mm ID; 0.25-jim film
DBXLB (J&W, or equivalent).
6.6.3 Amber Glass Sample Vials—1 to 2-mL with fluoropolymer-lined screw-
cap.
6.6.4 Amber Glass Vials—0.3-mL, conical, with fluoropolymer-lined screw or
crimp cap.
6.6.5 High Resolution Mass Spectrometer—28- to 40-eV electron ionization,
shall be capable of repetitively selectively monitoring 12 exact m/z's
minimum at high resolution (a 10,000) during a period less than 1.5
seconds, and shall meet all of the performance specifications in
Section 10.
6.6.6 HRGC/HRMS Interface—The high resolution mass spectrometer (HRMS)
shall be interfaced to the high resolution gas chromatograph (HRGC) such
that the end of the capillary column terminates within 1 cm of the ion
source but does not intercept the electron or ion beams.
6.6.7 Data System—Capable of collecting, recording, and storing MS data.
REAGENTS AND STANDARDS
Note: unless otherwise stated, al reagents, water, and solvents must be pesticide grade or
equivalent
7.1 Sample Preparation and Analysis Reagents
7.1.1 pH Adjustment and Acid and Base Partitioning
7.1.1.1 Potassium Hydroxide—Dissolve 20 g of pesticide grade (if
available) KOH in 100 mL reagent water.
7.1.1.2 Sulfuric Acid—Pesticide grade (if available; specific gravity
1.84).
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7.1.1.3 Hydrochloric Acid—Pesticide grade (if available), 6N.
7.1.1.4 Sodium Chloride—Pesticide grade (if available), prepare at 5
percent (w/v) solution in reagent water.
7.1.1.5 - Desiccant—EM Science silica gel Grade H Type IV Indicating
(6=16 mesh).
7.1.2 Solution Drying and Evaporation
7.1.2.1 Solution Drying—Sodium sulfate, pesticide grade (if available),
granular, anhydrous (Baker 3375, or equivalent), rinsed with
methylene chloride (20 mUg), baked at 400°C for 1 hour
minimum, cooled in a desiccator, and stored in a pre-cleaned
glass bottle with screw-cap that prevents moisture from entering.
If, after heating, the sodium sulfate develops a noticeable grayish
cast (due to the presence of carbon in the crystal matrix), that
batch of reagent is not suitable for use and should be discarded.
Extraction with methylene chloride (as opposed to simple
rinsing) and baking at a lower temperature may produce sodium
sulfate that is suitable for use.
7.1.2.2 Prepurified Nitrogen—99.9995% purity.
7.1.3 Extraction
Solvents—Acetone, n-hexane, methanol, methylene chloride, and nonane;
distilled in glass, pesticide quality, lot-certified to be free of interferences.
7.1.4 Extract Cleanup Adsorbents
7.1.4.1 Activated Silica Gel—100-200 mesh, Supelco 1 -3651 (or
equivalent), rinsed with methanol and methylene chloride, then
extracted with methylene chloride for 3 hours, baked at 45°C for
a half hour, then increased to 140-150°C for a minimum of 1
hour, cooled in a desiccator at room temperature, and stored in a
precleaned glass bottle with screw-cap that prevents moisture
from entering.
7.1.4.2 Acid Silica Gel (30 percent w/w)—Thoroughly mix 15 mL of
concentrated sulfuric acid with 35 g of activated silica gel in a
clean container. B-eak up aggregates with a starring rod until a
uniform mixture is obtained. Store in a screw-capped bottle with
fluoropolymer-Hned cap.
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7.1.4.3 Basic Silica Gel—Thoroughly mix 17 mL of IN sodium
hydroxide with 35 g of activated silica gel in a clean container.
Break up aggregates with a stirring rod until a uniform mixture is
obtained. Store in a screw-capped bottle with, fh: -re-
" lined cap.
7.1.4.4 Carbopak C—(Supelco 1-0258, or equivalent), and Celite 545—
(Supelco 2-0199, or equivalent). Thoroughly mix 18 g Carbopak
C and 18 g Celite 545 to produce a 50 percent w/w mixture.
Activate the mixture at 130°C far a minimum of 6 hours. Store
in a desiccator.
Standard Solutions
Standards purchased as solutions or mixtures with certification to their purity,
concentration, and authenticity, or prepared from materials of known purity and
composition. If the chemical purity is 98 percent or greater, the weight may be
used without correction to compute the concentration of the standard. Standards
should be stored in the dark in a freezer at sO°C in screw-capped vials with
fluoropolymer-lined caps when not being used. A mark is placed on the vial at the
level of the solution so that solvent loss by evaporation can be detected. If solvent
loss has occurred, or the shelf life has expired, the solution should be replaced.
7.2.1 Stock Standard Solutions
7.2.1.1 Prepared in nonane per the steps below or purchase as dilute
solutions (Cambridge Isotope Laboratories (CIL, Wobum, MA,
or equivalent). Observe the safety precautions in Section 5.
7.2.1.2 An appropriate amount of assayed reference material is dissolved
in solvent. For example, weigh 1 to 2 mg of PCB 126 to three
significant figures in a 10-mL ground-glass-stoppered volumetric
flask and fill to the mark with nonane. After the PCB is
completely dissolved, transfer the solution to a clean 15-mL vial
with fluoropolymer-lined cap.
7.2.1.3 Stock standard solutions should be checked for signs of
degradation prior to the prqjaration of calibration or performance
test standards. Reference standards that can be used to determine
the accuracy of calibration standards are available from several
vendors.
7.2.2 Precision and Recovery (PAR) Stock Solution
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Using the solutions in Section 7.2.1, prepare the PAR stock solution to
contain the PCBs of interest at the concentrations shown in Table 3.
When diluted, the solution will become the PAR spiking solution
(Section 12.1).
7.2.3 Internal Standard Solutions
7.2.3.1 Internal Standard Stock Solution
From stock standard solutions, or from purchased mixtures,
prepare this solution to contain the labeled internal standards in
nonane at the stock solution concentrations shown in Table 3.
This solution is diluted with methylene chloride prior to use
(Section 7.2.3.2).
7.2.3.2 Internal Standard Spiking Solution
Dilute a sufficient volume of the labeled compound solution
(Section 7.2.3.1) by a factor of 500 with acetone to prepare a
diluted spiking solution. Concentrations may be adjusted to
compensate for background levels. Each sample requires 1.0 mL
of the diluted solution.
7.2.4 Surrogate Standard Spiking Solution
7.2.4.1 Prepare labeled PCBs 81 and 111 in acetone at the levels shown
in Table 3.
7.2.4.2 The solution functions as a cleanup standard for the front half;
and is added to the filter/front half extract prior to cleanup to
measure the efficiency of the cleanup process.
7.2.4.3 Surrogate standards are not added to the XAD-2/back half
extract prior to cleanup, since labeled PCB 81 and 111 are spiked
onto the XAD-2 resin prior to shipment of the XAD-2 module
into the field (Section 9.1.2).
7.2.4.4 The efficiency of the cleanup process for the XAD-2/back half
extract can be measured by the recoveries of the internal
standards.
7.2.5 Recovery Standard(s) Spiking Solution
Prepare the recovery standard spiking solution to contain labeled PCBs 52,
101,138, and 178 in nonane at the level shown in Table 3.
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7.2.6 Calibration Standards (CS1 through CSS)
7.2.6.1 Combine the solutions in Sections 7.2.1 to product the five
calibration solutions shown in Table 4 in nonane,
72.6.2 - Calibration standards may also be purchased already prepared in
nonane (CD-).
72.6.3 The prepared solutions permit the relative response (labeled to
native) to be measured as a function of concentration. The CS3
standard is used for calibration verification (VER).
7.2.7 Precision and Recovery (FAR) Spiking Solution
7.2.7.1 Used for preparation of laboratory spike QC samples (Section
9.2.4).
72.72 Dilute 200 pL of the PAR stock solution (Section 7.2.2) to 10
mL with acetone. Each laboratory spike QC sample requires 1.0
mL.
7.2.8 GC Retention Time Window Defining and Isomer Specificity Test
Solution
7.2.8.1 This solution is used to define the beginning and ending retention
times for the PCB congeners and to demonstrate isomer
specificity of the GC columns.
7.2.8.2 The solution must contain the compounds listed in Table 8 (CEL.
or equivalent), at a minimum.
7.2.9 QC Check Sample
If available, a QC check sample should be obtained from a source
independent of the calibration standards. Ideally, this check sample
should be a certified standard reference material (SRM) containing the
PCBs in known concentrations in a sample matrix similar to the matrix
being analyzed.
7.2.10 Solution Stability
7.2.10.1 Standard solutions used for quantitative purposes (Section 7.2.6)
should be analyzed periodically, and should be assayed against
reference standards before further use.
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7.2.10.2 If the analysis yields standard concentrations that are not within
25% of the true value for any PCS, the solutions will be replaced
with solutions that, when analyzed, yield concentrations that are
within 25% of the true value.
SAMPLE COLLECTION, PRESERVATION, AND STORAGE
8.1 Sample Collection
Emission samples to be analyzed for toxic PCBs by this method are collected
according to EPA Modified Method 5 (MM5) procedures, or equivalent. Sample
collection procedures are fully described in EPA Method 0010, and are not
reproduced in this analytical method. The following sample fractions are
generated using MM5 sampling procedures and provided to the laboratory for
PCB determination:
Front Half Sample Fractions
• Particulate Filter (Container No. 1)
• Front Half Acetone/Methylene Chloride Reagent Rinses (Container No. 2)
Back Half Sample Fractions
• XAD-2 Module (Container No. 3)
• Back Half Acetone/Methylene Chloride Reagent Rinses (Container No. 4)
• Impingers Water Contents (Container No. 5)
• Impingers Acetone/Methylene Chloride Reagent Rinses (Container No. 6)
8.2 Storage
Solvent, filter, and XAD-2 sample fractions should be stored at the laboratory in
the dark at s4°C. Aqueous sample fractions should be stored at the laboratory in
the dark at 4°C to prevent freezing.
8.3 Holding Times
All samples must be extracted within 30 days of collection and analyzed within 45
days of extraction.
QUALITY CONTROL
9.1 Sampling Quality Assurance/Quality Control
The positive identification and quantification of PCBs in stationary source
emissions are highly dependent on the integrity of the samples received and the
precision and accuracy of the analytical procedures employed. The QA
15
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procedures described in this section are to be used to monitor the performance of
the sampling methods, identify problems, and effect solutions.
9.1.1 Field, Reagent, and Method Blanks
Field, reagent, and method blanks are collected to monitor the possibility
of contamination from train components, field reagents, glassware, and
shipment procedures.
9.1.2 XAD-2 Resin Pre-Spiked Surrogate Standards
Standards are pre-spiked onto each XAD-2 resin module prior to shipment
to the field. The XAD-2 resin pre-spiking procedure is described in
Appendix A of this method. The spiking compounds should be the stable,
isotopically labeled analog of the compounds of interest, or a compound
that will exhibit properties similar to the compounds of interest. Surrogate
standards function to monitor sampling efficiency and possible compound
breakthrough during sampling.
Analytical Method Quality Assurance/Quality Control
The minimum requirements of this method consist of spiking samples with
labeled compounds to evaluate and document analyte recovery, and preparation
and analysis of QC samples including blanks and duplicates. Laboratory
performance is compared to established performance criteria to determine if the
results of analyses meet the performance requirements of the method.
9.2.1 Laoeled Compounds
The laboratory shall spike all samples with the labeled standard spiking
solution (Sections 7.2.3.2 and 7.2.4) to assess method performance on the
sample matrix. Recovery of labeled standards from samples should be
assessed and records should be maintained.
9.2.1.1 Analyze each sample according to the procedures in Section 11.
Compute the percent recovery of the labeled standards (Section
12.2.3).
9.2.1.2 The recovery of each labeled compound will be compared with
the targeted limits in Table 5. If the recovery of any compound
falls outside of these limits the date will be flagged and impact
on reported concentration will be discussed in the reported
results.
16
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9.2.2 Laboratory Method Blanks
9.2.2.1 Prepare, extract, clean up, and concentrate a laboratory method
blank with each sample batch (samples of the same matrix started
-through the extraction process on the same 12-hour shift, to a
" mavimnffl of 20 samples). A laboratory method blank will
consist of clean XAD-2 resin, two particulate filters, and all
solvents/reagents in the approximate volumes normally received
from the field.
9.2.2.2 If any native PCB (Table 1) is found in the blank at greater than
20 percent of the concentration level found in the sample, the
reported data should be flagged as potentially containing some
contribution from laboratory procedures.
9.2.3 QC Check Sample
If available, analyze a QC check sample (Section 7.2.9) periodically to
assure the accuracy of calibration standards and the overall reliability of
the analytical process. It is suggested that the QC check sample be
analyzed at least quarterly.
9.2.4 Laboratory Spike Samples
9.2.4.1 With each sample batch, duplicate XAD traps not sent to the
field are spiked with PAR spiking solution (Section 7.2.7) and
processed through the same extraction, cleanup, and analysis
procedures as the field samples.
9.2.4.2 Calculate precision for the duplicate laboratory spike samples as
the relative percent difference (RPD). The RPD should be *30
percent
9.2.4.3 Calculate accuracy for the laboratory spike samples by
determining the percent recovery of spiked analytes. Accuracy
should be within 70-130 percent for analytes spiked 5 times the
background level of the train blank.
9.2.4.4 Any results outside of the above criteria will be flagged and the
impact on reported concentrations discussed in the reported
results.
9.2.5 The front half and back half fractions are processed and analyzed as
separate extracts. This approach enhances QA/QC by enabling the analyst
17
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to pinpoint possible contamination and analyte losses to either the font cr
back half fractions of the sampling train.
9.2.6 The specifications contained in this method can be n.ct If *1: -rr-
used is calibrated properly and then maintained in a calibrated state.
9.2.6.1 "* The standards used for calibration (Section 10), calibration
verification (Section 10.3.2), and for laboratory spike samples
(Section 9.2.4) should be identical, so that the most precise
results will be obtained.
9.2.62 A HRGC/HRMS instrument will provide the most reproducible
results if dedicated to the settings and conditions required for the
analyses ofPCBs by this method.
10.1 Operating Conditions
Establish the operating conditions necessary to meet the minimum retention times
~~ for the internal and recovery standards in Table 2.
10.1.1 Suggested HRGC Operating Conditions
Temperature program; 150 to 200°C at 10°C/min; 200 to 280°C at
NOTE: All portions of the column that connect the HRGC to the ion
source shall remain at or above the interface temperature specified above
during analysis to preclude condensation of less volatile compounds.
The HRGC conditions may be optimized for compound separation and
sensitivity. Once optimized, the same HRGC conditions must be used for
the analysis of all standards, blanks, and samples.
10.0 HRGC/HRMS CALIBRATION
Injector temperature:
Interface temperature:
Initial temperature:
Initial time:
290°C
290°C
150°C
2 min
29C/tnin
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10.12 High Resolution Mass Spectrometer (HRMS) Resolution
10.1.2.1 Obtain a selected ion current profile (SICP) of each analyte
listed in Table 3 at the two exact m/z's specified in Table 6 and
-" at * 10,000 resolving power by injecting an authentic standard
" of the PCBs either singly or as part of a mixture in which there
is no interference between closely eluted components.
10.1.2.2 The analysis time for PCBs may exceed the long-term mass
stability of the mass spectrometer. Because the instrument is
operated in the high-resolution mode, mass drifts of a few ppm
(e.g., 5 ppm in mass) can have serious adverse effects on
instrument performance. Therefore, a mass-drill correction is
mandatory and a lock-mass m/z from PFK is used for drift
correction. The lock-mass m/z is dependent on the exact m/z's
monitored within each descriptor, as shown in Table 6. The
level of PFK metered into the HRMS during analyses should
be adjusted so that the amplitude of the most intense selected
lock-mass m/z signal (regardless of the descriptor number)
does not exceed 10 percent of the full-scale deflection for a
given set of detector parameters. Under those conditions,
sensitivity changes that might occur during the analysis can be
more effectively monitored.
NOTE: Excessive PFK (or any other reference substance) may
cause noise problems and contamination of the ion source
necessitating increased frequency of source cleaning.
10.1.2.3 If the HRMS has the capability to monitor resolution during the
analysis, it is acceptable to terminate the analysis when the
resolution falls below 10,000 to save reanalysis time.
10.1.2.4 Using -a PFK molecular leak, tune the instrument to meet the
minimum required resolving power of 10,000 (10 percent
valley) at m/z 380.9760. For each descriptor (Table 6),
monitor and record the resolution and exact m/z's of three to
five reference peaks covering the mass range of the descriptor.
The resolution must be greater than or equal to 10,000, and the
deviation between the exact m/z and the theoretical m/z
(Table 6) for each exact m/z monitored must be less than
5 ppm.
10.1.3 Ion Abundance Ratios, Minimum Levels, Signal-to-Noise Ratios, and
Absolute Retention Times
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10.1.3.1 Choose an injection volume of either 1- or 2-uL, consistent
with the capability of the HRGC/HRMS instrument. Inject a 1-
or 2-pL aliquot of the CS1 calibration solution (Table 4) using
the GC conditions from Section 10.1.1.
10.1.3.2 Measure tie SICP areas for each analyte, and compute the ion
abundance ratios at the exact m/z's specified in Table 6.
Compare the computed ratio to the theoretical ratio given in
Table 7.
The exact m/z's to be monitored in each descriptor are shown m
Table 6. Each group or descriptor shall be monitored in succes-
sion as a function of GC retention time to ensure that all of the
toxic PCBs are detected. Additional m/z's may be monitored in
each descriptor, and the m/z's may be divided among more than
the descriptors listed in Table 6, provided that the laboratory is
able to monitor the m/z's of all the PCBs that may elute from
the GC in a given retention-time window.
The mass spectrometer shall be operated in a mass-drift
correction mode, using PFK to provide lock m/z's. The lock
mass for each group of m/z's is shown in Table 6. Each lock
mass shall be monitored and shall not vary by more than ±20
percent throughout its respective retention time window.
Variations of the lock mass by more than 20 percent indicate
the presence of coelutmg interferences that may significantly
reduce the sensitivity of the mass spectrometer. Reinjection of
another aliquot of the sample extract will not resolve the
problem. Additional cleanup of the extract may be required to
remove the interferences.
10.1.3.3 All PCBs and labeled compounds in the CS1 standard shall be
within the QC limits in Table 7 for their respective ion
abundance ratios; otherwise, the mass spectrometer shall be
adjusted and this test repeated until the mJz ratios fall within
the limits specified. If die adjustment alters the resolution of
the mass spectrometer, resolution shall be verified (Section
10.12) prior to repeat of the test
10.1.3.4 The peaks representing the PCBs and labeled compounds in the
CS1 calibration standard must have signal-to-noise ratios (S/N)
greater than or equal to 10.0. Otherwise, the mass spectrometer
shall be adjusted and this test repeated until the peaks have S/N
greater than or equal to 10.0.
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10.1,3.5 Retention Time Windows—Analyze the window defining
mixture (Section 7.2.8) using the optimized temperature
program in Section 10.1.1. Table 2 gives the elution order
(first/last) of the window-defining compounds.
10.1.4 Isomer Specificity
10.1.4.1 Analyze the isomer specificity test standard (Section 7.2.8)
using the procedure in Section 11.11 and the optimized
conditions for sample analysis (Section 10.1.1).
10.1.4.2 Compute the percent valley between the GC peaks for PCB
123 and PCB 118, and between the GC peaks for PCB 156 and
157.
10.1.4.3 Verily that the height of the valley between these closely eluted
isomers is less than 25 percent. If the valley exceeds 25
percent, adjust the analytical conditions and repeat the test or
replace the GC column and recalibrate.
10.2 Initial Calibration
10.2.1 Prepare a calibration curve encompassing the concentration range for
each compound to be determined. Referring to Table 2, calculate the
relative response factors for unlabeled target analytes (RFJ relative to
their appropriate internal standard (Table 5) and the relative response
factors for the nC12-labeled internal standards (RFj,) using the four
recovery standards (Table 5) according to the following formulae:
(aJ+aJ)* q,
np _ (Aj, +Aa)x Q„
* (Aj + An3) X Qu
where;
A J and A* «¦ sum of the integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for unlabeled PCBs,
A J and A* - sum of the integrated ion abundances of the quantitation ions (Tables 2,3 and
6) for the labeled internal standards,
A and A* ™ sum of the integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for the recovery standard,
Q„ « quantity of the internal standard injected (pg),
Q„ - quantity of the recovery standard injected (pg), and
Q„ « quantity of the unlabeled PCB analyte injected (pg).
RF, and the RFH are dimensionless quantities; the units used to express Qv Q„ and Q,
must be the same.
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10.2.2 Calculate the mean relative response factors and their respective percen'
relative standard deviation (%RSD) for the five calibration solutions. If
the mean relative response factors between the an^yt:;n;t 7
RSD, the instrument must be re-calibrated.
MJFn —
J~1
RF„0)
where n represents a particular PCB congener (n -= 1 to 13; Table 3), and j is the
injection or calibration solution number; (j« 1 to 5).
t ^
h0)
RF> -
where is represents a particular PCB internal standard (is = 14 to 23; Table 3), and j is
fee injection or calibration solution number; (j - 1 to 5).
10.3 Operation Verification
At the beginning of each 12-hour shift during which analyses are performed,
HRGC/HRMS system performance and calibration are verified for all native
PCBs and labeled compounds. For these tests, analysis of the CS3 calibration
verification (VER) standard (Section 7.2.6 and Table 4) and the isomer specificity
test solution (Section 7.2.8 and Table 8) shall be used to verify all performance
criteria. Adjustment and/or recalibration (Section 10) shall be performed until all
performance criteria are met Only after all performance criteria are met may
samples and blanks be analyzed.
10.3.1 HRMS Resolution
A static resolving power of at least 10,000 (10 percent valley definition)
must be demonstrated at the appropriate m/z before any analysis is
performed. Static resolving power checks must be performed at the
beginning and at the end of each analysis batch according to procedures
in Section 10.1.2. Corrective actions must be implemented whenever the
resolving power does not meet the requirement
10.3.2 Calibration Verification
10.3.2.1 Inject the VER standard using the procedure in Section 11.11.
22
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10.3.2.2 The m/z abundance ratios for all PCBs shall be within the
limits in Table 7; otherwise, the mass spectrometer shall be
adjusted until the m/z abundance ratios fall within the limits
specified, and the verification test shall be repeated. If the
" adjustment alters the resolution of the mass spectrometer, reso-
lution shall be verified (Section 10.1.2) prior to repeat of the
verification test.
10.3.2.3 The peaks representing each native PCB and labeled compound
in the VER standard must be present with a S/N of at least 10;
otherwise, the mass spectrometer shall be adjusted and the
verification test repeated.
10.3.2.4 Calculate the relative response factors (RF) for unlabeled target
analytes [RF(n); n = 1 to 13 from Table 3] relative to their
appropriate internal standards (Table 2), and the RFb for the
13C12-labeled internal standards [RP(U); is = 14-23] relative to
the recovery standards (Table 2) using the equations shown in
Section 10.2.1.
For each compound, compare the relative response factor with
those generated in the initial calibration. Relative response
factors should be within 35 percent of initial calibration results
for 70% of the analytes for the calibration to be verified. Once
verified, analysis of standards and sample extracts may
proceed. If, however, fewer than 70% of the response factors
are within the 35% limit, the measurement system is not
performing properly for those compounds. In this event,
prepare a fresh calibration standard or correct the problem
causing the failure and repeat the resolution (Section 10.3.1)
and calibration verification (Section 10.3.2) tests, or recalibrate
(Section 10). Per the analyst's discretion, results may also be
reported for these analytes using the average calibration
verification response factors bracketing the samples rather than
the mean response factor generated in the initial calibration. If
this option is chosen, data reported using an average calibration
verification response factor should be flagged and discussed in
the final report
10.3.3 Retention Times
The absolute retention times of the GC/MS internal standards in the
calibration verification shall be within ±15 seconds of the retention times
obtained during initial calibration.
23
10.3.2.5
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10.3 .4 HRGC Resolution
10.3.4.1 Inject the GC retention time window defining and isomer
specificity test solution (Section 7.2.8).
10.3.4.2 The valley height between PCBs 123 and 118 at m/z 325.8804
shall not exceed 25 percent, and the valley height bet* een
PCBs 156 and 157 shall not exceed 25 percent at m/z
359.8415 on the GC columns.
10.3.4.3 If the absolute retention time of any compound is not within
the limits specified or if the congeners are not resolve.i, the GC
is not performing properly. In this event, adjust the GC and
repeat the calibration verification test or recalibrate, or replace
the GC column and either verify calibration or recalibrate.
10.4 Data Storage
MS data shall be collected, recorded, and stored.
10.4.1 Data Acquisition
The signal at each exact m/z shall be collected repetitively throughout the
monitoring period and stored on a mass storage device.
10.4.2 Response Factors and Multipoint Calibrations
The data system shall be used to record and maintain lists of response
factors and multipoint calibration curves. Computations of relative
standard deviation (coefficient of variation) shall be used to test
calibration linearity.
11.0 PROCEDURE
The analyst will receive the following six analytical fractions for each sample collected in the
field:
Front Half Sample Fractions
• Particulate Filter (Container No. 1)
• Front Half Acetone/Methylene Chloride Reagent Rinses (Container No. 2)
Back Half Sample Fractions
• XAD-2 Module (Container No. 3)
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• Back Half Acetone/Methylene Chloride Reagent Rinses (Container No. 4)
• Impingers Water Contents (Container No. 5)
• Impingers Acetone/Methylene Chloride Reagent Rinses (Container No. 6)
The fractions corresponding to the front half of the sampling train, which are the particulate filter
(Container No. 1) and the front half rinses (Container No. 2), will be extracted, combined, and
cleaned for analysis using HRGC/HRMS.
The fractions corresponding to the back half of the sampling train, which are the XAD-2 resin
module (Container No. 3), back half rinses (Container No. 4), and the impingers water and rinses
(Containers Nos. 5 and 6, respectively) will be extracted, combined, and cleaned for a separate
analysis using HRGC/HRMS.
11.1 Front Half Sample Extraction
The front half consists of the particulate filter and the front half rinses. The front
half rinses are filtered to remove any particulate; the filter is combined with the
particulate filter (Container No. 1), and both extracted together using the Soxhlet
technique.
11.1.1 Front Half Acetone/Methylene Chloride Rinses (Container No. 2)
11.1.1.1 The front half rinse (Container No. 2) may contain particulate
material which has been removed from the probe. To separate
particulate matter from the front half rinse, filter the front half
rinse. To avoid introducing any contamination, use the same
type of filter which has been used in the sampling train, from
the same lot as the filter in the train. Pour the front half rinse
through the filter then rinse Container No. 2 three times with
10-mL aliquots of methylene chloride, and filter the methylene
chloride rinses.
11.1.1.2 With the filtrate, proceed to Section 11.2 for water removal.
11.1.1.3 With the filter, proceed to Section 11.1.2.2 for Soxhlet
extraction.
1J .1.2 Particulate Matter Filter (Container No. 1)
11.1.2.1 Using clean forceps, place 10 boiling chips into the bottom of
the round bottom flask of the Soxhlet extractor and connect the
Soxhlet extractor to the mind bottom flask.
25
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11.1.2.2 Using clean forceps, place the filter containing the particulate
from Section 11.1.1.3 into a glass thimble, or place the falter on
a plug of pre-clean glass wool.
11.1.2.3." Using clean forceps, place the particulate matter filter
- (Container No. 1) into the glass thimble or on the plug of pre-
cleaned glass wool from Section 11.1.2.2.
11.1.2.4 Using a clean syringe or volumetric pipet, add a 1-mL aliquot
of the internal standard spiking solution to the filter. If a
laboratory spike sample is being prepared (Section 9.2.4), the
PAR spiking solution will be added at this time. Add 1 raL of
spiking solution uniformly onto the particulate-coated surface
of the filter in the extractor by spotting small volumes at
multiple filter locations, using a syringe. Repeat the spiking
process with matrix spike solution, if these solutions are being
used. Place a piece of pre-cleaned glass wool on top of the
spiked filter in the extractor to keep the filters in place. Rinse
the filter container three times with methylene chloride and add
the rinses to the Soxhlet extractor.
11.1.2.5 Slowly add methylene chloride to the Soxhlet extractor
containing the two filters through the Soxhlet (with condenser
removed), allowing the Soxhlet to cycle. Add sufficient
solvent to fill the round bottom flask approximately more than
half lull and submerge the filters.
11.1.2.6 Place a heating mantle under the round bottom flask and
connect the upper joint of the Soxhlet to a condenser, making
sure that the coolant is flowing through the condenser.
11.1.2.7 Allow the sample to extract for, at least, 12 hours but not more
than 24 hours, adjusting the mantle temperature for cycling
(flushing solvent from the Soxhlet into the round bottom flask)
approximately once every 30 minutes.
11.1.2.8 After cooling, disconnect the extractor from the condenser.
Tilt the Soxhlet slightly until the remaining solvent has drained
into the round bottom flask.
11.1.2.9 Transfer the extract from the round bottom flask into a clean
500-mL amber glass bottle with PTFE-lined screw cap. Rinse
the round bottom flask three times with approximately 10-mL
aliquots of methylene chloride and transfer the rinses to the
26
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amber bottle. Store the filter extract at sO°C until the
preparation of the filtered front half rinse has been completed.
11.1.2.10 Archive the extracted filters at s4°C until the GC/HRMS
• analysis is completed.
11.2 Front Half Sample Water Removal
Water is removed from the front half rinses and the particulate filter extract using
sodium sulfate. During the drying procedure, the extracts are combined into a
Kudema-Danish setup.
11.2.1 Front Half Acetone/Methylene Chloride Rinses Filtrate (See Section
11.1.1.2)
11.2.1.1 Because the front half rinse sample consists of a mixture of
acetone and methylene chloride and the rinse may also contain
water, the water needs to be removed from the organic solvent
before combining with the filter extract. Add 20 g of sodium
sulfate (NajS04) to the rinse and allow to set for 10 minutes.
11.2.1.2 Using a clean pair of forceps, place a small portion of
precleaned glass wool in the bottom of a glass funnel and pour
a 2.45-m (1-in.) layer of Na^O* on top of the glass wool.
11.2.1.3 Rinse the Na^O, contained in the funnel three times with
methylene chloride; discard the rinses. Support the funnel in a
ring of clamp above the receiving container to pi event tipping.
11.2.1.4 Place the funnel into a clean KD concentrator, consisting of a
20 mL concentrator tube connected to a 500 mL evaporative
flask.. Slowly pour the extract from the dried front half rinse
through the NajSO^ Rinse the container containing the
extract/Na2S04 three times, using approximately 10 mL of
methylene chloride each time. Add rinses to the funnel. Rinse
the Na^O, with approximately 5 mL of methylene chloride to
complete the transfer.
NOTE: During this process, monitor the condition ofNajS04
to determine that the bed ofNajSC^ is not solidifying and
exceeding its drying capacity. If the Na^C^ bed can be stirred
and is rt?11 frep-flnwina, effective moisture removal from the
extracts is occurring. If the NajSO, bed is solidified, repeat
Steps 11.2.1.110 11.2.1.3 to make a new drying funnel, and
continue drying the extracts.
27
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11.2.1.5 If the volume of the extract is greater than 500 mL, collect :be
remaining dried sample extract into a clean amber bottle for
subsequent concentration using the same K-D setup.
11.2.1.6' Reduce the volume of the extract to <10 mL following the
~ procedures described in Section 11.3.
11.2.2 Particulate Filter Extract (See Section 11.1.2.9)
11.2.2.1 Prepare a NajSC^ drying funnel, as described in Sections
11.2.1.2 and 11.2.1.3.
11.2.2.2 Place the funnel exit into the same 500 mL evaporative flask
described in Section 11.2.1.4. Slowly pour the extract from
tie dried front half rinse through the NajSO.,. Rinse the
container containing the extract/Na^C^ three times, using
approximately 10 mL of methylene chloride each time. Add
rinses to the funnel. Rinse the Na^C^ with approximately
5 mL of methylene chloride to complete the transfer.
Note; Monitor the condition of the NajSO,, as noted in Section
11.2.1.4.
11.2.2.3 If the volume of the extract is greater than 500 mL, follow the
procedures in Sections 11.2.1.5 and 11.2.1.6.
11.2.2.4 Proceed to Section 11.3.
11.3 Fiont Half Combined Filter Extract and Front Half Rinse Sample Reduction
The combined particulate filter extract and front half rinse sample is reduced in
volume using a macro and micro Kudema-Danish (K-D) apparatus, and half cf the
total extract is archived. The other half of the total extract is cleaned according to
the procedures described in Section 11.4.
11.3.1 Using a clean pair of forceps, place five boiling chips into the
concentrator tube. Attach a three-ball macro Snyder column to the K-D
concentrator with clips or springs. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top. Attach the solvent vapor
recovery glassware (condenser and collection device) to the Snyder
column of the K-D apparatus. Place the K-D apparatus on a hot water
bath (70-75 °C) to remove methylene chloride; then to 80-85 °C to
remove acetone. Adjust the vertical position of the apparatus and the
water temperature as required to complete the concentration in 20 to 30
minutes. Rinse sides of the K-D apparatus during concentration with a
28
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small volume of methylene chloride. When the apparent volume of the
liquid reaches 6-8 mL, remove the K-D apparatus from the water bath and
allow the apparatus to cool and drain for at least 5 minutes If the volume
of extract to be concentrated is greater than 500 mL, repeat the
concentration as many times as required using the same 500-mL
evaporative flask and systematically add remaining extract (allow to cool
slightly before addition of more extract). If repeated concentrations are
performed, add two new boiling chips each time.
NOTE: Never let the extract in the concentrator tube go to dryness even
though additional solvent is present in the upper portion of the K-D
apparatus.
11.3.2 Remove the Snyder column and evaporative flask. With a clean pair of
forceps, add two new boiling chips to the concentrator tube. Attach a
micro Snyder column to the concentrator tube. Attach the solvent vapor
recovery glassware (condenser and collection device) to the Snyder
column of the K-D apparatus. Prewet the Snyder column with about 0.5
mL of methylene chloride. Place the K-D apparatus on the hot water bath
so that the concentrator tube is partially immersed in the hot watert while
supporting the tube with a clamp or by gloved hands. When the apparent
volume of the liquid reaches 4-5 mL, remove the K-D apparatus from the
water bath and allow the apparatus to cool and drain for at least
5 minutes. If the volume is greater than 10 mL, add a new boiling chip to
the concentrator tube, prewet the Snyder column, and concentrate again
on the hot water bath, Remove any moisture from the outside of the
concentrator tube.
11.3.3 Transfer the extract to a calibrated vial or a volumetric flask, rinse
concentrator tube with a minimum volume of methylene chloride and add
rinses to the vial, and add methylene chloride, if necessary, to attain a
final volume of 10 mL.
11.3.4 Transfer 5.0 mL of the extract to a 10-mL glass storage vial with a PTFE-
lined screw cap. Label the extract as "Archived Extract of Front Half'
store at <0°C. Mark the liquid level on the vial with a permanent marker
to monitor solvent evaporation during storage.
11.3.5 Place the remaining 5,0 mL of the extract through the sample cleanup
procedure described in Section 11.4.
11 a F-nnt Half Combined Extract Cleanup
The un-archived portion of the front half extract is cleaned using acid and base
partitioning, and silica gel and carbon column chromatography.
29
N-33
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11.4.1 Acid and Base Partitioning
11.4.1.1 Prior to acid and base partitioning, concentrate the extract to i
mL using K-D evaporation, then add 5 mL ofhexane and
/ concentrate to 2 mL using K-D evaporation. Dilute the extract
- with 50 mL ofhexane and transfer to a clean separatory funnel.
Spike a known amount (1 mL) of the surrogate standard
spiking solution (Section 7.2.4) into the filter/front half extract
11.4.1.2 Partition the extract against 50 mL of sulfuric acid (Section
7.1.1). Shake for two minutes with periodic venting into a
hood. Remove and discard the aqueous layer. Repeat the acid
washing until no color is visible in the aqueous layer, using up
to a maximum of four washings.
11.4.13 Partition the extract against 50 mL of 5 percent NaCl solution
(Section 7.1.1) in the same way as with the acid. Discard the
aqueous layer.
11.4.1.4 Partition the extract against 50 mL of potassium hydroxide
solution (Section 7.1.1) in the same way as with the acid.
Repeat the base washing until no color is visible in the aqueous
layer, using uptoa maximum of four washings. Minimize
contact time between the extract and the base to prevent
degradation of the PCBs.
11.4.1.5 Repeat the partitioning against the NaCl solution two more
times, each time discarding the aqueous layer.
11.4.1.6 Pour the extract through a drying column containing 7 to 10 cm
of granular anhydrous sodium sulfate (Section 7.1,2.1). Rinse
the separatory funnel with 30 to 50 mL ofhexane, and pour
through the drying column. Collect the extract in a round-
bottom flask. Concentrate the hexane extract to a volume of
4 mL for silica gel cleanup using either rotary evaporation,
Kudema-Danish apparatus, or Turbovap apparatus (Sections
11.4.1.6.1 and 11.4.1.6.3), then proceed to Section 11.4.2.
11.4.1.6.1 Rotaiy Evaporation
Note: Improper use of the rotary evaporator may
result in contamination of the sample extract(s).
Concentrate the extract in a round-bottom flask.
Assemble the rotaiy evaporator according to
30
N-34
-------
manufacturer's instructions, and warm the water
bath to 450 C. On a daily basis, preclean the
rotary evaporator by concentrating 100 mL of
clean extraction solvent through the system.
Archive both the concentrated solvent and the
solvent in the catch flask for a contamination
check if necessary. Between samples, use three 2-
to 3-mL aliquots of solvent to rinse the feed tube
between samples. Collect rinse in a waste beaker.
Attach the round-bottom flask containing the
sample extract to the rotary evaporator. Slowly
apply Vacuum to the system, and begin rotating
the sample flask. Lower the flask into the water
bath, and adjust the speed of rotation and the
temperature as required to complete concentration
in 15 to 20 minutes. At the proper rate of
concentration, the flow of solvent into the
receiving flask must be steady, with no bumping
or visible boiling of the extract occurring.
NOTE: If the rate of concentration is too fast,
analyte loss may occur.
When the liquid in the concentration flask has
reached an apparent volume of approximately
2 mL, remove the flask from the water bath and
stop the rotation. Slowly and carefully admit air
into the system. Be sure not to open the valve so
quickly that the sample is blown out of the flask.
Rinse the feed tube with approximately 2 mL of
solvent.
Kuderna-Danish (K-D) Evaporation—Described
in Sections 11.3.1 - 11.3.2.
Turbovap Evaporation—Concentrate the extracts
in separate 250-mL Turbotubes. The Turbovap
technique is used for solvents such as methylene
chloride and n-hexane.
11.4.2.1 Place a glass-wool plug in a 15-mm ID chromatography
column (Section 6.4.3.2). Pack the column bottom to top with
31
11.4.1.6.2
11.4.1.6.3
Silica Gel Cleanup
N-35
-------
1 g silica gel (Section 7.1.4.1), 4 g basic silica gel (Section
7.1.4.3), 1 g silica gel, 8 g acid silica gel (Section 7.1.4.2j, 2 g
silica gel, and 4 g granular anhydrous sodium sulfate (^Section
7.1.2.1). Tap the column to settle the adsorb0"*?
11.4.2.2 Pre-elute the column with 20 to 30 mL of n-hexane. Discard
theeluate. Check the column for channeling. If channeling is
present, discard the column and prepare another.
11.4.2.3 Apply the concentrated extract (4 mL) to the column. Open the
stopcock until the extract is within 1 mm of the sodium sulfate.
Rinse the receiver three times with 4-mL portions of n-hexane,
and apply separately to the column. Elute the PCB isomers
with 75 mL of n-hexane and collect the eluate.
11.4.2.4 Concentrate the eluate to 1 mL per Section 11.3.2, then proceed
to carbon column cleanup (Section 11.4.3).
11.4.3 Carbon Column
11.4.3.1 Cut both ends from a 25-mL disposable serological pipet
(Section 6.4.2.2) to produce a 20-cm column. Fire-polish both
ends and flare both ends if desired. Insert a glass-wool plug at
one end, and pack the column with 3.6 g of Carbopak/Celite
(Section 7.1.4.4) to form an adsorbent bed. Insert a glass-wool
plug on top of the bed to hold the adsorbent in place.
11.4.3.2 Pre-elute the column with 20 mL each in succession of toluene,
methylene chloride and n-hexane. When the solvent is within 1
mm of the column packing, apply the n-hexane sample extract
to the column. Rinse the sample container twice with 1 -mL
portions of n-hexane and apply separately to the column. Apph
2 mL of n-hexane to complete the transfer.
11.4.3.3 Elute the column with 25 mL of n-hexane and collect the
eluate. This fraction will contain the mono- and di-ortho PCBs.
11.4.3.4 Elute the column with 15 mL of methanol; collect and archive
this fraction. This fraction contains potential interferents. If
the recovery of labeled compounds is very low, this fraction
can be analyzed in order to potentially ascertain where losses
occurred.
11.4.3.5 Elute the column with 15 mL of toluene; collect the eluate.
32
W-Qfi
-------
11.4.3.6 Filter the combined hexane and toluene fractions if evidence of
carbon particles from the chromatography column is seen.
11.4.3.7 Concentrate the hexane and toluene fractions to a final volume
. of 1 mL using rotary, KD» and/or Turbovap (Section 11.4.1.6)
evaporation techniques.
11.5 Front Half Combined Sample Concentration to Final Volume
The extract is concentrated to final volume, and the recovery standards are added.
11.5.1 The extract is concentrated in a calibrated micro tube to a final volume of
20 /iL to 1 mL, per the analyst's discretion, under a gentle stream of
nitrogen.
11.5.2 Add 10 |iL of the appropriate recovery standard solution (Section 7.2.5)
to the sample extract.
11.5.3 Proceed to Section 11.11 for HRGC/HRMS analysis.
11.6 Back Half Sample Extraction
The back half consists of the XAD-2 module, the back half and impinger
acetone/methylene chloride rinses, and the impinger water. The XAD-2 module
is extracted using the Soxhlet technique, and the impinger water may be extracted
using the solid phase extraction (SPE) technique. ITie back half and impinger
acetone/methylene chloride rinses are not extracted, but combined during the
drying process in Section 11.7.
11.6.1 XAD-2 Module (Container No. 3)
11.6.1.1 Using clean forceps, place 10 boiling chips in the bottom of the
round flask of the Soxhlet extractor and connect the Soxhlet
extractor to the round bottom flask.
11.6.1.2 Place a piece of pre-cleaned glass wool in the bottom and the
side-arm of the Soxhlet extractor. Transfer the XAD-2 resin
directly to the Soxhlet extractor and place on the top of the
glass wool To remove the XAD-2 resin from the sampling
module, remove the glass wool from the end of the XAD-2
sampling module, and place this glass wool in the extractor. If
the XAD-2 resin is wet and difficult to transfer, follow the
procedure described in Section 7.4.2.2 of Method 3542. Rinse
the ground glass stoppers with methylene chloride and add the
rinse to the round bottom flask of the Soxhlet extractor. After
33
N-37
-------
transferring the XAD-2 resin to the extractor, rinse the XAD-?.
module thoroughly into the extractor using a teflon wash bottle
containing methylene chloride.
* NOTE: Under no circumstances should methanol or acetone
be used to transfer the XAD-2 resin.
11.6.1.3 With the XAD-2 resin in the Soxhlet extractor and glass wool
on top of the XAD-2 resin, use a clean syringe or volumetric
pipet to add a 1-mL aliquot of the internal standard spiking
solution (Section 1232) to the XAD-2 resin. Be sure thai the
needle of the syringe penetrates the XAD-2 resin bed to a depth
of at least 1.27 cm (0.5 in.). If a laboratory QC sample is being
prepared (Section 9.2.4), the XAD-2 resin should be spiked
with the PAR spiking solution at this time.
11.6.1.4 Pour approximately 300-400 mL of methylene chloride through
the XAD-2 bed so that the round bottom flask is approximately
half-full and the XAD-2 bed is covered.
11.6.1.5 Place a heating mantle under the round bottom flask and
connect the upper joint of the Soxhlet extractor to a condenser.
NOTE: Start the extraction process immediately after spiking
is completed to ensure that no volatilization of organic
compounds from the resin or any spiking solutions occurs
before the extraction process is started.
11.6.1.6 Allow the sample to extract for at least 16 hours but not more
than 24 hours, cycling once every 25-30 minutes.
NOTE: Be sure that cooling water for the condensers is cola
and circulating. Watch the extractor through two or three
cycles to ensure that the extractor is working properly.
11.6.1.7 After the Soxhlet extractor has been cooled., disconnect the
extractor from the condenser and tilt the extractor slightly until
the remaining solvent in the Soxhlet has drained into the round
bottom flask.
11.6.1.8 Inspect the contents of the round bottom flask to determine
whether there is a visible water layer on top of the methylene
chloride.
34
N-38
-------
11.6.1.8.1 If no water layer is observed, transfer the extract
through a clean filter into a 500-mL amber glass
bottle with PTFE-lined screw cap for subsequent
combination with the back-half rinse.
11.6.1.8.2 If a water layer is observed in the Soxhlet round
bottom flask, transfer the contents to a separately
funnel through a clean filter, rinsing the round
bottom flask three times with methylene chloride
and adding the rinsings to the separatory funnel.
Drain the methylene chloride from the separatory
funnel and store in a clean amber glass bottle.
Extract the aqueous layer using a C,g SPE column,
as described in Section 11.6.3.
11.6.1.9 Archive the extracted XAD-2 resin at <4°C until the
HRGC/HRMS analysis is completed.
11.6.1.10 Proceed to Section 11.7.1 for water removal.
11.6.2 Back Half Acetone/Methylene Chloride Rinses (Container No. 4) and
Impinger Acetone/Methylene Chloride Rinses (Container No. 6)
The back half solvent rinses (Container No. 4) and the impinger solvent
rinses (Container No. 6) are not extracted, but are combined during the
water removal process, described in Section 11.7.2.
11.6.3 Impinger Water Contents (Container No. 5)
11.6.3.1 Extract the impinger water using solid phase extraction (SPE).
Prepare the SPE cartridge by placing the SPE cartridge in a
vacuum manifold. Condition the cartridge with 15-mL aliquots
of methylene chloride, methanol, and deionized water. Do not
allow the cartridge to go dry from this point until the extraction
is completed.
11.6.32 Allow the aqueous sample to equilibrate for approximately 30
minutes to settle the suspended particles, if present. Allow the
sample to be pulled through the SPE cartridge. Adjust the
vacuum to complete the extraction in no less than 15 minutes.
An additional SPE cartridge may be used if clogging prevents
sufficient sample throughput.
35
N-39
-------
Before all of the sample has been pulled through the cartridge,
add approximately 20 mL of reagent water to 5-e s.vr.pV bcule.
swirl to suspend die solids (if present), and pour into the
second reservoir. Pull the remaining sample through the SPE
, cartridge. Use additional reagent HPLC w«ii11til mi
solids are removed.
Before all of the sample and rinses have been pulled through
the cartridge, rinse the sides of the reservoir with small portions
of reagent HPLC water. Dry the cartridges under vacuum for 2
hours.
11.6.3.3 Release the vacuum, remove the reservoir from the vacuum
manifold, and discard the extracted aqueous solution. Insert a
clean vial for eluant collection into the manifold. Each vial
should have sufficient capacity to contain the total volume of
the elution solvent (approximately 12 mL) and should fit
around the drip tip. The drip tip should protrude into the vial to
preclude loss of sample from spattering when vacuum is
applied. Reassemble the vacuum manifold.
11.6.3.4 Wet each cartridge with 6 mL of acetone. Allow the solvent to
soak the C„ beads 15-20 seconds. Pull all of the solvent
through the cartridges into the vials. Wet each cartridge with
6 mL of methylene chloride. Allow the solvent to soak the C18
beads 15-20 seconds. Pull all of the solvent through the
cartridge into the vial.
Release the vacuum, remove the vial containing the sample
solution. Add 10 g of NagS04 to the extract; allow the extract
to set for 10 minutes; then filter the extract.
11.6.3.5 Proceed to Section 11.7.2 for back half water removal..
11.7 Back Half Sample Water Removal
Water is removed from the XAD-2 extract, the back half and impinger solvent
rinses, and the impinger water extract using sodium sulfate. During the drying
procedure, the extracts are combined into a Kudema-Danish setup.
11.7.1 XAD-2 Extract (See Section 11.6.1,10)
11.7.1.1 Prepare a NajSC^ funnel, as described in Sections 11.2,1.2-
11.2.1.3.
36
N-40
-------
11.7.1.2 Place the funnel exit into a clean KD concentrator consisting of
a 20 mL concentrator tube connected to a 500 mL evaporative
flask. Slowly pour the XAD-2 extract through the NajS04.
Rinse the container containing the extract/NajSC^ three times,
. - using approximately 10 mL of methylene chloride each time.
„ Add rinses to the funnel. Rinse the NajSO* with approximately
5 mL of methylene chloride to complete the transfer.
Note: Monitor the condition of the NajSC^ as noted in Section
11.2.1,4.
11.7.1.3 Reduce volume of extract to <10 mL, following the K-D
concentration procedures described in Sections 11.3.1 and
11.3.2.
11.7.2 Back Half and Impinger Solvent Rinses, and Impinger Water Combined
Extract
11.7.2.1 Prepare a Na^C^ funnel, as described in Sections 11.2.12-
• 11.2.1.3.
11.7.2.2 Place the funnel into the same 500 mL evaporative flask
described in Section 11.7.1.2.
11.7.2.3 Slowly pour the impinger water extract (Section 11.6.3.5)
through the Na2SO
-------
11.7.2.5 If the volume of the extract is greater than 500 mL, follow the
procedures described in Sections 11.2.1.5 and ii.2.1.5.
11.7.2.6 Proceed to Section 11.8 for back half sample concentration,
*
11.8 Back Half Combined XAD-2 Extract, Back Half and Impinger Solvent Rinses,
and Impinger Water Extract Sample Reduction.
The combined XAD-2 extract, back half and impinger rinses, and impinger water
extract sample is reduced in volume using macro and micro Kudema-Danish (K-
D) apparatus, and hal f of the total extract is archived. The other half of the total
extract is cleaned according to the procedures described in Section 11.9.
11.8.1 Follow the concentration procedures described in Sections 11.3.1 and
11.32.
11.8.2 Transfer the combined, concentrated extract to a calibrated vial or a
volumetric flask, rinse the concentrator tube with a minimum volume cf
methylene chloride and add rinses to the vial, and add methylene
chloride, if necessary, to attain a final volume oflO mL,
11.8.3 Transfer 5.0 mL of the extract to a 10-mL glass storage vial with a PTFE-
lined screw cap. Label the extract as "Archived Extract of Back Half',
store at <0°C. Mark the liquid level on the vial with a permanent marker
to monitor solvent evaporation during storage.
11.8.4 Place the remaining 5.0 mL of the extract through the sample cleanup
procedure described in Section 11.9.
11.9 Back Half Combined Sample Cleanup
The un-archived portion of the back half extract is cleaned using acid and base
partitioning, and silica gel and carbon column chromatography.
11.9.1 Acid and Base Partitioning (see Section 11.4.1)
11.9.2 Silica Gel Column Chromatography (follow procedure described in
Section 11.4.2)
11.9.3 Carbon Column Chromatography (follow procedure described in Section
11.4.3)
11.10 Back Half Combined Sample Concentration to Final Volume
The extract is concentrated to final volume, and the recovery standards are added.
38
N-42
-------
11.10.1 The extract is concentrated in a calibrated microtube to a final volume of
20 fuL to 1 mL, per the analyst's discretion, under a gentle stream of
nitrogen.
11.10.2 Add iO p.L of the appropriate recovery standard solution (Section 7.2.5)
to the sample extract.
11.10.3 Proceed to Section 11.11 for HRGC/HRMS analysis.
11.11 HRGC/HRMS Sample Analysis
The operation of the HRGC/HRMS instrumentation is verified, and the separate
front half and back half extracts are analyzed.
11.11.1 Establish the operating conditions given in Section 10.1, perform initial
calibration if necessary (Section 10.2), or verily calibration (Section
10.3).
11.11.2 If an extract is to be reanalyzed and evaporation has occurred, do not add
more recovery standard solution. Rather, bring the extract back to its
previous volume (e.g., 19 jiL, or 18 jiL if 2 jiL injections are used) with
pure nonane.
11.11.3 Inject 1.0 or 2.0 jj.L of the concentrated extract containing the recoveiy
standard solution, using on-column or splitless injection. The volume
injected must be identical to the volume used for calibration (Section
10.1.3.1). Start the HRGC column initial isothermal hold upon
injection. Start HRMS data collection after the solvent peak elutes.
Stop data collection after the 13CI2-PCB 209 has eluted. Return the
column to the initial temperature for analysis of the next extract or
standard.
12.0 DATA ANALYSIS AND CALCULATIONS
12.1" Qualitative Determination
APCB or labeled compound is identified in a standard, blank, or sample when all
of the criteria in Sections 12.1.1 through 12.1.4 are met. If the criteria for
identification in Sections 12.1.1-12.1.4 are not met, the PCB analyte has not been
positively identified. If interferences preclude identification, an estimated
maximum possible concc^t—tlc,;: can reported (Section !?.? 6), cr
options for further cleanup can be explored depending on specific project
requirements.
39
N-43
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12.1.1 The signals for the two exact m/z's in Table 6 must be present and must
maximize within the same two seconds.
12.1.2 The signal-to-noise ratio (S/N) for the GC peak at each exact m/z must
be greater than or equal to 2.5 for each PCB analyte detected m a sampie
extract and greater than or equal to 10 for all PCB analytes in the
calibration standard (Section 7.2.6).
12.1.3 The ratio of the integrated areas of the two exact m/z's specified in
Table 6 must be within the limit in Table 7, or within ±10 percent of the
ratio in the midpoint (CS3) calibration or calibration verification (VER),
whichever is most recent.
12.1.4 The relative retention time of the peak for a toxic PCB analyte must be
within ±15 seconds of the retention times obtained during calibration.
12.2 - Quantitative Determination
12.2.1 For gas chromatographic peaks that have met the criteria outlined in
Section 12.1, calculate the concentration of the PCB compounds in the
extract, using the formula:
c . ^13"
x 4, xRFHxWs
where:
C, «* concentration of unlabeled PCS congeners in the front half or back
half extract (pg/dscm),
Ax m sum of the integrated ion abundances of the quantitation ions (Tobies
2,3 and 6) for unlabeled PCBs,
A„ - sum of the integrated ion abundances of the quantitation ions (Tables
2, 3 and 6) for the labeled internal standards,
Q„ « quantity, in pg, of the internal standard added to the sample before
extraction,
RF, - calculated mean relative response factorfor the analyte ( RF„ with n=l
to 13; Section 103.1),
W, - volume of air sampled (dscm),
12.2.2 Concentration in Emission Sample
The total concentration of a native PCB analyte in an emission sample is
computed by summing the concentration of the front half and the back
half, as follows:
40
N-44
-------
Concentration in emission sample (pgfdsan) - Cfi *
=¦ Concentration of the compound in the front half (pg/dacm), calculated per Section 12.2.1,
- Concentration of the compound in ike bade half (pgfdscm), calculated per Section 12.2 J.
12.2.3 Calculate the percent recovery of the internal standards measured in the
sample extract, using the formula:
Percent recovery = —~x 100
where:
A„
A„
e*
e»
RF.
Calculate the percent recovery of the cleanup standard similarly. The
percent recovery should meet the criteria shown in Table 5. If recoveries
are outside the limits of Table 5, the data should be flagged and the
impact on reported results discussed in the final report.
12.2.4 Outside Calibration Range
12.2.4.1 If the SICP area at either quantitation m/z for any compound
exceeds the calibration range of the system, the extract must be
diluted and re-analyzed.
12.2.4.2 Dilute the sample extract by a factor of 10, adjust the
concentration of the recovery standard to 100 pg/fiL in the
extract, and analyze an aliquot of this diluted extract
sum of the integrated ion abundances of the quantitation ions (Tables
2,3 and 6) for the labeled internal standard,
sum of the integrated ion abundances of the quantitation ions (Tables
2,3 and 6) for the labeled recovery standard,
quantity, in pg, of the internal standard added to the sample before
extraction,
quantity, in pg, of the recovery standard added to the cleaned-up
sample residue before HRGC/HRMS analysis, and
calculated mean relative response factor for the labeled internal
standard relative to the appropriate recovery standard This represents
the mean obtained in Section 10.2.2 (RFb with is -14 to 23, Table 3).
41
N-45
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12.2.5
Estimated Detection Limit (EDL)
2.5 (Hls+ H2S) (QiK)
EJ>L s n
(HJ^ H2k) (RF„) (Ws)
where:
El, and H2, m heights of the noise where the primary and secondary m/z's for
the PCSs would elute,
Hl„andH2b " heights of the response of the primary and secondary m/z*s for
the internal standard,
AndQ„
RFj, and W, are as described in Section 12.2.1.
12.2.6 Estimated Maximum Possible Concentration (EMPC)
When the response of a signal having the same retention time as a toxic
PCB congener has a S/N in excess of 2.5 but does not meet all of the
other qualitative identification criteria listed in Section 12.1 calculate the
Estimated Maximum Possible Concentration (EMPC). EMPC is
calculated using the expressions in Section 12.2.1, except that A, should
represent the sum of the area under the smaller peak and of the other
peak area calculated using the theoretical chlorine isotope ratio. The
value shall be noted as EMPC and the results reported.
12.2.7 Reporting Units and Levels
Results are reported to three significant figures for the PCBs and labeled
compounds found in all standards, blanks, and samples.
12.2.7.1 Air Emission Samples—Analytical results are reported ir
pg/FH or BH fraction, and are not to be corrected for field,
reagent, or laboratory method blanks.
12.2.7.2 Train or Proof Blanks—Results are reported in pg/FH or BH
fraction, and are not to be corrected for field, reagent, or
laboratory method blanks.
12.2.7.3 Dilutions (Section 12.2.4.2)
Results for PCBs in samples feat have been diluted: for this
EPA project, both the undiluted and diluted PCB results are to
be reported, whether or not all of the analytes are within the
calibration range.
42
N-46
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12.2.7.4 Non-Detects
Note the non-detected PCBs as ND and report the estimated
. detection limit established during the analysis.
13.0 METHOD PERFORMANCE
13.1 In a limited single laboratory demonstration of this method using simulated
emission samples, estimated detection limits of approximately 75 pg/sample were
achieved for pentachlorinated biphenyl (PeCB); 5 pg/sample for hexachlorinated
biphenyl (HxCB); and 25 pg/sample for heptachlorinated biphenyl (HpCB).
13.2 Interlaboratory testing of this method to determine overall precision and bias has
not been performed.
14.0 POLLUTION PREVENTION
This method uses solid phase extraction (SPE) techniques for the extraction of PCBs
from liquid matrices. SPE uses much less solvent, than traditional liquid-liquid
extraction techniques.
15.0 WASTE MANAGEMENT
PCB waste should be disposed of according to Toxic Substances Control Act (TSCA)
guidelines 40CFR 700-789, and hazardous waste should be disposed of according to
Resource Conservation and Recovery Act (RCRA) guidelines 40CFR 260-269.
16.0 REFERENCES
1. "Modified Method 5 Sampling Train," U.S. EPA Method 0010, Rev. 0, September, 1986.
2. Syhre, M„ Hanschmann, G, and Heber, K J of AOACInter., Vol. 81, No. 3,513- 517
(1998).
3. "Toxic Polychlorinated Biphenyls by Isotope Dilution High Resolution Gas
Chromatography/High Resolution Mass Spectrometry," U.S. EPA Method 1668, March,
iyyy.
43
N-47
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4. Obana, H, Kikuchi, IL, Okihashi, M., and Shinjiro, H. Analyst, Vol. 122,217-220
(1997).
5. Loos, R., Vollmuth, S.» and Niessner, R. Fres. J. Anal. Chem, 357(8), 1081 -1087 (1997).
6. Ferrario, J., Byrne, C., and Dupuy, A.B. Jr. Organohalogen Compounds (Dioxin "96),
123-127 (1996).
7. ''Determination ofPolychlorinated Dibenzo-p-dioxin (PCDD), Polychlorinated
Dibenzofuran (PCDF), and Polychlorinated Biphenyl Emissions from Stationary
Sources," State of California Air Resources Board Method 428, September, 1990.
8. AMborg, U.G., Becking, G.C., Bimbaum, L.S., Brouwer, A, Derks, H.J.G.M., feeley,
M., Golor, G., Hanberg, A, Larsen, J.C., Liem, A.K.D., Safe, S.H., Schlatter, C., Waern,
F., Younes, M., and Yxjanheikki, Chemosphere, Vol. 28, No. 6,1049-1067 (1994).
9. Strandell, M.E., Lexen, KLM., deWIt, CA., Jaemberg, U.G., Jansson, B., Kjeller, L-O.,
Kulp, S-E., Ljung, K., Soederstroem, G., et al. Organohalogen Compounds (Dioxin '94),
363-366 (1994)
10. Ramos, L., Blanch, G.P., Hernandez, L., Gonzalez, M.J., J. Chromatography A, Vol 690,
243-249(1994).
11. Fitzgerald, E.F., Hwang, S A., Brix, K., Bush, B., and Cook, K., Organohalogen
Compounds (Dioxin'94), 495-500 (1994).
12. Lazzari, L., Spemi, L., Salizzaio, M., and Pavoni, B., Chemosphere, Vol. 38, No. 8,
1925-1935 (1999).
13. Sewart, A., Harrad, S.J., McLachlan, M.S., McGrath, S.P., and Jones, K.C.,
Chemosphere, Vol. 30, 51-67 (1995).
14. " Dupont, G., Delteil, C., Camel, V., and Bermond, A, Analyst, Vol. 124, 453-458, (1999).
15. "Standard Guide for General Planning of Waste Sampling," ASTM D 4687,48-55,
(1995).
16. "Extraction of Semivolatile Analytes Collected Using Method 0010 (Modified Method 5
Sampling Train),*' U.S. EPA Method 3542, Rev. 0, December, 1996.
M-AJS
-------
17.0 TABLES AND FIGURES
Table 1. Toxic Polychlorinated Biphenyls Determined by High Resolution Gas
Chromatography (HRGC)/High Resolution Mass Spectrometry (HRMS)
Native compound IUPAC
PCB'
CAS Registry No,
No.1
Target Analytes
3,3\4,4'-7CB
32598-13-3
77
-2,3,3',4,4-PeCB
32598-14-4
105
2,3,4,4',5-PeCB
74472-37-0
114
2,3',4,4',5-PeCB
31508-00-6
118
2',3,4,4',5-PeCB
65510-44-3
123
3,3',4,4',5-PeCB
57465-28-8
126
2,3,3',4,4',5-HxCB
38380-08-4
156
2,3t3,,4,4',5'-HxCB
69782-90-7
157
2,3',4,4,,5^,-HxCB
52663-72-6
167
3,3',4,4',5,5-HxCB
32774-16-6
169
2,2',3,3',4,4',5-HpCB
35065-30-6
170
2,2,J3,4,4'J5,5 '-HpCB
35065-29-3
180
2,3,3',4,4,,5,5'-HpCB
39635-31-9
"189
Internal Standards
3,3',4,4'-TCB
160901-67-7
77L
2.3,3',4,4-PeCB
160901-70-2
105L
2,3,4,4',5-PeCB
160901-72-4
114L
2,3',4,4',5-PeCB
160901-73-5
118L
2',3,4,4',5-PeCB
160901-74-6
123L
3,3',4,4',5-PeCB
160901-75-7
126L
2,3,3',4,4',5-HxCB
160901-77-9
156L
2,3,3',414',5'-HxCB
160901-78-0
157L
2,3',4,4',5,5,-HxCB
161627-18-5
167L
3,J',4,4',5,5'-HxCB
160901-79-1
169L
2,2',3,3',4,4',5-HpCB
160901-80-4
170L
2,2',3,4,4',5,5 '-HpCB
160901-82-6
180L
2,3,3 ',4,4',5,5 '-HpCB
160901-83-7
189L
Surrogate Standards
l3Cu-3,4,4',5-TCB
160901-68-8
81
"Cu-2,3,3',5,5'-PeCB
160901-71-3
111
Recovery Standards
uCn-2,2',5,5'-TCB
160901-66-6
52
I3C12-2,2',4,4,5'-FeCB
160901-69-9
101
uCu-2^'>3,4>4,^,-HxCB
160901-76-8
138
uCn-2,2,,3,3',5,5\6-HpCB
160901-81-5
178
Final Eluter Standard
UCU-DCB
160901-84-8
209
' Polvrblnrmated biphenyls:
TCB = Tetrachlorobiphenyl
PcCB = Pentaehlorobiphenyl
HxCB = Hexachlorobiphenyl
HpCB = Heptachlorobiphenyl
DCB = Decachlorobiphenyl
1 Suffix "L" designates a labeled compound.
N-49
-------
Table 2.
Retention Time (RT) References, Quantitation References, and Retention Times
(RTs) for the Toxic PCBs
iuTAC
ItJrAC
Retention time and
No.1
PCB congener
No.1
quantitation reference
(min)
52L
13Cl2-2t2',5,5,-TCB
13012-2,2',5,5'-TCB
28.66
81L
13C12-3,4,4',5-TCB4
52L
13C12-2,2',5,5'-TCB
37.89
77L
13012-3,3',4,4'-tcb
52L
13C12-2,2',5,5,-TCB
38.85
77
33\4,4'-TCB
77L
13C12-3,3',4,4'-TCB
38.85
101L
13C12-2,2',4,5,5'-PeC3
—
13C12-2,2',4,5,5'-PeCB
35.02
111L
13C12-2,3,3 ',5,5'-PeOB4
101L
13C12-2,2',4,5,5'-PeCB
37.13
123 •
2',3,4,4',5-PeCB
118L
13C12-2,3',4,4',5-PeCB
39.90
118L
13C 12-2,3',4,4',5-PeCB
101L
13C12-2^',4,5,5'-PeCB
40.17
118
23',4,4',5-PeCB
118L
13C12-2,3',4,4'f5-PeCB
40.17
114
2,3,4,4',5-PeCB
105L
13012-2,3,3'A4'-PeCB
40.79
105L
13012-2,3,3'»4,4*-PeCB
101L
13C12-2,2',4,5,5'-PeCB
42.22
105
2,3,3,,4,4'-PeCB
105L
13C12-2,3,3',4,4'-PeCB
42.22
126L
13C12-3,3'J4)4',5-PeCB
101L
13C12-2,2',4,5,5,-PcCB
44.75
126
33'A4\5-PeCB
126L
13012-3,3', 4,4', 5-PeCB
44.75
138L
nC^^A^'-HxCB
_
13012-2^2',4,5,5'-PeCB
43.23
\6TL
13C12-2,3',4,4,,5,5'-HxCB
138L
13012-2^*3,4,4',S'-HxOB
45.72
167
23,A4*,5,5'-HxCB
167L -
13012-2,3»,4,4',5,5'-HxOB
45.72
156L
13C12-2,3,3 ',4,4',5 -HxCB
138L
13012-2^*3,4,4',5'-HxCB
47.37
157L
13C12-2,3,3,,4,4,,5,-HxCB
138L
13012-2,2',3,4,4',5'-HxCB
47.79
156
2,3,3 ',4,4',5 -HxCB
156L
13C12-2,3,3',4)4',5-HxCB
47.37
157
233\4,4',5'-HxCB
1571
13C12-2,3,3',4,4',5,-HxCB
47.79
169L
13C12-3,3',4,4',5,5-HxCB
138L
13012-2^2'3,4,4*,5'-HxCB
50.25
169
3,3'A4\5.5'-HxCB
169L
13012-33*,4,4',5,5'-HxCB
50.25
178L
13012-2,2',3,3',5,5',6-HpCB
—
13012-2,2',4,5,5'-PeCB
42.88
180L
13012-2,2',3 A4,5,5'-HpCB
178L
13012-2,2',3,3',5,5',6-HpCB
47.88
180
2,2',3,4,4',5,5'-HpCB
180L
13C12-2J2',3,4,4',5,5'-HpCB
47.88
170
2^',3,3',4,4',5-HpCB
180L
13C12-2r2',3,4,4',5,5'-HpCB
49.90
189L
13C12-2,3,3',4,4',5,5,-HpCB
178L
13012-2,2', 3,3', 5,5', 6-HpCB
52.56
189
2,3 3 ',4,4',5,5'-HpCB
189L
13 012-2,3,3' ,4,4',5,5'-HpCB
52.56
209L
13C12-DCR5
178L
13C12-2.2*.3.3'.S.5'6-Rt,CR
56.63
1 Suffix indicates labeled compound.
1 Retention time data are for HT-8 column (per manufacturer).
3 Absolute recovery standards.
4 Surrogate standard.
3 Final eluter.
46
N-50
-------
Table 3. Concentrations of Stock and Spiking Solutions Containing the Native PCBs and
Labeled Compounds
Stock1
Spiking
Spikixij
m/z
Solution2
Level
Cpd. No.
Compound
type
(ng/mL)
(ng/mL)
(ng)
Precision and Recovery
Standards'
1
3,3',4,4-TCB
77
20 .
0.8
0.8
2
2,3,3',4,4,-FeCB
105
1000
40
40
3
2,3,4,4',5-PeCB
114
1000
40
40
4
2,3',4,4',5-PeCB
118
1000
40
40
5
2',3,4,4',5-PeCB
123
1000
40
40
6
3,3',4,4',5-PeCB
126
100
4
4
7
2,3,3',4,4',5-HxCB
156
1000
40
40
S
233',4,4,,5,-HxCB
157
1000
40
40
9
2,3,,4,4,,5,5'-HxeB
167
1000
40
40
10
3,3',4,4',5,5-HxCB
169
200
8
8
11
2,2',3^',4,4',5-HpCB
170
200
8
8
12
2^',3»4,4,,5,5'-HpCB
180
1000
40
40
13
2,3,3'.4>4',5,5,-HpCB
189
200
8
8
-
Internal Standards4
14
13C12-3,3',4,4'-TCB
77L
1000
2
2
15
13C12-2,3,3',4,4'-PeCB
105L
1000
2
2
16
13C12-2,3',4,4'.5-PeCB
118L
1000
2
2
17
13 C12-3,3'»4,4',5-PeCB
126L
1000
2
2
18
13C12-2,3,3,,4,4,,5-HxCB
156L
1000
2
2
15
13C12-2,3,3'.4,4',5'-HxCB
157L
1000
2
2
20
13C12-2,3 ',4,4',5,5'-HxCB
, 167L
1000
2
2
21
13 C12-3,3 ',4,4',5,5-HxCB
169L
1000
2
2
22
13C12-2,2',3,4,4',5,5-HpCB
180L
1000
2
2
23
13C12-2,3,3'»4,4',5,5-HpCB
Surrogate/Cleanup Standards5
189L
1000
2
2
24
13C12-3,4,4\5-TCB
81L
200
1.0
1.0
25
13C12-2,3,3',5,5'-PeCB
Recovery Standards*
111L
1000
5.0
5.0
26
i3C12-2,2,,5,5'-TCB
52L
1000
200
2
27
13C12-2,2,,4,5,5,-PeCB
101L
1000
200
2
28
13C12-2T2',3,4,4',5-HxCB
138L
1000
200
2
29
13 C12-2,2',3,3',5,5',6-HpCB
Final Eluter
178L
1000
200
2
W
i^rn-TVB
*
8
1 Section 7.2.7-prepared in nonane and diluted to prepare spiking solution.
' 7 2.2.2, "*,2,4,, 72.5,7-2.7-prcparec" in acetone torn stock solution daily.
3 Section 7.2.1-prepared in nonane and diluted to prepare spiking solution. Concentrations are adjusted for
expected background levels.
* Eirion 7.2.3 2-prepared in acetone from stock solution daily. Concentrations are adjusted for expected
background levels.
5 Section 7.2.4-prepared in acetone; added to XAD-2 prior to shipment into the field; add to filter before cleanup.
4 Section 7.2.5-prepared in nonane; added to concentrated extract prior to injection.
47
N-51
-------
Table 4. Concentrations ofPCBs in Calibration and Calibration Verification Solutions
IUPAC CS1 CS2 CS31 CS4 CS5
No.1 (ng/mL) (ng/mL) (ig/ml ^ fxiff'rnT %
Precision and Recovery
Standards
3,3',4,4'-TCB
77
OS
2
10
40
200
23^',4,4,-PeCB
105
2.5
10
50
200
1000
2,3,4,4',5-PeCB
114
2.5
10
50
200
1000
2,3',4,4',5-PeCB
118
2.5
10
50
200
1000
2',3,4,4',5-PeCB
123
2.5
10
50
200
1000
33',4,4',5-PeCB
126
2.5
10
50
200
1000
23,3',4,4',5-HxCB
156
5
20
100
400
2000
233,,4,4',5'-HxCB
157
5
20
100
400
2000
2j3',4,4',5,5,-HxCB
167
5
20
100
400
2000
3,3',4,4',5,5'-HxCB
169
5
20
100
400
2000
2,2',3,3,,4,4,,5-HpCB
170
5
20
100
400
2000
2,2',3,4,4',5,5 '-HpCB
180
5
20
100
400
2000
2r3,3',4,4',5,5,-HpCB
189
5
20
100
400
2000
Internal Standards
13C\2-3,3'A,4'-TCB
77L
100
100
100
100
100
13C 12-2,3,3 ',4,4-PeCB
105L
100
100
100
100
100
13C12-2,3',4,4',5-PeCB
118L
100
100
100
100
100
13C12-3,3,,4,4,,5-PeCB
126L
100
100
100
100
100
13012-2,3,3',4,4',5-HxCB
156L
100
100
100
100
100
13C12-2,3,3',4,4',5'-HxCB
157L
100
100
100
100
100
13 C 12-2,3 ',4,4',5,5-HxCB
167L
100
100
100
100
100
13C12-3,3 ',4,4',5,5-HxCB
169L
100
100
100
100
100
13C12-2^',3,4,4',5,5,-HpCB
180L
100
100
100
100
100
13C12-2,3,3',4,4',5,5'-HpCB
189L
100
100
100
100
100
Surrogate Standards
13C12-3,4,4',5-TCB
81L
0.5
2
10
40
200
13C12-2,3,3',5,5'-PeCB
111L
2.5
10
50
200
1000
Recovery Standards
13C12-2^,5'-TCB
52L
100
100
100
100
100
13C12-2,2',4,5,5,-PeCB
101L
100
100
100
100
100
13C12-2^^,4,4,,5,-HxCB
138L
100
100
100
100
100
13C12-2,2',3,3',5,5',6-HpCB
178L
100
100
100
100
100
Final Eluter
nn?.nm
^200
?nn
700
?nn
1 Suffix "Ln indicates labeled compound.
2 Sections 72.6, calibration verification solution.
48
N-S2
-------
Table 5. Labeled Compound Target PCB Recoveries
,, _~ Labeled compound
Test recovery
IUPAC cone
Labeled PCB No. (ng/mL) (%)
Internal Standards
ocn^.v-TCB
77
100
30-150
30-150
13C12-2,3,3',4,4'-PeCB
105
100
30-150
30-150
13C12-23',4,4',5-PeCB
118
100
30-150
30-150
13C12-3.3,,4,4,,5-PeCB
126 '
100
30-150
30-150
13 C 12-2,3,3 ',4,4',5-HxCB
156
100
30-150
30-150
13C12-2,3,3',4>4',5,-HxCB
157
100
30-150
30-150
13C 12-2,3',4,4',5,5-HxCB
167
100
30-150
30-150
13C12-3,3,,4,4\5,5,-HxCB
169
100
30-150
30-150
13C12-2r2',3,4,4',5,5 '-HpCB
180
100
30-150
30-150
13C12-2,3,3',4,4',5,5'-HpCB
189
100
30-150
30-150
Surrogate Standards
13C12-3,4,4',5-TCB
81
50
5-75
10-150
13C12-2,3,3',5,5'-PeCB
111
250
50-325
20-130
1 Based on 20 final extract volume.
49
N-53
-------
Table 6. Descriptors, Exact m/z's, m/z Types, and Elemental Compositions of the PCBs
Exact m/z
Descriptor mb? type Elemental composition Subsianca'
289.9224
M
C12 H6 35C14
291.9194
• M+2
C12 H6 35C13 37C1
TCB
301.9626
•M
13C12 H6 35C14
TCBJ
303.9597
M+2
13C12 H6 35C13 37C1
TCBJ
318.9792
Lock Mass
PFK
325.8804
M+2
C12 H5 35C14 37C1
PeCB
327.8775
M+4
C12 H5 35C13 37C12
PeCB
330.9793
Lock Mass Check
—
PFK
337.9207
M+2
13C12 H5 35C14 37C1
PeCB'
339.9178
M+4
13C12 H5 35C13 37C12
PeCB1
325.8804
M+2
C12 H5 35C14 37C1
PeCB
327.8775
M+4
C12 H5 35C13 37C12
PeCB
337.9207
M+2
13C12 H5 35C14 37C1
PeCB1
339.9178
M+4
13C12 H5 35C13 37G2
PeCBJ
354.9792
Lock Mass
_
PFK
354.9792
Lock Mass Check
—
PFK
393.8025
M+2
C12 H3 35C16 37CI
HpCB
395.7996
M+4
C12 H3 35C15 37C12
HpCB
405.8428
M+2
13C12 H3 35C16 37C1
HpCBJ
407.8398
M+4
13C12 H3 "35C15 37C12
HpCB'
359.8415
M+2
C12 H4 35C15 37C1
HxCB
361.8385
M+4
C12 H4 35Q4 37C12
HxCB
371.8817
M+2
13C12 H4 35C15 37C1
HxCB'
373.8788
M+4
13C12 H4 35C14 37C12
HxCB*'
380.9760
Lock Mass
—
PFK
380.9760
Lock Mass Check
PFK
393.8025
M+2
C12 H3 35C16 37C1
HpCB
395.7996
M+4
C12 H3 35Q5 37C12
HpCB
405.8428
M+2
13C12 H3 35C16 37C1
HpCB"
407.8398
M+4
13C12 H3 35C15 37C12
HpCB''
504.9696
Lock Mass
•M,
PFK
504.9696
Lock Mass Check
—
PFK
509.7229
M+4
13C12 35C18 37C12
DCB'
511.7199
M+€
13C12 35C17 37C13
DCBJ
1 Nuclidic masses used were:
H« 1.007825 C» 12.00000
13C - 13.003355 35CI- 34.968853 37C1 - 36.965903
2 TCB * Tetrachlorobiphenyl
PeCB = Pentachlorobiphenyl
HxCB » Hexachlorobiphenyl
HpCB» Heptachlorobiphenyl
DCB * Detachlorobiphenyl.
3 13C labeled compound.
50
N-54
-------
Table 7. Theoretical Ion Abundance Ratios and QC Limits
Chlorine
atoms
m/z's forming
ratio
Theoretical
ratio
QC limit1
Lower
Upper
4
M/(M+2)
0.77
0.65
0.89
5
(M+2)/(M+4)
1.55
1.32
1.78
6
(M+2)/(M+4)
1.24
1.05
1.43
7
(M+2)/(M+4)
1.05
0.88
1.20
10
(M+4)/(M+6)
1.17
0.99
135
1 QC limits represent +/-15 percent windows around the theoretical ion abundance ratio. These limits
are preliminary.
51
N-5*
-------
Table 8. GC Retention Time Window Defining Solution and Congener Specificity
Test Standard1 (Section 7.2.8)
Congener
group . • First elated Last eluted
TCB 54 2r2',6,6' 77 2,3'AA'
PeCB 104 2,2',4,6,6' 126 , 3,3',4,4\5
HxCB 155 2^,4,4',6,6' .169 3,3',4,4',5,5'
HpCB 188 2^'3,4,,5,6,6' 189 2,3,3\4,4',5,5
Resolution test componnds
123 2^,4,4',5-PeCB 156 233',4,4',5-HxCB
118 2,3',4,4',5-PeCB 157 2,3,3',4,4',5'-HxCB
1 All compounds are at a concentration of 100 ng/mL in nonane.
52
KJ.RP
-------
Appendix A
Recommended XAD-2 Resin Cleaning and Pre-Spiking Procedures
A-l
N-57
-------
1 r
5mL for
Archive
5 mLfbr
Cleanup
Soxhlet Extract
with CH,CI,
Concentrate
to 10 mL
Remove Moisture
with Na,SO,
Split Combined Extract
into Two Portions
Combine CH2CI2
Extract with
Front Half Rinse
Repeat
Drying Process
If Needed
Dry Filtrate
with
Na,SO
Spike with
Internal Standard
Solution
Filter, Add Filter to
Particulate
Filter
Particulate
Fitter
(Container 1}
CHzCI?'Aretone
Front Half Rinse
Figure 1. Sample Extraction Procedure for Stationary Source Emission Sample
(Front Half Sample Fraction)
N-58
-------
5 mLfor
Cleanup
Remove Moisture
with Na2S04
Concentrate to
10 mL
Split Combined Extract
into Two Portions
Combine CH2CI2 Extract
and Rinses
Extract
Water
Sample
with
C1S-SPE
Repeat
Drying
Process
If Needed
Impinger
Contents
(Container 5)
CHjClj/Acetone
Back Half Rinse
(Container 4)
Spike with
Internal Standard
Solution
XAD-2
(Container 3)
Soxhlet Extract
with CHjClj
If Water is Present
In XAD-2 Extract,
Extract Water Layer
with C18-SPE
Figure 1. (Continued - Back Half Sample Fraction)
54
N-59
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Silica Ge!
Cleanup
* The surrogate standard solution
is not added to the XAD-2 back half rinse
extract because these surrogates are used
in pre-sampllng spike of XAD-2.
Extract
Cleanup
Concentrate
PCS Fraction
Carbon Column
Cleanup
Add Recovery
Standard Solution
Solvent Exchange
Into Hexane
Spike Surrogate
Standard Solution'
Extract Hexane Extract
with Sulfuric Acid
Discard the
Aqueous Layer
Discard the
Aqueous Layer
Discard the
Aqueous Layer
Discard the
Aqueous Layer
Wash the Hexane
Layer with
NaCI Solution
Dry
Extract with
Na,S04
Extract the Hexane
with
KOH Solution
Wash the Hexane
Layer with NaCI
Solution
Figure 2. Extract Cleanup Procedure
55
N-5C
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XAD-2 Resin Cleaning Procedure
Pre-cleaned XAD-2 resin (Supelco) is extracted in methylene chloride for at least 24 hours and
dried using high-purity nitrogen. The extraction procedure is performed in a large Soxhlet
extractor, which will contain approximately 100 g of Amberlite XAD-2. Multiple Soxhlet
extraction setups may be employed, depending upon the number of XAD-2 traps needed. The
resin must be carefully retained between two glass wool plugs inside the Soxhlet extractor,
because it floats on methylene chloride. The XAD-2 resin is dried by placing the extracted
resin (-200 g) in a Pyrex column (10 cm x 40 cm). The drying column has sufficient space for
fluidi ring the XAD-2 bed, while generating a minimum resin load at the exit of the column.
The nitrogen was purified by passing it through a charcoal trap between the nitrogen cylinder
(size 1A) and the column. The rate of nitrogen flow (ca 40 L/min) through the column should
be set to agitate the bed gently to remove the residual solvent.
Storage of Clean XAD-2 Resin
XAD-2 resin cleaned and dried as prescribed above is suitable for immediate use in the field,
provided it passes the QC contamination check described below. However, precleaned dry
XAD-2 resin may develop unacceptable levels of contamination if stored for periods exceeding
one month. If precleaned XAD-2 resin is not to be used immediately, it should be stored in a
clean jar that is sealed with Teflon tape. An aliquot shall then be taken for the QC
contamination check for determining the background levels of target analytes.
If the stored resin fails the QC check, it may be recleaned by repeating the methylene chloride
extraction described above. The QC contamination check shall be repeated after the resin is
recleaned and dried.
QC Contamination Check of XAD-2 Resin
The XAD-2 resin shall be subjected to a QC check to confirm the absence of any contaminants
that might cauie interferences in the subsequent analysis of field samples. An aliquot of resin,
equivalent in size (-40 g) to one XAD-2 module charge, shall be used to check a single batch
of resin for its quality control.
Hie XAD-2 resin aliquot shall be subjected to the same extraction, concentration, cleanup, and
analytical procedures as those applied to the field samples. The quantitative criteria for
acceptable resin quality will depend on the detection limit criteria established for the field
sampling and analysis program.
Resin which yields a background or blank value equal to or greater than that corresponding to
me leveis oi concern for the analyte(s) shall be rejected for field use. Note that the acceptance
limit for resin cleanliness depends not only on the inherent detection limit of the analysis
A-2
N-61
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method but also on the expected field sample volume and on the desired limit of detection in
the sampled stream.
Pre-Sampling Surrogate Spike
Prepare the Surrogate Spike .solution as described in Section 7.2.4 of this method. The XAD-2
sampling module (trap) has sealed ball and socket joints and is wrapped in pre-muffled
aluminum foil and bubble wrap. The technician must wear clean cotton or nylon gloves prior
to opening the sealed joints. The teflon tape and clamp on the exit end are removed, and the
trap carefully unwrapped. The foil is then placed on a clean, stable flat surface with the clean
side, the inner surface, facing up. The trap is placed on the foil with the open end toward the
technician.
The technician must prerinse a syringe six to eight times with methylene chloride. The syringe
volume should be as close as possible to the volume of spiking solution to be added. The
syringe is then placed on the clean foil alongside the trap. The clean syringe is then used to
withdraw 1 mL of the surrogate spike solution. The needle is positioned at the center of the
glass wool plug and inserted through the glass wool and into approximately one centimeter of
the XAD-2 resin- The needle should be in the resin, not between the resin and glass wall. The
syringe contents are injected and the syringe withdrawn. The trap is then sealed and placed in
sO°C for storage. The syringe is rinsed again several times with dichloromethane to clean the
spiking solution from it. The gloves are discarded and a fresh pair is used for spiking the
Second or next trap. The spiked traps will then be packed with dry ice and sent to the field for
sampling.
The date of spiking, identity of the XAD-2 module, identity and volume of the spiking solution
used, and the name of the technician who performed the spiking are recorded in the study
laboratory record book.
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Appendix B
Recommended Procedure for Cleaning the Particulate Filter
B-l
N-63
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Recommended Procedure For Cleaning the Filter
Prior to use in the field, each lot of filters shall be subjected to precleaning and a quality
control or contaminantion check to confirm that there are no contaminants present that will
interfere with the analysis qf selected species at the target detection limits.
Filters will be precleaned by placing in a muffle oven at >400°C for 1245 hours. As a QC
check, a filter will be extracted, and subjected to the same concentration, clean-up and analysis
procedures to be used for the field samples.
The quantitative criterion for acceptable filter quality will depend on the detection limit criteria
established for the field sampling and analysis program. Filters that give a background or blank
signal per filter greater than or equal to the target detection limit for the analyte(s) of concern
shall be rejected for field use. Note that acceptance criteria for filter cleanliness depend not
only on the inherent detection limit of the analysis method but also on the expected field sample
volume and on the desired limit of detection in the sampled stream.
If the filters do not pass the QC check, they shall be re-muffled, re-extracted, and re-analyzed
until an acceptably low background level is achieved.
B-2
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N-l-2
Draft Sewage Sludge Method
N-65
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Proposed Analytical Method for
Determination of Toxic Poly chlorinated Biphenyls in
Sewage Sludge using Isotope Dilution High Resolution
Gas Chromatography/High Resolution Mass Spectrometry
July 20,1999
Prepared by
Marielle C. Brinkman
Study Coordinator
And
Jane C. Chuang
Work Assignment Leader
for
C.E. (Gene) Riley
Work Assignment Manager
Kathy Weant
Project Officer
Emissions, Monitoring, and Analysis Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
Battelle
505 King Avenue
Columbus, Ohio 43201-2693
N-66
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Proposed Analytical Method for Determination of Toxic Polychlorinated
Biphenyls in Sewage Sludge by Isotope Dilution High Resolution Gas
Chromatography/High Resolution Mass Spectrometry
1.0 SCOPE AND APPLICATION
1.1 This analytical method is for determination of the toxic polychlorinated biphenyls (PCBs)
in sewage sludge by high resolution gas chromatography/high resolution mass
spectrometry (HRGC/HRMS). The method is for use in the Emission Measurement
Center's (EMC) data gathering effort to support a Maximum Achievable Control
Technology (MACT) standard to limit emissions of hazardous air pollutants at two
sewage sludge incinerators. The method is based on a compilation of methods from the
technical literature and EPA Method 1668 (references 1-14).
1.2 The method presented here is intended to determine toxic PCBs in samples containing
PCBs as single congeners or as complex mixtures. The target analytes are listed in
Table 1.
1.3 The method is restricted for use only by or under the supervision of analysts experienced
in the use of high resolution gas chromatography (HRGC)Zhigh resolution mass
spectrometry (HRMS), and skilled in the interpretation of mass spectra.
1.4 Because of the extreme toxicity of these compounds, the analyst must take necessary
precautions to prevent exposure to himselfTherself, or to others, of materials known or -
believed to contain PCBs.
2.0 SUMMARY OF METHOD
2.1 An analytical flow diagram depicting the sewage sludge extraction procedure is shown in
Figure 1. Labeled PCBs are spiked into a well-mixed 2 g aliquot of the wet sludge.
Solids are homogenized into a slurry, the slurry is mixed with drying agent, and that
mixture is extracted in a Soxhlet apparatus with methylene chloride. The extract is
concentrated and spiked with cleanup standards.
2.2 A flow diagram depicting the sewage sludge extract cleanup procedure is shown in
Figure 2. The sewage sludge extracts are cleaned using acid and base partitioning,
granular copper (for removal of sulfur), and silica gel and activated carbon column
:h-?~r*crr2phy. Oily hydrocarbons are removed using High Performance Liquid
Chromatography (HPLC)/Gel Permeation Chromatography (GPC).
1
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2.3 After cleanup, the extract is concentrated to a final volume between 20 /jL -1.0 mL, per
the analyst's discretion. Prior to HRMS/HRGC injection, recovery standards are aaded to
each extract, and an aliquot of the extract is injected into the gas chromalcgraph. The
analytes are separated by the GC and detected by a high resolution mass spectrometer.
Two exact m/z's are monitored for each analyte.
2.4 An individual PCB congener is identified by comparing the GC retention time and ioa-
abundance ratio of two exact m/z's with the corresponding retention time of an authentic
standard and the theoretical or acquired ion-abundance ratio of the two exact m/z's.
Isomer specificity for the toxic PCBs is achieved using GC columns that resolve these
congeners from the other PCB analytes. Results are quantified using relative response
factors.
. 2.5 The quality of the analysis is assured through reproducible calibration and verification of
operation for the extraction, cleanup, and GC/MS systems.
3.0 DEFINITIONS AND ABBREVIATIONS
3.1 Definitions and Acronyms
*
3.1.1 Analyte - a PCB compound measured by this method. The analytes are listed in
Table 1.
3.1.2 Calibration Standard (CS) - a solution prepared from a secondary standard
and/or stock solutions and used to calibrate the response of the instrument with
respect to analyte concentration.
3,! J Calibration Verification Standard (VER) - the mid-point calibration standard
(CS3) that is used to verify calibration (see Table 4).
3.1.4 Congener - refers to a particular compound of the same chemical family.
3.1.5 CS1, CS2, CS3, CS4, CSS - see calibration standards in Table 4
3.1.6 Field Blank - an aliquot of 4% (v/v) HN03 acid that is placed in a sample
container in the laboratory or the field, and treated as a sample in all respects,
including exposure to sampling site conditions, storage, preservation, and all
analytical procedures. The purpose of the field blank is to determine if the field
or sample transporting procedures and environments have contaminated the
sample.
3.1.7 HRGC - high resolution gas chromatography or gas chromatograph.
2
M fiQ
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3.1.8 HRMS - high resolution mass spectrometry or mass spectrometer.
3.1.9 Internal Standard (IS) - a component which is added to every sample and is
present in the same concentration in every blank, quality control sample, and
calibration solution. The IS is added to the sample before extraction and is used
to measure the concentration of the analyte and surrogate compound. The IS
recovery serves as an indicator of the overall performance of the analysis.
3.1.10 K-D - Kudema-Danish concentrator; a device used to concentrate the analytes in
a solvent.
3.1.11 Laboratory Blank - see Laboratory Method Blank.
3.1.12 Laboratory Method Blank - an aliquot of reagent water or solvent that is
treated exactly as a sample including exposure to all laboratory glassware,
equipment, solvents, reagents, internal standards, and surrogates that are used
with samples. The laboratory method blank is used to determine if analytes or
interferences are present in the laboratory environment, the reagents, or the
apparatus.
3.1.13 Laboratory Spike Sample - a laboratory-prepared matrix blank spiked with
known quantities of analytes. The laboratory spike sample is analyzed exactly
like a sample. Its purpose is to assure that the results produced by the laboratory
remain within the limits specified in the method for precision and recovery.
3.1.14 May - this action, activity, or procedural step is neither required nor prohibited.
3.1.15 May not - this action, activity, or procedural step is prohibited.
3.1.16 Must - this action, activity, or procedural step is required.
3.1.17 m/z Scale - the molecular mass to charge ratio scale.
3.1.18 PAR - precision and recovery standard; secondary standard used to prepare
laboratory spike samples.
3.1.19 Percent Relative Standard Deviation (%RSD) - the standard deviation times
100 divided by the mean. Also termed "coefficient of variation."
3.120 PFK - perfluorokerosene; the mixture of compounds used to calibrate the exact
m/z scale in the HRMS.
3.1.21 Primary Dilution Standard - a solution containing the specified analytes that is
purchased or prepared from stock solutions and diluted as needed to prepare
calibration solutions and other solutions.
3'
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3.1.22 QC Check Sample - a sample containing all or a subset of the analytes at
known concentrations. The QC check sample is obtained from a hovscc e.wc/oal
to the laboratory or is prepared from a source of standards different from the
source of calibration standards. It is used to check laboratory nerfornisrse? will-
test materials prepared external to the normal preparation process.
3.1.21 Reagent Water - water demonstrated to be free from the analytes of interest and
potentially interfering substances at the analyte estimated detection limit; e.g.,
HPLC grade water.
3.1.24 Recovery Standard - a known amount of component added to the concentrated
sample extract before injection. The response of the internal standards relative to
the recovery standard is used to estimate the overall recovery of the internal
standards.
3.1.25 Relative Response Factor - the response of the mass spectrometer to a known
amount of an analyte relative to a known amount of an internal standard.
3.1.26 RF - response factor (see Section 10.2.2).
3.1.27 RPD - relative percent difference, defined as the absolute value of the difference
between two values divided by the mean of the two values, expressed as a
percentage.
3.1.28 S/N - signal to noise ratio.
3.1.29 Should - this action, activity, or procedural step is suggested but not required.
3.1.30 SICP - selected ion current profile; the line described by the signal at an exact
miz.
3.1.31 Specific Isomers - a specific isomer is designated by indicating the exact
positions (carbon atoms) where chlorines are located within the molecule For
example, 2,3,3',4,4-PeCB refers to only one of the 209 possible PCB isomers -
that isomer which is chlorinated in the 2,3t3',4,4'-position of the biphenyl ring
structure.
3.1.32 Specificity - the ability to measure an analyte of interest in the presence of
interferences and other analytes of interest encountered in a sample,
3.1.33 Stock Solution - a solution containing an analyte that is prepared using a
reference material traceable to EPA, the National Institute of Science and
Technology (NISI), or a source that will attest to the purity and authenticity of
the reference material.
4
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3.1.34 Toxic PCB - any or all of the toxic polychlorinated biphenyl isomers shown in
Table 1.
3.1.35 VER — see Calibration Verification Standard (Section 3.1.3).
3.2 Abbreviations
3.2.1 PCB - any or all of the 209 possible polychlorinated biphenyl isomers.
3.2.2 TCB- abbreviation for tetrachlorinated biphenyl.
3.2.3 PeCB - abbreviation for pentachlorinated biphenyl.
3.2.4 HxCB - abbreviation for hexachlormated biphenyl.
3.2.5 HpCB - abbreviation for heptachlorinated biphenyl.
3.2.6 DCB - abbreviation for decachlorinated biphenyl.
4.0 CONTAMINATION AND INTERFERENCES'
4.1 Method interferences may be caused by contaminants in solvents, reagents, glassware,
and other sample processing hardware that lead to discrete artifacts and/or elevated
backgrounds at the ions monitored. All of these materials must be routinely demonstrated
to be free from interferences under the conditions of the analysis by analyzing field and
laboratory blanks as described in Sections 9.1.1 and 9.2.2.
4.2 Solvents, reagents, glassware, and other sample processing hardware may yield artifacts
and/or elevated baselines causing misinterpretation of chromatograms. Specific selection
of reagents and purification of solvents by distillation in all-glass systems may be
required. Where possible, reagents are cleaned by extraction or solvent rinsing. The toxic
PCB congeners 105, 114,118,123, 156,157, 167, and 180 have been shown to be very
difficult to completely eliminate from the laboratory, and baking of glassware in a kiln or
furnace at 450-500°C may be necessary to remove these and other contaminants.
4.3 Proper cleaning of glassware is extremely important because glassware may not only
contaminate the samples but may also remove the analytes of interest by adsorption onto
the glass surface. . .
4.3.1 Glassware should be rinsed with methanol and washed with a detergent solution
as soon after use as is practical. Sonication of glassware containing a detergent
solution for approximately 30 seconds may aid in cleaning. Glassware witn
5'
N-71
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removable parts, particularly separatory funnels with fluoropolymer stopcocks,
must be disassembled prior to detergent washing.
4.3.2 After detergent washing, glassware should be rinsed immediately first with
methanol, thai with hot tap water. The tap water rinse is followed by distilled
water, methanol, and then methylene chloride rinses.
4.3.3 Baking of glassware in kiln or other high temperature furnace (450-500°Q may
be warranted after particularly dirty samples are encountered. However, baking
should be minimized, as repeated baking of glassware may cause active sites on
the glass surface that may irreversibly adsorb PCBs.
4.3.4 Immediately prior to use, the Soxhlef apparatus should be pre-extracted with
methylene chloride for 3 hours to remove any possible background
contamination.
4.4 The use of high purity reagents minimizes background contamination and interference
problems. Purification of solvents by distillation in all-glass systems may be required.
4.5 Matrix interferences may be caused by contaminants that are co-extracted from the
sample. The extent of matrix interferences may vary considerably with the source being
sampled. Toxic PCBs are often associated with other interfering chlorinated compounds
which are at concentrations several orders of magnitude higher than that of the PCBs of
interest. The cleanup procedures in Section 11.3 can be used to reduce many of these
interferences, but unique samples may require additional cleanup approaches.
4.6 Two high resolution capillary columns, a J&W DBXLB, 60 m x 0.25 mm x 0.25 ^tr.
(J&W), and a 50 m x 0.23 mm x 0.25 turn HT-8 (SGE), are recommended for PCB
analysis because both of these columns will resolve all 13 toxic PCBs. Equivalent
columns that sufficiently resolve the toxic PCBs may also be used.
4.7 If other gas chromatographic conditions or other techniques are used, the analyst is
required to support the data through an adequate quality assurance program.
5.0 SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely
defined. Nevertheless, each chemical compound should be treated as a potential health
hazard. Therefore, exposure to these chemicals must be reduced to the lowest possible
level by whatever means available.
5.2 The laboratory is responsible for maintaining a current file of OSHA regulations
regarding the safe handling of the chemicals specified in this method. A reference file of
6
N-72
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material safety data sheets should also be made available to all personnel involved in the
chemical analysis.
5.3 PCBs and methylene chloride have been classified as known or suspected human or
mammalian carcinogens.
5.4 Unsterilized raw sewage sludge may be a human health risk because pathogens contained
within the sample, e.g., salmonella, E. coli, hepatitis, may be aerosolized and transported
to the human host via inhalation or dermal contact with mucous membranes. All sewage
sludge samples should be sterilized by 4% (v/v) nitric acid that is added to the sampling
bottles prior to shipment into the field for sampling (Section 8.2). In addition, sewage
sludge should only be collected and stored in bottles containing vents that prevent
pressure buildup, thus avoiding the possibility of the sample spraying forcefully out of
the sample container when it is opened.
6.0 APPARATUS, EQUIPMENT, AND SUPPLIES
6.1 Glassware Cleaning Equipment—Laboratory sink with overhead fume hood.
6.2 Sample Preparation Equipment
v
6.2.1 Laboratory fume hood of sufficient size to contain the sample preparation
equipment listed below.
6.2.2 Glove box (optional).
6.2.3 Oven—For determining percent moisture; capable of maintaining a temperature
of 110± 5°C
6.2.4 Desiccator.
6.2.5 Balances
6.2.5.1 Analytical—Capable of weighing 0.1 mg.
6.2.5.2 Top loading—Capable of weighing 10 mg.
6.3 Extraction Apparatus
6.3.1 Soxhlet Apparatus
7
N-73
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6.3.1.1 Soxhlet—50-mm ID, 200-mL capacity with 500-mL flask (Cal-Glass
LG-6900, or equivalent, except substitute 500-mL round-bottom
for 300-mL flat-bottom flask).
6.3.1.2 Thimble—43 mm * 123 mm to fit Soxhlet (Cal-Glass LG-6901-122, or
equivalent).
6.3.1.3 Heating mantle—Hemispherical, to fit 500-mL round-bottom flask (Cal-
Glass LG-8801-112, or equivalent).
6.3.1.4 Variable transformer—Powerstat (or equivalent), 110-volt, 10-amp.
6.3.2 Beakers—400- to 500-mL.
6.3.3 Spatulas—Stainless steel.
6.4 - Filtration Apparatus
6.4.1 Pyrex glass wool—Heated in an oven at 450-500 *C for 8 hours minimum.
6.4.2 Glass funnel—125- to 250-mL.
6.4.3 Glass-fiber or quartz fiber filter paper—Whatman GF/D (or equivalent).
6.4.4 Drying column—15- to 20-mm ID Pyrex chromatographic column equipped with
coarse-glass frit or glass-wool plug.
6.5 Cleanup Apparatus
6.5.1
6.5.2
Pipets
6.5.1.1 Disposable, Pasteur, 150-mm long * 5-mm ID (Fisher Scientific 13-675-
6A, or equivalent).
6.5.1.2 Disposable, serological, 50-mL (8- to 10- mm ID).
Glass chromatographic columns
6.5.2.1 150-mm long * 8-mm ID, (Kontes K-420155, or equivalent) with
coarse-glass frit or glass-wool plug and 250-mL reservoir.
6.5.2.2 200-mm long * 15-mm ID, with coarse-glass frit or glass-wool plug and
250-mL reservoir.
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6.6.2.1 Concentrator tubes—10-mL, graduated (Kontes K-570050-1025, or
equivalent), and 1.0 mL (Kontes K-570050-1000, or equivalent) with
calibration verified. Ground-glass stopper (size 19/22 joint) is used to
prevent evaporation of extracts.
6.6.2.2 Evaporation flask—500-mL (Kontes K-570001-0500, or equivalent),
attached to concentrator tube with springs (Kontes K-662750-0012 or
equivalent).
6.6.2.3 Snyder column—Three-ball macro (Kontes K-503000-0232, or
equivalent).
6.6.2.4 Boiling chips
6.6.2.4.1 Glass or silicon carbide—Approximately 10/40 mesh,
extracted with methylene chloride and baked at 450°C for 1
hour minimum.
6.6.2.4.2 Fluoropolymer (optional)—Extracted with methylene
_ chloride.
6.6.2.5 Water bath—Heated, with concentric ring cover, capable of maintaining
a temperature within ±2°C, installed in a fume hood.
6.6.3 Nitrogen blowdown apparatus—Equipped with water bath controlled in the range
of 30 - 60°C (N-Evap, Organomation Associates, Inc., or equivalent), installed in
a fume hood.
6.6.4 TurboVap Nitrogen blowdown apparatus—Equipped with water bath controlled
in the range of 30 - 60°C, and concentrator tubes (Turbotubes, or equivalent),
(Turbovap H, Zymark, or equivalent).
6.6.5 Sample vials
6.6.5.1 Amber glass, 2- to 5-mL with fluoropolymer-lined screw-cap.
6.6.5.2 Glass, 0.3-mL, conical, with fluoropolymer-lined screw or crimp cap.
6.7 Gas Chromatograph—Shall have splitless or on-column injection port for capillary
column, temperature program with isothermal hold, and shall meet all of the performance
specifications m Section 10.
6.7.1 GC Columns—Each of the GC columns listed below is capable of resolving the
13 toxic PCB congeners analyzed for in Ms method. Other GC columns may be
10
N-75
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used when resolution of the PCB congeners of concern from their most closely
eluting leading and trailing congeners can be demonstrated,
6.7.2 Column #1—50 m long * 0.25±0.02-mm ID; 0.25-jim film HT-8 (SGE. or
equivalent). «
6.7.3 Column #2—60 m long x 0.25±0,02-mm ED; 0.25-^m film DBXLB (J&W, or
equivalent).
6.8 High Resolution Mass Spectrometer—28- to 40-eV electron impact ionization, shall be
capable of repetitively selectively monitoring 12 exact m/z's minimum at high resolution
(i 10,000) during a period less than 1.5 seconds, and shall meet all of the performance
specifications in Section 10.
6.9 HRGC/HRMS Interface—The high resolution mass spectrometer (HRMS) shall be
interfaced to the high resolution gas chromatograph (HRGC) such that the end of the
capillary column terminates within 1 cm of the ion source but does not intercept the
electron or ion beams.
6.10 Data System—Capable of collecting, recording, and storing MS data.
7.0 REAGENTS AND STANDARDS
Note: unless otherwise stated, all reagents, water, and solvents must be pesticide grade (if
available) or equivalent
7.1 Acid and Base Partitioning
7.1.1 Potassium hydroxide—Dissolve 20 g pesticide grade (if available) KOK m 100
mL reagent water.
7.1.2 Sulfuric acid—Pesticide grade (if available; specific gravity 1.84).
7.1.3 Hydrochloric acid—Pesticide grade (if available), 6N.
7.1.4 Sodium chloride—Pesticide grade (if available), prepare at 5% (w/v) solution in
reagent water.
7.2 Solution Drying and Evaporation
7.2.1 Solution drying—Sodium sulfate, reagent grade, granular, anhydrous (Baker
3375, or equivalent), rinsed with methylene chloride (20 mL/g), baked at 400 °C
for 1 hour minimum, cooled in a desiccator, and stored in a pre-cleaned glass
11
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bottle with screw-cap that prevents moisture from entering. If, after heating, the
sodium sulfate develops a noticeable grayish cast (due to the presence of carbon in
the crystal matrix), that batch of reagent is not suitable for use and should be
discarded Extraction with methylene chloride (as opposed to simple rinsing) and
baking at a lower, temperature may produce sodium sulfate that is suitable for use.
7.2.2 Prepurified nitrogen - 99.9995% purity.
7.2.3 Diatomaceous earth drying agent, Extrelut, Hydromatrix, or equivalent
7.2.4 Desiccant—EM Science silica gel Grade H Type IV Indicating (6-16 mesh).
7.3 Extraction
7.3.1 Solvents—Acetone, n-hexane, methanol, methylene chloride, and nonane;
distilled in glass, pesticide quality, lot-certified to be free of interferences.
7.4 Adsorbents for Sample Cleanup
7.4.1 Silica gel
7.4.1.1 Activated silica gel—100-200 mesh, Supelco 1 -3651 (or equivalent),
rinsed with methylene chloride, baked at 180°C for a minimum of 1
hour, cooled in a desiccator, and stored in a precleaned glass bottle with
screw-cap that prevents moisture from entering.
7.4.1.2 Acid silica gel (30% w/w)—Thoroughly mix 44 g of concentrated
sulfuric acid with 100 g of activated silica gel in a clean container. Break
up aggregates with a stirring rod until a uniform mixture is obtained.
Store in a screw-capped bottle with fluoropolymer-lined cap.
7,4.1.3 Basic silica gel—Thoroughly mix 30 g of IN sodium hydroxide with
100 g of activated silica gel in a clean container. Break up aggregates
with a stirring rod until a uniform mixture is obtained. Store in a screw-
capped bottle with fluoropolymer-lined cap.
7.4.2 Carbon
7.4.2.1 Carbopak C—(Supelce 1-0258, or equivalent).
7.4.2.2 Celite 545—(Supelco 2-0199, or equivalent).
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7.4.2.3 Thoroughly mix 18 g Carbopak C and 18 g Celite 545 to produce a 50%
w/w mixture. Activate the mixture at 130°C for a minimum of 6 hoars.
Store in a desiccator.
7.5 Copper (granular)—Copper must be used within one hour of being activated using the
following procedure: ..
7.5.1 Add sufficient copper to process the sample set (one sample uses approximately
2 g of copper).
7.5.2 Add sufficient reagent water to the beaker so that the water level is above the
copper.
7.5.3 Add an equal amount of 12N HC1 to the beaker.
7.5.4 Stir mixture for approximately 30 seconds, and then discard the liquid into acid
waste.
7.5.5 Rinse copper three times each with the following (listed in order); reagent water,
acetone, and methylene chloride.
7.6 Standard Solutions
Standards purchased as solutions or mixtures with certification to their purity,
concentration, and authenticity, or prepared from materials of known purity and
composition. If the chemical purity is 98 percent or greater, the weight may be used
without correction to compute the concentration of the standard. Standards should be
stored in the dark in a freezer at sO°C in screw-capped vials with fluoropolymer-lined
caps when not being used. A marie is placed on the vial at the level of the solution so that
solvent loss by evaporation can be detected. If solvent loss has occurred, or the shelf life
has expired, the solution should be replaced.
7.6.1 Stock Standard Solutions
7.6.1.1 Prepared in nonane per the steps below or purchase as dilute solutions
(Cambridge Isotope Laboratories/CIL, Wobum, MA, or equivalent).
Observe the safety precautions in Section 5.
7.6.1.2 An appropriate amount of assayed reference material is dissolved in
solvent For example, weigh 1 to 2 mg ofPCB '126 to three significant
figures in a 10-mL ground-glass-stoppered volumetric flask and fill to
the mark with nonane. After the PCB is completely dissolved, transfer
the solution to a clean 15-mL vial with fluoropolymer-lined cap.
13
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7,6,1.3 Stock standard solutions should be checked for signs of degradation
prior to the preparation of calibration or performance test standards.
Reference standards that can be used to determine the accuracy of
calibration standards are available from several vendors.
7.6.2 Precision and Recovery (PAR) Stock Solution
Using the solutions in Section 7.6.1, prepare the PAR stock solution to contain the
PCBs of interest at the concentrations shown in Table 3. When diluted, the
solution will become the PAR spiking solution (Section 7.6.7).
7.6.3 Internal Standard Solutions
7.6.3.1 Internal Standard Stock Solution
From stock standard solutions, or from purchased mixtures, prepare this
solution to contain the labeled internal standards in nonane at the stock
solution concentrations shown in Table 3. The solution is diluted with
acetone prior to use (Section 7.6.3.2).
1.632 Internal Standard Spiking Solution
Dilute a sufficient volume of the labeled compound solution (Section
7.6.3.1) by a factor of 500 with acetone to prepare a diluted spiking
solution. Concentrations may be adjusted to compensate for background
levels. Each sample requires 1.0 mL of the diluted solution,
7.6.4 Cleanup Standard Spiking Solution
7.6.4.1 Prepare labeled PCBs 81 and 111 in acetone at the level shown in
Table 3.
7.6.4.2 The cleanup standard is added to the sludge extract prior to cleanup to
measure the efficiency of the cleanup process.
7.6.5 Recovery Standard(s) Spiking Solution
Prepare the recovery standard spiking solution to contain labeled PCBs 52,101,
138, and 178 in nonane at the level shown in Table 3.
7.6.6 Calibration Standards (CS1 through CS5)
7 6.6.1 Combine the solutions in Sections 7.6 to produce the five calibration
solutions shown in Table 4 in nonane.
14
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7.6.6.2
Calibration standards may also be purchased already prepared in nonane
(CIL).
7.6.6.3 These solutions permit the relative response factor (labeled to native) to
be measured as a function of concentration. The CS3 standard is used for
calibration verification (VER).
7.6.7 Precision and Recovery (PAR) Spiking Solution
7.6.7.1 Used for preparation of laboratory spike samples (Section 9.5).
7.6.7.2 Dilute 200 ^L of the PAR stock solution (Section 7.6.2) to 10 mL with
acetone. 1.0 mL is required for each laboratory spike sample.
Concentrations of individual PCBs may be adjusted in this solution to
compensate for background levels.
7.6.8 GC Retention Time Window Defining and Isomer Specificity Test Solution
7.6.8.1 This solution is used to define the beginning and ending retention times
for the PCB congeners and to demonstrate isomer specificity of the GC
columns.
7.6.8.2 The solution must contain the compounds listed in Table 8 (CIL, or
equivalent), at a minimum.
7.6.9 QC Check Sample
If available, a QC check sample should be obtained from a source independent of
the calibration standards. Ideally, this check sample would be a certified standard
reference material (SRM) containing the PCBs in known concentrations in a
sample matrix similar to the matrix being analyzed.
7.6.10 HPLC Fractionation Time Standard "
Prepare a solution containing both 4,4'-dibromooctafluorobiphenyl (DBOFB) and
perylene at aconcentration level of 20 tx%!rnL in methylene chloride.
7.6.11 Solution Stability
7.6.11.1 Standard solutions used for quantitative purposes (Section 7.6.6) should
be analyzed periodically, and should be assayed against reference
standards before further use.
7.6.11.2 If tiie analysis yields standard concentrations that are not within 25% of
the true value for any PCB, the solutions will be replaced with solutions
15
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that, when analyzed, yield concentrations that are within 25% of the true
value.
8.0 SAMPLE COLLECTION, PRESERVATION, STORAGE, AND
HOLDING TIMES
8.1 Sample Collection
Sewage sludge sample bottles must be equipped with a stainless steel vent to prevent
pressure buildup.
8.2 Pre-Treatment/Sterilization
Sample bottle must contain enough 1:1 HN03 to give 4% HN03 (v/v) for sterilization.
8.3 Sample Storage
Maintain semi-solid sludge samples in the dark at s4°C from the time of collection until
receipt at the laboratory.
8.4 Holding Times
8.4.1 Samples are stored in the dark at s4°C.
8.4.2 Sample extracts are stored in the dark at <-10°C until analyzed.
8.4.3 A maximum of 30 days between sample collection and extraction, and a
maximum of 45 days between extraction and analysis is recommended.
9.0 QUALI rY ASSURANCE/QUALITY CONTROL
9.1 The minimum requirements of this method consist of spiking samples with labeled
compounds to evaluate and document analyte recovery, and preparation and analysis of
QC samples including blanks and duplicates. Laboratory performance is compared to
target performance criteria to establish the performance requirements of the method.
9.2 Labeled Compounds
The laboratory shall spike all samples with the labeied standard spiking solutions
(jti,uuiii 7.6.3.2 and 7.6.4) to assess method performance ol the sample matrix.
Recovery of labeled standards from samples should be assessed and records should be
maintained.
16
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9.2.1 Analyze each sample according to the procedures in Section 11. Compute the
percent recovery of the labeled standards as described in Section 12.2.2.
9.2.2 The recovery of each labeled compound will be compared to the target limits in
Table 5. If the recovery of any compound falls outside of these limits, the data
will be flagged and impact on reported concentration will be discussed in the
reported results.
Laboratory Method Blanks
9.3.1 Prepare, extract, clean up, and concentrate a laboratory method blank with each
sample batch (samples of the same matrix started through the extraction process
on the same 12-hour shift, to a maximum of 20 samples).
9.3.2 If any native PCB analytes (Table 1) are found in the blank at greater than 20
percent of the concentration level found is the sample, the reported data should be
flaggged as potentially containing some contribution from laboratory procedures.
If method blank contamination is severe, sample preparation and analysis
procedures should be reviewed and reprocessing the sample set should be
considered depending on specific project requirements.
QC Check Sample
If available, analyze a QC check sample (Section 7.6.9) periodically to assure the
accuracy of calibration standards and the overall reliability of the analytical process. It is
suggested that the QC check sample be analyzed at least quarterly.
Laboratory Spike Samples
9.5.1 With each sample batch, spike duplicate sludge samples with PAR spiking
solution (Section 7.6.7) and process through extraction, cleanup, and analysis
procedures as the field samples.
9.5.2 Calculate precision for the duplicate laboratory spike samples as the relative
percent difference (RPD). The RPD should be < 50 percent.
9.5.3 Calculate accuracy for the laboratory spike samples by determining the percent of
recovery of spiked analytes. Accuracy should be within 40 -160 percent for
analytes spiked five times the background level of the sludge samples.
Method Specifications
9.6.1 The specifications contained in this method can be met if the apparatus used is
calibrated properly and then maintained in a calibrated state.
17
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9.6.2 The standards used for calibration (Section 7.6.6), calibration verification
(Section 7.6.6.3), and for laboratory spike samples (Section 7.6.7) should be
identical, so that the most precise results will be obtained.
9.6.3 A HRGC/HRMS instrument will provide the most reproducible results if
dedicated to the. settings and conditions required for the analyses ofPCB analytes
by this method.
10.0 HRGC/HRMS CALIBRATION
10.1 Operating Conditions
Establish the operating conditions necessary to meet the minimum retention times for the
internal and recovery standards in Table 2.
10.1.1 Suggested HRGC Operating Conditions
Injector temperature: 290°C
Interface temperature: 290 °C
Initial temperature: 150°C
Initial time: .2 min
Temperature program: 150 to 200°C at 10°C/min; 200 to 280°C at
• 2°C/mio
NOTE: All portions of the column that connect the HRGC to the ion source
shall remain at or above the interface temperature specified above during
analysis to preclude condensation of less volatile compounds.
The HRGC conditions may be optimized for compound separation and
sensitivity. Once optimized, the same HRGC conditions must be used for the
analysis of all standards, blanks, and samples.
10.1.2 High Resolution Mass Spectrometer (HRMS) Resolution
10.1.2.1 Obtain a selected ion current profile (SICP) of each analyte listed in
Table 3 at the two exact m/z's specified in Table 6 and at 210,000
resolving power by injecting an authentic standard of the PCBs
either singly or as part of a mixture in which there is no interference
between closely eluted components.
10.1.2.1 The analysis ti'm* for PCRs may exceed the long-term mass stability
of the mass spectrometer. Because the instrument is operated in the
high-resolution mode, mass drifts of a few ppm (e.g., 5 ppm in mass)
18
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can have serious adverse effects on instrument performance.
Therefore, a mass-drift correction is mandatory and a locK-mas;- m'z
from PFK is used for drift correction. The lock-mass m/z is depen-
dent on the exact m/z's monitored within each descriptor, as shown
in Table 6. The level of PFK metered into the HRMS during
analyses should be adjusted so that the amplitude of the most intense
selected lock-mass m/z signal (regardless of the descriptor number)
does not exceed 10 percent of the full-scale deflection for a given set
of detector parameters. Under those conditions, sensitivity changes
that might occur during the analysis can be more effectively
monitored
NOTE: Excessive PFK (or any other reference substance) may cause
noise problems and contamination of the ion source necessitating
increased frequency of source cleaning.
10.1.2.3 If the HRMS has the capability to monitor resolution during the
analysis, it is acceptable to terminate the analysis when the
resolution falls below 10,000 to save reanalysis time.
10.1.2.4 Using a PFK molecular leak, tune the instrument to meet the
minimum required resolving power of 10,000 (10 percent valley) at
m/z 380.9760. For each descriptor (Table 6), monitor and record the
resolution and exact m/z's of three to five reference peaks covering
the mass range of the descriptor. The resolution must be greater than
or equal to 10,000, and the deviation between the exact m/z and the
theoretical m/z (Table 6) for each exact m/z monitored must be less
than 5 ppm.
10.1.3 Ion Abundance Ratios, Minimum Levels, Signal-to-Noise Ratios, and Absolute
Retention Times
10.1.3.1 Choose an injection volume of either!- or 2-\iL, consistent with the
capability of the HRGC/HRMS instrument Inject a 1- or 2-^L
aliquot of the CS1 calibration solution (Table 4) using the GC
conditions from Section 10.1.1.
10.1.3.2 Measure the SICP areas for each analyte, and compute the ion
abundance ratios at the exact m/z's specified in Table 6. Compare
the computed ratio to the theoretical ratio given in Table 7.
The exact m/z's to be monitored in each descriptor are shown in
Table 6. Each group or descriptor shall be monitored in succession
as a function of GC retention time to ensure that all of the toxic
PCBs are detected. Additional m/z's may be monitored in each
19
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descriptor, and the m/z's may be divided among more than the
descriptors listed in Table 6, provided that the laboratory is able to
monitor the m/z's of all the PCBs that may elute from the GC in a
given retention-time window.
The mass spectrometer shall be operated in a mass-drift correction
mode, using PFK to provide lock m/z's. The lock mass for each
group of m/z's is shown in Table 6. Each lock mass shall be
monitored and shall not vary by more than ±20 percent throughout
its respective retention time window. Variations of the lock mass by
more than 20 percent indicate the presence of coeluting interferences
that may significantly reduce the sensitivity of the mass
spectrometer. Reinjection of another aliquot of the sample extract
will not resolve the problem. Additional cleanup of the extract may
be required to remove the interferences.
10.1.3.3 All PCB analytes and labeled compounds in the CS1 standard shall
be within the QC limits in Table 7 for their respective ion abundance
ratios; otherwise, the mass spectrometer shall be adjusted and this
test repeated until the m/z ratios fall within the limits specified. If
the adjustment alters the resolution of the mass spectrometer,
resolution shall be verified (Section 10.1.2) prior to repeat of the test.
10.1.3.4 The peaks representing the PCBs and labeled compounds in the CS1
calibration standard must have signal-to-noise ratios (S/N) greater
than or equal to 10.0. Otherwise, the mass spectrometer shall be
adjusted and this test repeated until the peaks have signal-to-noise
ratios (S/N) greater than or equal to 10.0.
10.1.3.5 Retention Time Windows—Analyze the GC retention time window
defining and isomer specificity test solution (Section 7.6.8) using the
optimized temperature program in Section 10.1.1. Table 2 gives the
elution order (first/last) of the window-defining compounds.
10.1.4 Isomer Specificity
10.1.4.1 From the analysis of the GC retention time window and isomer
specificity test solution (Section 10.1.3.5), compute the percent
valley between the GC peaks for PCB 123 and PCB 118, and
between the GC peaks for PCB 156 and 157,
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10.1.4.2 Verily that the height of the valley between these closely eluted
isomers and the PCBs given in Section 10.1.4.1 is less than
25 percent. If the valley exceeds 25 percent, adjust the analytical
conditions and repeat the test or replace the GC column and
recalibrate.
10.2 Initial Calibration
10.2.1 Prepare a calibration curve encompassing the concentration range for each
compound to be determined. Referring to Table 2, calculate the relative
response factors for unlabeled target analytes (RFJ relative to their appropriate
internal standard (Table 3) and the relative response factors for the I3Cu-labeled
internal standards (Riy using the four recovery standards (Table 3) according
to the following formulae:
jyr _ (An + A*) x Qk
(Aj + Aj)* Q„
Aa' and A,3 - sum of the Integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for unlabeled PCBs,
Aj and Aj ¦ sum of the integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for the labeled internal standards,
A J and A„3 m sum of the integrated ion abundances of the quantitation ions (Tables 2,3 and
6) far the recovery standard,
Qt, - quantity of the internal standard injected (pg),
Q„ « quantity of the recovery standard injected (pg), and
Qm m quantity of the unlabeled PCB anafyte injected (pg).
RF„ and the RFk are dimensionless quantities; the units used to express Q„ Q„ and Q.
must be the same.
1022 Calculate the mean relative response factor values and their respective percent
relative standard deviation (%RSD) for the five calibration solutions. If the
mean relative response factors between the analytes is not within 35% RSD, the
instrument must be re-calibrated.
»*r _ + ) x
(Aj + Aj)*Qk
where:
s
RF„ — JzL
S
21
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where n represents a particular PCB congener (nml to 13; Table 3), and j is the
injection or calibration solution number; (j**lto 5).
„ . X R^isO)
RF„ =
where is represents a particular PCB internal standard (is — 14 to 23; Table 3), and j
is the injection or calibration solution number; Q -1 to 5).
10.3 Operation Verification
At the beginning of each 12-hour shift during which analyses are performed,
HRGC/HRMS system performance and calibration are verified for all native PCBs and
labeled compounds. For these tests, analysis of the CS3 calibration verification (VER)
standard (Section 7.6.6 and Table 4) and the isomer specificity test solution (Section 7.6.8
and Table 8) shall be used to verily all performance criteria. Adjustment and/or
recalibration (Section 10) shall be performed until all performance criteria are met. Only
after all performance criteria are met may samples and blanks be analyzed.
10.3.1 HRMS Resolution
A static resolving power of at least 10,000 (10 percent valley definition) must be
demonstrated at the appropriate m/z before any analysis is performed. Static
resolving power checks must be performed at the beginning and at the end of
each analysis batch according to procedures in Section 10.1.2. Corrective
actions must be implemented whenever the resolving power does not meet the
requirement.
10.3.2 Calibration Verification
10.3.2.1 Inject the VER standard using the procedure in Section 11.12.3.
10.3.2.2 The m/z abundance ratios for all PCBs shall be within the limits in
Table 7; otherwise, the mass spectrometer shall be adjusted until the
m/z abundance ratios fall within the limits specified, and the
verification test shall be repeated. If the adjustment alters the
resolution of the mass spectrometer, resolution shall be verified
(Section 10.1.2) prior to repeat of the verification test.
10.3.2.3 The peaks representing each native PCB and labeled compound in
the VER standard must be present with a S/N of at least 10;
otherwise, the mass spectrometer shall be adjusted and the
verification test repeated.
22
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10.3.2.4 Calculate the relative response factors (RF) for unlabeled target
analytes n = 1 to 13 from Table 3] relative to taeir appiouriate
internal standards (Table 2), and the RFU for the nC12-kbeltc
internal standards [RF(U); is = 14-23] relative to the recoverv
standards (Table 2) using the equations shown in Section 10.2.1.
10.3.2.5 For each compound, compare the relative response factor with those
generated in the initial calibration. Relative response factors should
be within 35 percent of initial calibration results for 70% of the
analytes for the calibration to be verified. Once verified, analysis of
standards and sample extracts may proceed. If, however, fewer than
70% of the response factors are within the 35% limit, the
measurement system is not performing properly for those
compounds. In this event, prepare a fresh calibration standard or
correct the problem causing the failure and repeat the resolution
(Section 10.3.1) and calibration verification (Section 10.3.2) tests, or
recalibrate (Section 10), Per the analyst's discretion, results may
also be reported for these analytes using the average calibration
verification response factors bracketing the samples rather than the
mean response factor generated in the initial calibration. If this
option is chosen, data reported using an average calibration
. verification response factor should be flagged and discussed in the
final report
10.3.3 Retention Times
The absolute retention times of the GC/MS internal standards in the calibration
verification shall be within ±15 seconds of the retention times obtained during
initial calibration.
10.3.4 HRGC Resolution
Inject the GC retention time window defining and Isomer specificity
test solution (Section 7.6.8).
The valley height between PCBs 123 and 118 at mix 325.8804 shall
not exceed 25 percent, and the valley height between PCBs 156 and
157 shall not exceed 25 percent at m/z 359.8415 on the GC
columns.
If the absolute retention time of any compound is not within the
limits specified or if the congeners are not resolved, the GC is not
performing properly. In this event, adjust the GC and repeat the
calibration verification test or recalibrate, or replace the GC column
and either verify calibration or recalibrate,
23
10.3.4.1
10.3.4.2
10.3.4.3
W.flfl
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where n represents a particular PCS congener (n*=l to 13; Table 3), and j is the
injection or calibration solution number; (j~l to 5).
5
, X RFhQ)
» j? _
ILtfa ^
where is represents a particular PCB internal standard (is -14 to 23; Table 3), and j
is the injection or calibration solution number; Q~1 to S).
10.3 Operation Verification
At the beginning of each 12-hour shift during which analyses are performed,
HRGC/HRMS system performance and calibration are verified for all native PCBs and
labeled compounds. For these tests, analysis of the CS3 calibration verification (VER)
standard (Section 7,6.6 and Table 4) and the isomer specificity test solution (Section 7.6.8
and Table 8) shall be used to verify all performance criteria. Adjustment and/or
recalibration (Section 10) shall be performed until all performance criteria are met. Only
after all performance criteria are met may samples and blanks be analyzed.
10.3.1 HRMS Resolution
A static resolving power of at least 10,000 (10 percent valley definition) must be
demonstrated at the appropriate m/z before any analysis is performed. Static
resolving power checks must be performed at the beginning and at the end of
each analysis batch according to procedures in Section 10.1.2. Corrective
actions must be implemented whenever the resolving power does not meet the
requirement.
10.3.2 Calibration Verification
10.3.2.1 Inject the VER standard using the procedure in Section 11.12.3.
10.3.2.2 The m/z abundance ratios for all PCBs shall be within the limits in
Table 7; otherwise, the mass spectrometer shall be adjusted until the
m/z abundance ratios fall within the limits specified, and the
verification test shall be repeated. If the adjustment alters the
resolution of the mass spectrometer, resolution shall be verified
(Section 10.1.2) prior to repeat of the verification test.
10.3.2.3 The peaks representing each native PCB and labeled compound in
the VER standard must be present with a S/N of at least 10;
otherwise, the mass spectrometer shall be adjusted and the
verification test repeated.
22
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10.3.2.4 Calculate the relative response factors (RF) for unlabeled target
analytes [RF(a); n = 1 to 13 from Table 3] relative to their appiopriate
internal standards (Table 2), and the RFU for the ,3C12-labeled
internal standards [RF(il); is = 14-23] relative to the recoverv
standards (Table 2) using the equations shown in Section 10.2.1.
10.3.2.5 For each compound, compare the relative response factor with those
generated in the initial calibration. Relative response factors should
be within 35 percent of initial calibration results for 70% of the
analytes for the calibration to be verified. Once verified, analysis of
standards and sample extracts may proceed. If, however, fewer than
70% of the response factors are within the 35% limit, the
measurement system is not performing properly for those
compounds. In this event, prepare a fresh calibration standard or
correct the problem causing the failure and repeat the resolution
(Section 10.3.1) and calibration verification (Section 10.3.2) tests, or
recalibrate (Section 10). Per the analyst's discretion, results may
also be reported for these analytes using the average calibration
verification response factors bracketing the samples rather than the
mean response factor generated in the initial calibration. If this
option is chosen, data reported using an average calibration
. verification response factor should be flagged and discussed in the
final report
10.3.3 Retention Times
The absolute retention times of the GC/MS internal standards in the calibration
verification shall be within ±15 seconds of the retention times obtained during
initial calibration.
10.3.4 HRGC Resolution
10.3.4.1 Inject the GC retention time window defining and isomer specificity
test solution (Section 7.6.8).
10.3.4.2 The valley height between PCBs 123 and 118 at mJz 325.8804 shall
not exceed 25 percent, and the valley height between PCBs 156 and
157 shall not exceed 25 percent at m/z 359.8415 on the GC
columns.
10.3.4.3 If the absolute retention time of any compound is not within the
limits specified or if the congeners are not resolved, the GC is not
performing properly. In this event, adjust the GC and repeat the
calibration verification test or recalibrate, or replace the GC column
and either verify calibration or recalibrate.
23
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10.4
Data Storage
MS data shall be collected, recorded, and stored.
10.4.1 Data Acquisition
The signal at each exact m/z shall be collected repetitively throughout the
monitoring period and stored on a mass storage device.
10.4.2 Response Factors and Multipoint Calibrations
The data system shall be used to record and maintain lists of response factors
and multipoint calibration curves. Computations of relative standard deviation
(coefficient of variation) shall be used to test calibration linearity.
11.0 PROCEDURE
11.1 Sample preparation involves mixing the wet sludge sample with a drying agent so that the
toxic PCBs can be extracted efficiently. For samples known or expected to contain high
levels of the PCBs, the smallest sample size representative of the entire sample should be
used. With each sample set, a laboratory method blank and duplicate laboratory spike
samples must be processed through the same steps as the sample to check for
contamination and losses in the preparation processes. Percent moisture is determined
using the procedures in Section 11.2, and a 2 g sample aliquot (wet weight) is extracted as
described in Section 11.3.
11.2 Percent Moisture Determination
Note: This aliquot is used for determining the moisture content of sewage sludge
samples and not for determination of PCBs.
11.2.1 Weigh or tare a weighing pan or beaker to three significant figures
11.2.2 Transfer 10.0 ± 0.02 g of well-mixed sample to the pan or beaker
11.2.3 Weigh and record the wet sample plus beaker
11.2.4 Dry the sample for a minimum of 12 hours at 110 ± 5°C and cool in a
desiccator until the sample has equilibrated to room temperature. Weigh the dry
sample plus beaker.
24"
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11.2.5 Calculate percent moisture as follows:
% moisture * * 100
101
where: _
Whff " weight of sample plus beaker before drying (g),
W^s ¦» weight of sample plus beaker after drying (g),
11.3 Preparation of Sewage Sludge Samples
11.3.1 Weigh a well-mixed 2.0 g aliquot of the wet sludge sample into a clean beaker
or glass jar.
11.3:2 Spike the diluted labeled internal standard solution (Section 7.6.3.2) into the
sample.
X1.3.3 For each sample or sample batch (to a maximum of 20 samples) to be extracted
during the same 12 hour shift, prepare a laboratory method blank by spiking the
internal standard solution into an empty, clean beaker or glass jar.
11.3.4 If a laboratory spike sample is being prepared, add 1 mL of the PAR spiking
solution at this time.
11.3.5 Stir or tumble, and then equilibrate the aliquots for 1 to 2 hours.
11.3.6 Homogenize the sample into a slurry using a glass rod.
11.3.7 Mix the slurry with sufficient drying agent (Section 7.2.3) to provide a 1:1 ratio
(2 g), and extract the mixture using the Soxhlet procedure described in
Section 11.4.1,
11.4 Extraction and Concentration
The sewage sludge sample is extracted using the Soxhlet technique. Macro-concentration
procedures include rotary evaporation, Tuibovap, and Kuderna-Danish (K-D)
evaporation. Micro-concentration uses nitrogen blowdown.
11.4.1 Soxhlet Extraction
11.4.1.1 Place a clean extraction thimble (Section 6.3.1.2) in a clean
extractor.
25
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11.4.1.2 Place 30 to 40 mL of methylene chloride in the receiver and 200 to
250 mL of methylene chloride in the flask.
11.4.1.3 Load the sample mixture into the thimble. For laboratory method
blanks and spikes, rinse the contents of the beaker or glass jar four
times with methylene chloride. Add the rinses to the extractor.
11.4.1.4 Reassemble the Soxhlet apparatus, and apply power to the heatmg
mantle to begin extracting. Frequently check the apparatus for
foaming during the first 2 hours of extraction. If foaming occurs,
reduce the extraction rate until foaming subsides.
11.4.1.5 Extract the sample for a total of 16 to 24 hours. Cool and
disassemble the apparatus.
11.4.1.6 Concentrate the extract to approximately 10 mL; split the sample
extract into two equal portions (5 mL each). Transfer 5 mL of the
extract to a glass storage vial with a PTFE lined cap. Label the
extract, mark the liquid level on the vial with a permanent marker to
monitor solvent evaporation during storage, and store at 0°C.
11.4.1.7 Solvent exchange the other half of the extract (5 mL) into hexane by
adding 10 mL of hexane, concentrating down to 1 mL using K-D
evaporation, adding 10 mL hexane, and concentrating down again to
2mL. Transfer the extract with three aliquots (15 mL each) of
hexane into a 250-mL separately funnel. Proceed to Section 11.5 to
start cleanup procedures.
11.5 Acid and Base Partitioning
11.5.1 Spike 1.0 mL of the cleanup standard (Section 7.6.4) into the separatory funnels
cor raining the sample, laboratory method blank, and duplicate laboratory spike
sample extracts from Section 11.3.
11.5 J2 Partition the extract against 50 mL of sulfuric acid (Section 7.1.2). Shake for 2
minutes with periodic venting into a hood. Remove and discard the aqueous
layer. Repeat the acid washing until no color is visible in the aqueous layer to a
maximum of four washings.
11.5.3 Partition the extract against 50 mL of sodium chloride solution (Section 7.1.4)
in the same way as with the acid. Discard the aqueous layer.
11.5.4 Partition the extract against 50 mL of potassium hydroxide solution (Section
7.1.1) in the same wa> as with the acid. Repeat the base washing until no color
is visible in the aqueous layer to a maximum of four washings. Minimize
26
N-91
-------
contact time between the extract and the base to prevent degradation of the
PCBs.
11.5.5 Repeat the partitioning against sodium chloride solution two more times, each
time discarding the aqueous layer.
11.5.6 Pour each extract through a drying column containing 7 to 10 cm of granular
anhydrous sodium sulfate (Section 7.2.1). Rinse the separatory funnel with 30 to
50 mL of solvent, and pour through the drying column. Collect each extract in a
round-bottom flask.
11.5.7 Concentrate the extract to 1 mL using either rotovap, K-D concentration, or
Turbovap (Section 11.6). After concentration, proceed to Section 11.7 for sulfur
cleanup.
Macro-Concentration—Extracts in methylene chloride or n-hexane are concentrated
using rotary evaporation, a Kudema-Danish, or Turbovap apparatus.
11.6.1 Rotary evaporation—Concentrate the extracts in separate round-bottom flasks.
Note: Improper use of the rotary evaporator may cause contamination of the
sample extract
Assemble the rotary evaporator according to manufacturer's
instructions, and warm the water bath to 45 °C. On a daily basis,
preclean the rotary evaporator by concentrating 100 mL of clean
extraction solvent through the system. Archive both the concentrated
solvent and the solvent in the catch flask for a contamination check if
necessary. Between samples, use three 2- to 3-mL aliquots of
solvent to rinse the feed tube between samples. Collect waste in a
waste beaker.
Attach the round-bottom flask containing the sample extract to "the
rotary evaporator. Slowly apply vacuum to the system, and begin
rotating the sample flask.
Lower the flask into the water bath, and adjust the speed of rotation
and the temperature as required to complete concentration in 15 to 20
minutes. At the proper rate of concentration, the flow of solvent into
the receiving flask must be steady, with no bumping or visible
boiling of the extract occurring.
Note: If the rate of concentration is too fast, analyte loss may occur.
27
N-92
11.6.1.1
11.6.1.2
11.6.1.3
-------
11.6,1.4 When the liquid in the concentration flask has reached an apparent
volume of approximately 2 mL, remove the flask from the water bath
and stop the rotation. Slowly and carefully admit air into the system.
Be sure not to open the valve so quickly that the sample is blown out
of the flask. Rinse the feed tube with approximately 2 mL of solvent.
11.6.2 Kudema-Danish (K-D)—Concentrate the extracts in separate 500-mL K-D
flasks equipped with 10-mL concentrator tubes. The K-D technique is used for
solvents such as methylene chloride and n-hexane.
11.6.2.1 Add 1 to 2 clean boiling chips to the receiver. Attach a three-ball
macro-Snyder column. Pre-wet the column by adding approximately
1 mL of solvent through the top. Place the K-D apparatus hi a hot
water bath so that the entire lower rounded surface of the flask is
bathed with steam.
11.6.2.2 Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 15 to 20
minutes. At the proper rate of distillation, the balls of the column
will actively chatter but the chambers will not flood.
11.6.2.3 When the liquid has reached an apparent volume of 1 mL, remove
the K-D apparatus from the bath and allow the solvent to drain and
cool for at least 10 minutes.
11.6.2.4 Remove the Snyder column and rinse the flask and its lower joint
into the concentrator tube with 1 to 2 mL of solvent. A 5-mL syringe
is recommended for this operation.
11.6.2.5 Remove the three-ball Snyder column, add a fresh boiling chip, and
attach a two-ball micro-Snyder column to the concentrator tube. Pre-
wet the column by adding approximately 0.5 mL of solvent through
the top. Place the apparatus in the hot water bath.
11.6.2.6 Adjust the vertical position and the water temperature as required to
complete the concentration in 5 to 10 minutes. At the proper rate of
distillation, the balls of the column will actively chatter but the
chambers will not flood.
11.6.2.7 When the liquid reaches an apparent volume of 0.5 mL, remove the
apparatus from the water bath and allow to drain and cool for at least
10 minutes.
28
N-93
-------
11.6.3 Turbovap —Concentrate the extracts in separate 250-mL Turbotubes. The
Turbovap technique is used for solvents such as methylene chjonu? 3rd n-he;:ane.
11.7 Sulfur Cleanup
11.7.1 Add approximately 2 g of clean copper (Section 7.5) to a centrifuge tube.
11.7.2 "Vigorously mix the extract and the copper powder for at least 1 minute.
11.7.3 Allow the extract to react with the copper powder for 1 hour.
11.7.4 Separate the extract from the copper by drawing off the extract with a
disposable pipet and transfer to a clean concentrator vial. Rinse the copper
powder with three additional 5-mL aliquots of n-hexane and add rinses to the
vial.
11.7.5 The extract is concentrated to 1 mL. Proceed to Section 11.8 for silica gel
cleanup.
11.8 Silica Gel Cleanup
¦ 11.8.1 Place a glass-wool plug in a 15-mm ID chromatography column
(Section 6.5.2.2). Pack the column bottom to top with 1 g silica gel
(Section 7.4.11), 4 g basic silica gel (Section 7.4.1.3), 1 g silica gel, 8 g acid
silica gel (Section 7.4.1.2), 2 g silica gel, and 4 g granular anhydrous sodium
sulfate (Section 7.2.1). Tap the column to settle the adsorbents.
11.8.2 Pre-elute the column with 50 to 100 mL of n-hexane. Close the stopcock when
the n-hexane is within 1 mm of the sodium sulfate. Discard the eluate. Check
the column for channeling. If channeling is present, discard the column and
prepare another.
~ 11.8.3 Apply the concentrated extract to the column. Open the stopcock until the
extract is within 1 mm of the sodium sulfate.
11.8.4 Rinse the receiver twice with 1-mL portions of n-hexane, and apply separately
to the column. Elute the PCBs with 75 mL of n-hexane and collect the eluate.
11.8.5 Concentrate the eluate per Section 11.6 and proceed to Section 11,9 for carbon
column cleanup.
11.8.6 For extracts of samples known to contain large quantities of other organic
compounds, it may be advisable to increase the capacity of the silica gel
column. This may be accomplished by increasing the strengths of the acid and
basic silica gels. The acid silica gel (Section 7.4.1.2) may be increased in
29
N-94
-------
strength to as much as 44% w/w (7.9 g sulfuric acid added to 10 g silica gel).
The basic silica gel (Section 7.4.1.3) may be increased in strength to as much as
33% w/w (50 mL IN NaOH added to 100 g silica gel). Additional acid silica
(only) columns may be used until the extract has no appearance of color.
•• *
11.9 Carbon Column Cleanup
11.9.1 Cut both ends from a 50-mL disposable serological pipet (Section 6.5.1.2) to
produce a 20-cm column. Fire-polish both ends and flare both ends if desired.
Insert a glass-wool plug at one end, and pack the column with 3.6 g of
Carbopak/Celite (Section 7.4.2.3) to form an adsorbent bed 20 cm long. Insert a
glass-wool plug on top of the bed to hold the adsoibent in place.
11.9.2 Pre-elute the column with 20 mL each in succession of methylene chloride, and
n-hexane.
11.9.3 When the solvent is within 1 mm of the column packing, apply the n-hexane
sample extract to the column. Rinse the sample container twice with 1-rnL
portions of n-hexane and apply separately to the column. Apply .2 mL of n-
hexane to complete the transfer. •
11.9.4 Elute the column with 25 mL of n-hexane and collect the eluate. This fraction
will contain the mono- and di-ortho PCBs.
11.9.5 Elute the column with 15 mL of methanol and archive the eluate. This fraction
will contain residual lipids and other potential interferents, if present.
11.9.6 Elute the column with 15 mL of toluene and collect the eluate. This fraction will
contain PCBs 77,126, and 169.
11.9.7 Combine the first and third fractions. If carbon particles are present in the
combined eluate, filter through glass-fiber filter paper.
11.9.8 Concentrate the combined elute to 1 mL using rotary evaporation, K-D, or
Turbovap (Section 11.6).
11.9.9 Proceed to Section 11.10 for HPLC/GPC cleanup.
11.10 High Performance Liquid Chromatography (HPLC)/Gel Permeation Chromatography
(GPC)
11.10.1 GPC columns
Purchased pre-packed (see Section 6.5.3.7).
30
N-95
-------
11.10.2 HPLC fractionation time determination
11.10.2.1 Analyze the HPLC fractionation time standard (Section 7.5.10) at
least twice. If the RT differences between runs is greater than 0.1
,min, reanalyze until acceptable RTs are obtained from two
consecutive runs.
11.10.2.2 Set the collection window to allow for the collection of solvent
between 0.5 minutes after the elution time of DBOFB to 0.5
minutes after the elution time of perylene (Section 7.7).
11.10.2.3 The collection window should allow for the inclusion ofPCBs
from the extract, while eliminating contaminants such as lipids and
sulfur.
11.10.2.4 Verify the calibration every 10 to 12 samples.
11.10.3 Extract cleanup
Filter the extract to remove any particulates.
Load the extract onto the autosampler and inject 600 p.L onto the
HPLC.
Elute the extract using the calibration data determined in
Section 11.10.2.
Collect the eluate in a clean 60 mL fraction collector vial/tube. If a
particularly dirty extract is encountered, a methylene chloride
blank shall be run through the system to check for carry-over
Proceed to Section 11.11 for concentration to final volume.
11.11 Concentration to Final Volume
11.11.1 The extract is concentrated in a calibrated concentrator tube to a final volume
of 20 (J.L to 1 mL, par the analyst's discretion, under a gentle stream of
nitrogen. A final extract volume of 150 jxL is recommended based on the
limited method demonstration.
11.11.2 Add 15 fiL of the recovery standard spiking solution (Section 7.6.5) to the
sample extract.
31
11.10.3.1
11.10.3.2
11.10.3.3
11.10.3.4
11.10.3.5
N-96
-------
11.12 HRGC/HRMS Analysis
11.12.1 Establish the operating conditions given in Section 10.1, perform initial
calibration if necessary (Section 10.2), or verify calibration (Section 10.3).
11.12.2 If an extract js to be reanalyzed and evaporation has occurred, do not add more
recovery standard solution. Instead, bring the extract back to its previous
volume (e.g., 19 pL, or 18 jtL if 2 (iL injections are used) with pure nonane.
11.12.3 Inject 1,0 or 2.0 jiL of the concentrated extract containing the recovery
standard solution, using on-column or splitless injection. The volume injected
must be identical to the volume used for calibration (Section 10.1.3.1).
11.12.4 Start the HRGC column initial isothermal hold upon injection. Start HRMS
data collection after the solvent peak elutes. Stop the data collection after the
uCi2-PCB 209 has eluted. Return the column to the initial temperature for
analysis of the next extract or standard.
12.0 DATA ANALYSIS AND CALCULATIONS
12.1 Qualitative Determination
A PC3 analyte or labeled compound is identified in a standard, blank, or sample when
all of the criteria in Sections 12.1.1 through 12.1.4 are met. If the criteria for
identification in Sections 12.1.1-12.1.4 are not met, the PCB analyte has not been
positively identified. If interferences preclude identification, an estimated maximum
possible concentration (EMPC) can be reported (Section 12.2.6), or a new aliquot of
sample may be extracted, further cleaned up, and analyzed.
-12.1.1 The signals for the two exact m/z's in Table 6 must be present and must
maximize within the same two seconds.
12.1.2 The signal-to-noise ratio (S/N) for the GC peak at each exact m/z must be
greater than or equal to 2.5 for each PCB detected in a sample extract, and
greater than or equal to 10 for all PCBs in the calibration standard (Section
7.6.6).
12.1.3 The ratio of the integrated areas of the two exact m/z's specified in Table 6
must be within the limit in Table 7, or within ±10 percent of the ratio in the
midpoint (CS3) calibration or calibration verification (VER), whichever is
most recent.
32
N-97
-------
12.1.4 The relative retention time of the peak for a toxic PCB must be within ± 15
seconds of the retention times obtained during calibration.
12 ? Quantitative Determination
12.2.1 For gas chromatographic peaks that have met the criteria outlined in Section
12.1, calculate the concentration of the PCB compounds in the extract, using
the formula:
c Q «
x ~~ At X RF„ X W3
where:
C, ¦ concentration of unlabeled PCB congeners in the sample (pg/g, dry weight),
Ax ¦ sum of the integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for unlabeled PCBs,
Ak ~ sum of the integrated ion abundances of the quantitation ions (Tables 2,3 and
6) for the labeled internal standards,
Qh ~ quantity, in pg, of the internal standard added to the sample before extraction,
RF, - calculated mean relative response factor for the analyte ( RFm with n=l to 13;
\ Section 10.2.1),
; w, - weight of sample extracted (g, dry weight),
12.2.2 Calculate the percent recovery of the internal standards measured in the sample
extract, using the formula:
A. x Q
Percent recovery — — x 100
QisxArsxRFis
where;
Ak * sum of the integrated ion abundances of the quantitation ions (Tables 2, 3
and 6) for the labeled internal standard,
A„ •* sum of the integrated ion abundances of the quantitation ions (Tables 2, 5
and 6) for the labeled recovery standard,
Qa ¦ quantity, In ng, of the internal standard added to the sample before
extraction,
Qn - quantity, In ng, of the recovery standard added to the cleaned sample
extract before HM.GC/HRMS analysis, and
RFk » calculated mean relative response factor for the labeled internal standard
relative to the appropriate recovery standard. This represents the mean
obtained in Section 10.2.2 (RF„with is -14 to 23, Table 3).
33
N-98
-------
The percent recovery of the cleanup standards is calculated similarly.
The percent recovery should meet the criteria shown in Table 5. If
recoveries are outside the limits of Table 5, the data should be flagged
and the impact on reported results discussed in the final report.
12.2.3 Outside Calibration Range
12.2.3.1 If the SICP area at either quantitation mlz for any compound exceeds
the calibration range of the system, the extract must be diluted and
re-analyzed.
12.2.3.2 Dilute the sample extract by a factor of 10, adjust the concentration
of the recovery standard to 100 pg/^iL in the extract, and analyze an
aliquot of this diluted extract.
12.2.4 Estimated Detection Limit (EDL)
2.5 (Hls+ H2S) (Qfc)
EDL (pg/ g)-
(Hljs* (t&n)
-------
12.2.6.1 Sewage Sludge—Report results in pg/g based on the dry weight of
the sample.
12.2.6.2 Blanks—Report results above the EDL. Do not blank-correct results.
If a blank accompanying a sample result shows contamination above
the EDL for the congener, flag the sample result and report the
results for the sample and the accompanying blank.
12.2.6.3 Dilutions (Section 12.2.3.2)
Results for PCB analytes in samples that have been diluted; for this
EPA project, both the undiluted and diluted PCB results are to be
reported, whether or not all of the analytes are within the calibration
range.
12.2.6.4 Non-Detects
Note the non-detected PCB analytes as ND and report the estimated
detection limit established during the analysis
\
13.0 METHOD PERFORMANCE
13.1 In a limited single laboratory demonstration of this method for sewage sludge samples,
estimated detection limits of approximately 40 pg/g were achieved for pentachlorinated
biphenyl (PeCB); 65 pg/g for hexachlorinated biphenyl (HxCB); and 55 pg/g for
heptachlorinated biphenyl (HpCB).
13.2 Interlaboratory testing of this method to determine overall precision and bias has not beer,
performed.
14.0 POLLUTION PREVENTION
None.
15.0 WASTE MANAGEMENT
PCB waste should be disposed of according to Toxic Substances Control Act (TSCA)
guidelines 40CFR 700-789, and hazardous waste should be disposed of according to
Resource Conservation and Recovery Act (RCRA) guidelines 4GCFR 260-269.
35
N-100
-------
16.0 REFERENCES
1. Syhre, M., Hanschmann, G., and Heber, R. J. of AOACInter., Vol. 81, No. 3,513- 517
(1998).
2. 'Toxic Polychlorinated Biphenyls by Isotope Dilution High Resolution Gas
Chromatography/High Resolution Mass Spectrometry," U.S. EPA Method 1668, March,
1997.
3. Ob ana, H, Kikuchi, K., Okihashi, M., and Shinjiro, H. Analyst, Vol. 122,217-220 (1997).
4. Loos, R., Vollmuth, S., and Niessner, R Fres. J. Anal Chem, 357(8), 1081-1087 (1997).
. * 5. Ferrario, J., Byrne, and Dupuy, A.E. Jr. Organohalogen Compounds (Dioxin '96), 123-
127 (1996).
6. AWborg, U.G., Becking, G.C., Bimbaum, L.S., Brouwer, A., Derks, H J.G.M., Feeley, M.,
Golor, G., Hanberg, A., Larsen, J.C., Liem, A.K.D., Safe, S.H., Schlatter, Waern, F.,
Younes, M., and Yiianbeikki, Chemosphere, Vol. 28, No. 6,1049-1067 (1994).
7. Strandell, M.E., Lexen, K.M., deWit, C.A., Jaemberg, U.G., Jansson, B., Kjeller, L-O.,
Kulp, S-E., Ljung, K., Soederstroem, G., et al. Organohalogen Compounds (Dioxin '94),
363-366 (1994).
8. Ramos, L., Blanch, G.P., Hernandez, L., Gonzalez, M.J., J. Chromatography A, Vol. 690,
243-249 (1994).
9. Fitzgerald, E.F., Hwang, S.A., Brix, K., Bush, B., and Cook, K., Organohalogen
Compound5 (Dioxin '94), 495-500 (1994).
10. Lazzari, L., Spemi, L., Salizzato, M., and Pavoni, B., Chemosphere, Vol. 38, No. 8, 1925-
1935 (1999).
11. Sewart, A.. Harrad, S J., McLachlan, M.S., McGrath, S.P., and Jones, K.C., Chemosphere,
Vol. 30, No. 6,51-67 (1995).
12. "Sulfur Cleanup," U.S. EPA SW 846 Method 3660 B, Rev, 2, December, 1996.
13. Dupont, G., Delteil, C., Camel, V., and Bermond, A., Analyst, Vol. 124,453-458 (1999).
14. "Standard Guide for General Planning of Waste Sampling," ASTM D 4687,48-55 (1995).
36
N-101
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17.0 TABLES AND FIGURES
Table 1. Toxic Polychlorinated Biphenyls Determined by High Resolution Gas Chioinatosrsphy
(HRG€)/High Resolution Mass Spectrometry (HRMS)
Native compound
ItTAC
FCBJ
CAS Registry No.
No.2
Target Analytes
3,3',4,4'-TCB
32598-13-3
77
2,3,3*,4,4'-PeCB
32598-14-4
105
2,3,4,4',5-PeCB
74472-37-0
114
2,3',4,4',5-PeCB
31508-00-6
118
2',3,4,4',5-PeCB
65510-44-3
123
3,3',4,4',5-PeCB
57465-28-8
126
2,3,3',4,4',5-HxCB
38380-08-4
156
2,3,3',4,4',5'-HxCB
69782-90-7
157
2,3',4,4',5,5'-HxCB
52663-72-6
167
32774-16-6
169
2,2',3,3',4,4',5-HpCB
35065-30-6
170
2,2',3,4,4\5,5'-HpCB
35065-29-3
180
23,3',4,4',5,5-HpCB
39635-31-9
189
Internal Standards
33'»4,4'-TCB
160901-67-7
77L
2,3,3',4,4'-PeCB
160901-70-2
105L
2,3,4,4',5-PeCB
160901-72-4
114L
2,3',4,4',5-PeCB
160901-73-5
118L
2',3,4,4',5-PeCB
160901-74-6
123L
3,3',4,4',5-PeCB
160901-75-7
126L
2,3,3',4,4',5-HxCB
160901-77-9
156L
2,3,3,,4,4',5,-HxCB
160901-78-0
157L
2,3',4,4'J5,5'-HxCB
161627-18-5
167L
3,3',4,4',5,5'-HxCB
160901-79-1
169L
2,2',3,3',4,4',5-HpCB
160901-80-4
170L
2^',3,4,4',5,5'-HpCB
160901-82-6
180L
2,3,3',4,4',5,5l-HpCB
160901-83-7
189L
Cleanup Standards
uCu-3,4,4',5-TCB
160901-68-8
81
"C l2-2,3,3 ',5,5'-PeCB
160901-71-3
111
Recovery Standards
uCir2,2,,5t5,-TGB
160901-66-6
52
I3Cl2-2,2',4,4,5'-PeCB
160901-69-9
101
uCl2-2r2'3»4l4'^,-HxCB
160901-76-8
138
uCl2-2^'3,3,,5,5,,6-HpCB
160901-81-5
178
Final Eluter Standard
UCU-DCB
160901-84-8
209
1 Polychlorinated biphenyls:
TCB - Tetrachlorobiphenyl
PeGB ¦ Pentachlorobiphenyl
HxCB - Hexachlotobiphenyl
HpCB - Heptachlorobiphenyl
DCB - Decachlorobiphenyl
1 Suffix "L" designates a labeled compound.
37
M-109
-------
Table 2.
Retention Time (RT) References, Quantitation References, and Retention Times
(RTs) for the Toxic PCBs
IUPAC
IUPAC
Retention time and
RT2
No.1
PCB congener
No.1
quantitation reference
(min)
52L
13C12-2^'^3'-TCB
_3
13C12-2,2',5,5'-TCB
28.66
81L
13C12-3,4,4',5-TCB4
52L
13C12-2,2',5,5'-TCB
37.89
77L
13C12-3,3*,4,4'-TCB
52L
13C12-2T2',5,5'-TCB
38.85
77
3,3\4,4'-TCB
77L
13Cl2-3,3'.4,4'-TCB
38.85
1G1L
13C12-2,2',4,5,5'-PeCB
_
13 C12-2,2',4,5,5-PeCB
35.02
111L
13C12-2,3,3',5,5'-PeCB4
101L
13C12-2^,4,5,5'-PeCB
37.13
123
2',3,4,4',5-PeCB
118L
13C12-2,3',4,4',5-PeCB
• 39.90
118L
13C12-2,3',4,4',5-PeCB
101L
13C12-2,2',4,5,5'-PeCB
40.17
118
2,3',4,4',5-PeCB
118L
13C12-2,3',4,4',5-PeCB
40.17
114
2,3,4,4',5-PeCB
105L
13C12-2,3J3,,4,4'-PeCB
40.79
105L
13C12-2,3,3',4,4'-PeCB
101L
13C12-2^54,5,5'-PeCB
42.22
105
2,3,3',4,4'-PeCB
105L
13 C12-2,3,3 ',4,4'-PeCB
42.22
126L
13 C12-3,3 ',4,4',5-PeCB
101L
13C12-2,2',4,5,5'-PeCB
44.75
126
3,3',4,4',5-PeCB
126L
13Cl2-3,3'.4,4\5-PeCB
44.75
138L
13C12-2,2,,3J4,4',5,-HxCB
—
13C12-2,2',4f5,5'-PeCB
43.23
167L
13C12-2,3 's4,4',5,5-HxCB
138L
13C12-2,2',3,4,4',5'-HxCB
45.72
167
2,3',4>4',5,5'-HxCB
167L
13C12-2,3,,4,4',5,5,-HxCB
45.72
156L
13C12-2,3,3'»4,4',5-HxCB
138L
13 CI 2-2,2',3,4,4', 5'-HxCB
47.37
157L
13C12-2,3,3 ',4,4',5 '-HxCB
138L
13C12-2^',3I4,4',5'-HxCB
47.79
156
2,3,3',4»4',5-HxCB
156L
13C12-2,3,3',4,4',5-HxCB
47.37 ¦
157
2,3,3 '.4,4',5 '-HxCB
157L
13C12-2,3,3,,4,4,,5,-HxCB
47.79
169L
13C12-3,3,,4,4',5,5,-HxCB
138L
13C12-2^',3,4,4',5'-HxCB
50.25
169
3,3',4,4',5,5'-HxCB
169L
13C12-3,3\4,4',5,5'-HxCB
50.25
178L
13C12-2^,,3,3',5,5,,6-HpCB
—
13C12-2^',4,5,5'-PeCB
42,88
180L
i 3012-2,2',3,4,4*,5,s'-HpCB
178L
13C12-2,2',3,3',5,5',6-HpCB
47.88
180
2,2',3,4,4',5,5'-HpCB
180L
13C12-2,2',3,4,4',5,5 '-HpCB
47.88
170
2^,3,3' 4,4',5-HpCB
180L
13C12-2,2',3,4,4',5,5'-HpCB
49.90
189L
13C12-2,3,3',4,4',5,5'-HpCB
J78L
13C12-2^',3,3,,5,5',6-HpCB
52.56
189
2,3,3',4,4',5,5-HpCB
189L
13C12-2,3,3',4,4,,5,5'-HpCB
52.56
209L
1 "C12-DCR5
17MT
56.63
1 Suffix "L" indicates labeled compound.
2 Retention time data are for HT-8 column (per manufacturer).
3 Internal standards.
4 Cleanup standard.
5 Final eluter.
38
N-103
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Table 3.
Concentrations of Stock and Spiking Solutions Containing the Native PCBs and
Labeled Compounds
Spiking Spiking
m/z Stock3 Solution2 Level
Cpd. No. Compound , . type (ug/mL) (ng/mL) (ng)
Precision and Recovery Standards'
1
3,3',4,4-TCB
77
20
0.8
0.8
2
2f3,3't4,4'-PeCB
105
1000
40
40
3
2,3,4,4',5-PeCB
114
1000
40
40
4
2,3',4,4',5-PeCB
118
1000
40
40
5
2',3,4,4\5-PeCB
123
1000
40
40
6
3,3',4,4',5-PeCB
126
100
4
4
7
2,3,3',4,4',5-HxCB
156
1000
40
40
8
2>3,3',4,4',5'-HxCB
157
1000
40
40
9
2,3',4,4',5,5,-HxCB
167
1000
40
40
10
3»3'A4,,5,5,-HxCB
169
200
8
8
11
2,2'3,3',4,4',5-HpCB
170
200
8
8
12
2t2',3,4,4,,5,5'-HpCB
180
1000
40
40
13
2,3,3',4,4,f5,5,-HpCB
Internal Standards4
189
200
8
8
14
13C12-3,3,,4,4,-TCB
77L
1000
50
50
\s
13C12-2,3,3',4,4'-PeCB
105L
1000
50
50
16
13C12-2,3*,4,4',5-PeCB
118L
1000
. 50
50
17
13C12-3,3,,4,4',5-PeCB
126L
1000
50
50
18
13 C12-2,3,3 ',4,4',5-HxCB
156L
1000
50
50
19
13C12-2,3,3',4,4',5'-HxCB
157L
1000
50
50
20
13C12-2,3',4,4',5,5'-HxCB
167L
1000
50
50
21
13C12-3,3'>4,4',5,5'-HxCB
169L
1000
50
50
22
13C12-2t2,,3,4,4,)5,5'-HpCB
180L
1000
50
50
23
13C 12-2,3,3 ',4,4',5,5'-HpCB
Cleanup Standards'
189L
1000
50
50
24
13 C12-3,4,4',5-TCB
81L
200
10
10
25
13C12-2,3^',5,5'-PeCB
Recovery Standards*
111L
1000
50
50
26
13C 12-2,2',5,5-TCB
52L
1000
1000
15
27
13C12-2^,,4,5,5,-PeCB
101L
1000
1000
15
28
13C12-2^',3,4,4',5,-HxCB
138L
1000
1000
15
29
13C 12-2,2',3,3 ',5,5',6-HpCB
Final Eluter
178L
1000
1000
15
30
13C12-DCB
209L
2000
100
100
1 Section 7.6.7-prepared is nonane and diluted to prepare spiking solution.
1 Sections 7.6.3.2,7.6.4., 7.6.5,7.6.7-prepared in acetone from stock solution daily.
1 Section 7.6.1-prepared in nonane and diluted to prepare spiking solution. Concentrations are adjusted for
expected background levels.
4 Section 7.6.3.2-prepared in acetone from stock solution daily. Concentrations are adjusted for expected
background levels.
5 Section 7.6.4-prepared in acetone; added to sanqsle extracts before cleanup.
4 Section 7.6.5-prepared in nonane; added to concentrated extract prior to injection.
39
N-104
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Table 4. Concentrations ofPCBs in Calibration and Calibration Verification Solutions
IUPAC
CS1
CS2
CS3J
CS4
CSS
No.1
(ng/mL)
(ng/mL)
(ng/mL)
(ng/mL)
(ng/ral
Precision and Recovery
-
Standards
3,3\4,4'-TCB
77
0.5
2
10
40
200
2,3,3',4,4-PeOB
105
2.5
10
50
200
1000
2,3,4,4',5-PeOB
114
2.5
10
50
200
1000
2,3',4,4',5-PeCB
118
2.5
10
50
200
1000
2',3,4,4',5-PeCB
123
2.5
10
50
200
1000
3,3',4,4',5-PeCB
126
2.5
10
50
200
1000
2,3,3',4,4',5-HxCB
156
5
20
100
400
2000
2,3,3 ',4,4', 5-HxCB
157
5
20
100
400
2000
2,3',4,4',5,5'-HxCB
167
5
20
100
400
2000
3,3',4,4',5,5'-HxOB
169
5
20
100
400
2000
2,2',3,3',4,4',5-HpCB
170
5
20
100
400
2000
2,2',3,4,4',5,5'-HpOB
180
5
20
100
400
2000
2,3,3',4,4',5,5'-HpCB
189
5
20
100
400
2000
Internal Standards
_
l£C12-3,3',4,4'-TCB
77L
100
100
100
100
100
13C12-2f3,3\4,4'-PeCB
- 105L
100
100
100
100
100
13 C12-2,3 ',4,4',5-PeCB
118L
100
100
100
100
100
13012-3,3',4,4»,5-PeOB
126L
100
100
100
100
100
13012-2,3,3', 4,4',5-HxOB
156L
100
100
100
100
100
13 C12-2,3,3 ',4,4',5'-HxCB
. 157L
100
100
100
100
100
13C12-2,3',4,4,,5,5,-HxCB
167L
100
100
100
100
100
13012-3,S'^'^S'-HxCB
169L
100
100
100
too
100
13C12-2,2',3,4,4',5,5'-HpCB
180L
100
100
100
100
100
13C12-2,3,3',4,4',5,5'-HpCB
189L
100
100
100
100
100
Cleanup Standards
13012-3,4,4',5-TOB
81L
0.5
2
10
40
200
13012-2,3,3', 5,5-PeCB
111L
2.5
10
50
200
1000
Recovery Standards
13012-2,2',5,5-TOB
52L
100
100
100
100
100
13012-2,2',4,5,S'-PeCB
101L
100
100
100
100
• 100
l3Cl2-2^.',3,A,
138L
100
100
100
100
100
13012-2,2',3,3',5,5',6-HpCB
178L
100
100
100
100
100
Final Eiuter
13012-DCB
209L
200
200
200
200
200
1 Suffix 'X" indicates labeled compound.
2 Sections 7.6.6, calibration verification solution.
40
N-105
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Table 5. Labeled Compound Recovery in Samples When All PCBs are Tested
Labeled compound
Test recovery
IUPAC cone :
Labeled PCB No. (ng/mL)1 (ng/mL) (e/o)
Internal Standards
l3Cl2-3,3,,4,4'-TCB
77
100
20-160
20-160
l3Cl2-2,3,3',4,4'-PeCB
105
100
20-160
20-ICC
13 C12-2,3',4,4',5-PeCB
l IS
100
20-160
20-160
l3Cl2-3,3'»4,4',5-PeCB
126
100
20-160
20-160
l3Cl2-2,3,3',4f4',5-HxCB
156
100
20-160
20-160
13C12-2,3,3,»4»4',5'-HxCB
157
100
20-160
20-160
13C12-2,3',4,4',5,5'-HxCB
167
100
20-160
20-160
l3Cl2-3,3',4,4',5,5-HxCB
169
100
20-160
20-160
l3Cl2-2^,3,4,4^,5'-HpCB
180
100
20-160
20-16C
l3Cl2-2,3,3',4,4',5,5'-HpCB
189
100
20-160
20-160
Cleanup Standards
l3Cl2-3,4,4',5-TCB
81
50
4-32
20-160
l3Cl2-2,3,3'»5,5'-PeCB
111
250
40-140
40-140
1 Based on 20 fiL final extract volume.
41
M 1Afi
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Table 6. Descriptors, Exact m/z's, m/z Types, and Elemental Compositions of the PCBs
Exact
m/z
Descriptor
m/z1
type
Elemental composition
Snbstance7
1.
289.9224
" M
C12 H6 35C14
TCB
291.9194
M+2
C12 H6 35C13 37C1
TCB
301.9626
M -
13C12 H6 35C14
TCB1
303.9597
M+2
13C12 H6 350 3 370
TCB*
318.9792
Lock Mass
—
PFK
325.8804
M+2
C12 H5 35C14 37C1
PeCB
327.8775
M+4
C12 H5 35C13 37C12
PeCB
330.9793
Lock Mass Check
_
PFK
337.9207
M+2
13C12 H5 35C14 37C1
PeCBJ
339.9178
M+4
13C12 H5 35C13 37C12
PeCB5
2.
325.8804
M+2
C12 H5 35C14 37C1
PeCB
327.8775
M+4
C12 H5 35C13 37C12
PeCB
-337.9207
M+2
13C12 H5 35C14 37C1
PeCB1
339.9178
M+4
13C12 H5 35C13 37C12
PeCB1
354.9792
Lock Mass
_
PFK
354.9792
Lock Mass Check
—
PEK
393.8025
¦ M+2
C12 H3 35C16 37C1
HpCB
395.7996
M+4
C12 H3 35C15 37C12
HpCB
405.8428
M+2
13C12 H3 35Q6 37C1
HpCB*
407.8398
M+4
13C12 H3 35C15 37C12
HpCB1
3.
359.8415
M+2
C12 H4 35C15 37C1
HxCB
361.8385
M+4
C12 H4 35C14 37C12
XIawD
371.8817'
M+2
13C12 H4 35C15 37C1
HxCBJ
373.8788
M+4
13C12 H4 35C14 37C12
HxCB1
380.9760
Lock Mass
_
PFK
380.9760
Lock Mass Check
_
PFK
393.8025
M+2 ¦
C12 H3 35C16 37C1
HpCB
395.7996
M+4
C12 H3 35C15 37C12
HpCB
405.8428
M+2
13C12 H3 35C16 37C1
HpCBJ
407.8398
M+4
13C12 H3 35C15 37C12
HpCB1
4,
504.9696
Lock Mass
—
PFK
504.9696
Lock Mass Check
—
PFK
509.7229
M+4
13C12 35C18 37C12
DCBJ
511 7199
M+6
13C12 35C17 37C13
TX7RJ
1 Nuclidic masses used were:
H « 1.007825 C - 12.00000
13C = 13.003355 35Q-34.968853 37C1« 36.965903
3 TCB - Tetrachlorobiphrayi
PeCB ¦= Pentachlorobiphenyl
HxCB = Hexachlorobiphenyl
HpCB - Heptachlorobiphenyl
DCB Decicblorobiphenyl.
¦' 13C labeled compound.
42
N-107
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Table 7. Theoretical Ion Abundance Ratios and QC Limits
Chlorine
atoms
m/z's forming
ratio
Theoretical
ratio
QC Limit1
Lower
Upper
4
M/(M+2)
0.77
0.65
0.89
5
(M+2)/(M+4)
1.55
1.32
1.78
6
(M+2)/(M+4)
124
1.05
1.43
7
(M+2)/(M+4)
1.05
0.88
1.20
10
(M+4)/(M+6)
1,17
0.99
1.35
1 QC limits represent +/-15 percent windows around the theoretical ion abundance ratio. These limits
are preliminary.
43
N-108
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Table 8. GC Retention Time Window Defining and Isomer Specificity Test Solution1
(Section 7.6.8) •
Congener
group • - First elnted Last eluted
TCB
54
2,2',6,6'
77 '
3,3',4,4'
PeCB
104
2?, 4,6,6'
126
3,3',4,4',5
HxCB
155
2,2', 4,4', 6,6'
169
3,3',4,4',5,5'
HpCB
188
2,2',3,4',5,6,6'
189
2,3,3',4,4',5,5'
Isomer specificity test compounds
123
2',3,4,4',5-PeCB
156
2,3,3 ',4,4',5-HxCB
118
2,3',4,4',5-PeCB
157
2»3,3',4,4',5'-HxCB
1 All compounds are at a concentration of 100 ng/mL in nonane.
44
N-109
-------
Spike with Cleanup
Standard
Soxblet Extract
Concentrate to 10 mi-
Mix with Drying Agent
to Produce 1:1 Ratio
Sewage Sludge Sample
Solvent Exchange 5 mL
of Sample Extract to
Hexane (50 mL)
Proceed to Sample
Cleanup Flow Diagram
(Figure 2)
Spike with Labeled
fntamal Standards
Take 2 g Aliquot of wet
sample
Determine Percent
Moisture of 10 g aliquot
Figure 1. Sample Extraction Procedure for Sewage Sludge Sample
45
N-110
-------
" '"Repeat this step until the
aqueous layer is clear
HRGC/HRMS
Analyses
Discard the
Aqueous Layer
Discard the
Aqueous Layer
Discard the
Aqueous Layer
Add Recovery
Standard Solution
Carbon Column
Cleanup
Silica Gel
Cleanup
Concentrate
to Final Volume
Sulfur Cleanup
Using Copper
Extract Hexane Extract
with Sulfuric Acid*
Discard the
Aqueous Layer
Extract the Hexane
with
KOH Solution
Wash the Hexase
Layer with
Nad Solution
Wash the Hexane
Layer with NaCl
Solution
See Figure 1 for
Description of
Sample Extraction
Figure 2. Sample Cleanup Procedure for Sewage Sludge Sample
46
N-111
-------
N-l-3
Draft Scrubber Water Method
N-112
-------
Proposed Analytical Method
Determination of Toxic Polychlorinated Biphenyls in Sewage
Incinerator Scrubber Water nsing Isotope Dilution High Resolution
Gas Chromatography/High Resolution Mass Spectrometry
July 20,1999
Prepared by
Marielle C. Brinkman
Study Coordinator
And
Jane C. Chuang
Work Assignment Leader
for
C.E. (Gene) Riley
Work Assignment Manager
Katby Weant
Project Officer
Emissions, Monitoring, and Analysis Division
Office of Air Quality Planning and Standards
U.S. Environmental Protection Agency
BatteUe
505 King Avenne
Columbus, Ohio 43201-2693
N-113
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Proposed Analytical Method for Determination of Toxic Polychlorinated
Biphenyls in Sewage Incinerator Scrubber Water by Isotope Dilution ffigit
. Resolution Gas Chromatography/High Resolution Mass Spectrometry
1.0 SCOPE AND APPLICATION
1.1 This analytical method is for determination of the toxic polychlorinated biphenyls (PCBs)
in sewage incinerator scrubber water by high resolution gas chromatography/high
resolution mass spectrometry (HRGC/HRMS), The method is for use in the Emission
Measurement Center's (EMC) data gathering effort to support a Maximum Achievable
Control Technology (MACT) standard to limit emissions of hazardous air pollutants at
two sewage sludge incinerators. The method is based on a compilation of methods from
the technical literature, and EPA Method 1668 (References 1-14).
1.2 The toxic PCBs listed in Table 1 may be determined by this method.
1.3 The detection limits and quantitation levels listed in this method may be dependent on the
level of interferences rather than instrumental limitations.
1.4 The HRGC/HRMS portions of this method are for use only by analysts experienced with
HRGC/HRMS, or under the close supervision of such qualified persons.
2.0 SUMMARY OF METHOD
2.1 Extraction
An analytical flow diagram depicting the scrubber water extraction procedure is shown in
Figure 1. _
2.1.1 Scrubber water samples (samples containing s 5% solids upon visual inspection)
- 2.1.1.1 Stable isotopically labeled analogs of tile toxic PCBs are spiked into a
1 L sample, and die sample is vacuum-filtered through a Ci, solid-phase
extraction (SPE) column.
2.1.1.2 The column is eluted with acetone and methylene chloride, the eluant i s
concentrated for cleanup and spiked with cleanup standard
2.1.2 Scrubber water samples (samples containing > 5% solids upon visual inspection)
1
N-114
-------
AIL aliquot of the sample is filtered; the filtrate is spiked with stable
isotopically labeled analogs of the toxic PCBs, and the sample is
vacuum-filtered through a Clg solid-phase extraction (SPE) column.
The column is eluted with acetone and methylene chloride.
The soHds are extracted using the Soxhlet technique, and the filtrate
extract and the solids extract are combined, concentrated, and spiked
with cleanup standards.
2.2 An analytical flow diagram depicting the scrubber water cleanup procedure is shown in
Figure 2. The scrubber water extract is cleaned using acid and base partitioning, and silica
gel and activated carbon chromatography.
2.3 After cleanup, the extract is concentrated to a final volume between 20 fiL - 1.0 mL, per
the analyst's discretion. Prior to injection recovery standards are added to each extract,
and an aliquot of the extract is injected into the gas chromatograph. The analytes are
separated by the GC and detected by a high resolution mass spectrometer. Two exact
m/z's are monitored for each analyte.
2.4 An individual PCB congener is identified by comparing the GC retention time and ion-
abundance ratio of two exact m/z's with the corresponding retention time of an authentic
standard and the theoretical or acquired ion-abundance ratio of the two exact m/z's.
Isomer specificity for the toxic PCBs is achieved using GC columns that resolve these
congeners from the other PCBs.
2.1.2.1
2.1.2.2
2.1.2.3
2.5 Results are quantified using relative response factors.
2.6 The quality of the analysis is assured through reproducible calibration and verification of
operation for the extraction, cleanup, and GC/MS systems.
3.0 DEFINITIONS AND ABBREVIATIONS
3.1 Definitions and Acronyms
3.1.1 Analyte - a PCB compound measured by this method. The analytes are listed in
Table 1.
3.1.2 Calibration Standard (CS) - a solution prepared from a secondary standard
and/or stock solutions and used to calibrate the response of the instrument with
respect to analyte concenu-ation.
2
N-115
-------
3.1.3 Calibration Verification Standard (VER) - the mid-point calibration standard
(CS3) that is used to verify calibration (see Table 4).
3.1.4 Congener - refers to a particular compound of the same cher"'"*1
3.1.5 CS1, CS2, CS1, CS4, CSS - see calibration standards in Table 4.
3.1.6 Field Blank - an aliquot of reagent water or other reference matrix that is placed
in a sample container in the laboratory or the field, and treated as a sample in all
respects, including exposure to sampling site conditions, storage, preservation,
and all analytical procedures. The purpose of the field blank is to determine if ih:
field or sample transporting procedures and environments have contaminated the
sample.
3.1.7 HRGC - high resolution gas chromatography or gas chromatograph,
3.1.8 HRMS - high resolution mass spectrometry or mass spectrometer.
3.1.9 Internal Standard (IS) - a component which is added to every sample and is
present in the same concentration in every blank, quality control sample, and
calibration solution. The IS is added to the sample before extraction and is used
to measure the concentration of the analyte and surrogate compound. The IS
recovery serves as an indicator of the overall performance of the analysis
3.1.10 K-D - Kudema-Danish concentrator; a device used to concentrate the analytes ir
a solvent.
3.1.11 Laboratory Blank - see Laboratory Method Blank.
3.1.12 Laboratory Method Blank - an aliquot of reagent water or solvent that is trent?
exactly as a sample including exposure to all laboratory glassware, equipment
solvents, reagents, internal standards, and surrogates that are used with sample -
The laboratory method blank is used to determine if analytes or interferences ar
present in the laboratory environment, the reagents, or the apparatus.
3.1.13 Laboratory Spike Sample - a laboratory-prepared matrix blank spiked with
known quantities of analytes. The laboratory spike sample is analyzed exactly like
a sample. Its purpose is to assure that the results produced by the laboratory
remain within the limits specified in the method for precision and recovery.
3.1.14 May - this action, activity, or procedural step is neither required nor prohibited
3.1.15 May not - this action, activity, or procedural step is prohibited.
3.1.16 Must - this action, activity, or procedural step is required.
3
N-110
-------
3.1.17 m/z Scale - the molecular mass to charge ratio scale.
3.1.13 PAR - precision and recovery standard; secondary standard used to prepare
laboratory spike samples.
3.1.19 Percent Relative Standard Deviation (%RSD) - Hie standard deviation times
100 divided by the mean. Also termed "coefficient of variation."
3.1.20 PFK - perfluorokerosene; the mixture of compounds used to calibrate the exact
m/z scale in the HRMS.
3.1.21 Primary Dilution Standard - a solution containing the specified analytes that is
purchased or prepared from stock solutions and diluted as needed to prepare
calibration solutions and other solutions.
3.122 QC Check Sample - a sample containing all or a subset of the analytes at known
concentrations. The QC check sample is obtained from a source external to the
laboratory or is prepared from a source of standards different from the source of
calibration standards. It is used to check laboratory performance with test
materials prepared external to the normal preparation process.
3.1.23 Reagent Water - water demonstrated to be free from the analytes of interest and
potentially interfering substances at the analyte estimated detection limit; e.g.,
HPLC grade water.
3.1.24 Recovery Standard - a known amount of component added to the concentrated
sample extract before injection. The response of the internal standards relative to
the recovery standard is used to estimate the overall recovery of the internal
standards.
3.1.25 Rei ative Response Factor - the response of the mass spectrometer to a known
amount of an analyte relative to a known amount of an internal standard.
3.1.26 RF - response factor (see Section 10.2.2).
3.1.27 RPD - relative percent difference, defined as the absolute value of the difference
between two values divided by the mean of the two values, expressed as a
percentage.
3.1.28 S/N - signal to noise ratio.
t i oo _ this action, activity, or procedural step is suggested but not required.
3.1.30 SICP - selected ion current profile; the line described by the signal at an exact
m/z.
4 •
N-117
-------
3.1.31 SPE - solid-phase extraction; an extraction technique in which an analyte is
extracted from an aqueous sample by passage over or through a inatc.»ial caaable
of reversibly adsorbing the analyte. Also termed liquid-solid extraction.
3.1.32 Specific Isomers - a specific isomer is designated by indicating the exact
positions (carbon atoms) where chlorines are located within the molecule. For
example, 2,3,3',4,4-PeCB refers to only one of the 209 possible PCB isomers -
that isomer which is chlorinated in the 2,3,3',4,4-position of the biphenyl r'ng
structure.
3.1.33 Specificity - the ability to measure an analyte of interest in the presence of
interferences and other analytes of interest encountered in a sample.
3.1.34 Stock Solution - a solution containing an analyte that is prepared using a
reference material traceable to EPA, the National Institute of Science and
Technology (NIST), or a source that will attest to the purity and authenticity of
the reference material.
3.1.35 Toxic PCB - any or all of the toxic chlorinated biphenyl isomers shown m
Table 1.
3.1.36 VER - see Calibration Verification Standard (Section 3.1.3).
Abbreviations
3.2.1 PCB - any or all of the 209 possible polychlorinated biphenyl isomers.
3.2.2 TCB - abbreviation for tetrachlorinated biphenyl.
3.2.3 PeCB - abbreviation for pentachlorinated biphenyl.
3.2.4 HxCB - abbreviation for hexachlorinated biphenyl.
3.2.5 HpCB - abbreviation for heptachlorinated biphenyl.
3.2.6 DCB -.abbreviation for decachlorinated biphenyl
• 5
N-118
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4.0 CONTAMINATION AND INTERFERENCES
4.1 Method interferences may be caused by contaminants in solvents, reagents, glassware,
and other sample processing hardware that lead to discrete artifacts and/or elevated
backgrounds at the ions-monitored. All of these materials must be routinely
demonstrated to be free from interferences under the conditions of the analysis by
analyzing field and laboratoiy blanks as described in Sections 9.1.1 and 922.
4.2 Solvents, reagents, glassware, and other sample processing hardware may yield artifacts
and/or elevated baselines causing misinterpretation of chromatograms. Specific selection
of reagents and purification of solvents by distillation in all-glass systems may be
required. Where possible, reagents are cleaned by extraction or solvent rinsing. The toxic
PCB congeners 105,114,118,123,156,157, 167, and 180 have been shown to be very
difficult to completely eliminate from the laboratory, and baking of glassware in a kiln or
furnace at 450-500°C may be necessary to remove these and other contaminants.
4.3 Proper cleaning of glassware is extremely important because glassware may not only
contaminate the samples but may also remove the analytes of interest by adsorption onto
the glass surface.
4.3.1 Glassware should be rinsed with methanol and washed with a detergent solution
as soon after use as is practical. Sonication of glassware containing a detergent
solution for approximately 30 seconds may aid in cleaning. Glassware with
removable parts, particularly separatory funnels with fiuoropolymer stopcocks,
must be disassembled prior to detergent washing.
4.3.2 After detergent washing, glassware should be rinsed immediately; first with
methanol, then with hot tap water. The tap water rinse is followed by distilled
water, methanol, and then methylene chloride rinses.
4.3.3 Baking of glassware in kiln or other high temperature furnace (450-500°C) may
be warranted after particularly dirty samples are encountered. However, baking
should be minimized, as repeated baking of glassware may cause active sites on
the glass surface that may irreversibly adsorb PCBs.
4.3.4 Immediately prior to use, the Soxhlet apparatus should be pre-extracted with
methylene chloride for 3 hours to remove any possible background contamination.
4.4 The use of high purity reagents minimizes background contamination and interference
problems. Purification of solvents by distillation in all-glass systems may be required.
6
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4.5 Matrix interferences may be caused by contaminants that are co-extracted from tbe
sample. The extent of matrix interferences may vary considerably with the source being
sampled. Toxic PCBs are often associated with other interfering chlorinated compound::
which are at concentrations several orders of magnitude higher than tf»ot nf
interest. The cleanup procedures in Section 11.3 can be used to reduce many of these
interferences, but unique samples may require additional cleanup approaches.
4.6 Two high resolution capillary columns, a J&W DBXLB, 60 m x 0.25 mm x 0.25 yum
(J&W), and a 50 m x 0.23 mm x 0.25 pan HT-8 (SGE), are recommended for PCB
analysis because both of these columns will resolve all 13 toxic PCBs. Equivalent
columns that sufficiently resolve the toxic PCBs may also be used.
4.7 If other gas chromatographic conditions or other techniques are used, the analyst is
required to support the data through an adequate quality assurance program.
5.0 SAFETY
5.1 The toxicity or carcinogenicity of each reagent used in this method has not been precisely
defined. Nevertheless, each chemical compound should be treated 2S a potential health
hazard. Therefore, exposure to these chemicals must be reduced to the lowest possible
hvel by whatever means available.
5.2 The laboratory is responsible for maintaining a current file of OSHA regulations
regarding the safe handling of the chemicals specified in this method. A reference file of
material safety data sheets should also be made available to all personnel involved in the
chemical analysis.
5.3 PCBs and methylene chloride have been classified as known or suspected human or
mammalian carcinogens.
5.4 Unsterilized sewage incinerator scrubber water may be a human health risk because
pathogens contained within the sample, e.g., salmonella, E. coli, hepatitis, may be
aerosolized and transported to the human host via inhalation or dermal contact with
mucous membranes. Scrubber water samples that have not been pre-treated with chlorine
(minimum of 4 ppmv) should be sterilized by adding 4% (v/v) nitric acid to the sampling
bottles prior to collection in the field (see Section 8.2).
6.0 APPARATUS, EQUIPMENT, AND SUPPLIES
6.1 Glassware Cleaning Equipment—Laboratory sink with overhead fume hood.
6.2 Sample Preparation Equipment
7
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6.2.1 Laboratory fume hood of sufficient size to contain the sample preparation
equipment listed below.
6.2.2 Glove box (optional).
6.2.3 Equipment for determining percent solids
6.2.3.1 Oven - For determining percent solids; capable of maintaining a
temperature of 110 ±50 C.
6.2.3.2 Desiccator.
6.2.4 Balances
6.2.4.1 Analytical - Capable of weighing 0.1 mg.
6.2.4.2 Top loading—Capable of weighing 10 mg.
Extraction Apparatus
6.3.1 Graduated cylinder, 1 -L capacity.
6.3.2 Solid-phase extraction
6.3.2.1 Solid phase extraction manifold.
6.3.2.2 Vacuum source capable of maintaining 25 in. Hg, equipped with shutoff
valve and vacuum .gauge.
6.3.2.3 Solid-phase extraction cartridge containing octadecyl (Clg) bonded silica
uniformly enmeshed in an inert matrix—Fisher Scientific 14-378F (or
equivalent).
6.3.3 Soxhlet Apparatus
6.3.3.1 Soxhlet - 50-mm ID, 200-mL capacity with 500-mL flask (Cal-Glass
LG-6900, or equivalent, except substitute 500-mL round-bottom flask
for 300-mL flat-bottom flask).
6.3.3.2 Thimble - 43 mm * 123 mm to fit Soxhlet (Cal-Glass LG-69Q1-122, or
equivalent).
6.3.3.3 Heating mantle - Hemispherical, to fit 500-mL round-bottom flask (Cal-
Glass LG-8801-112, or equivalent).
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6.3.3.4 Variable transformer - Powerstat (or equivalent), 110-volt, 10-amp.
6.3.4 Beakers - 400- to 500-mL.
6.3.5 Spatulas - Stainless steel.
Filtration Apparatus
6.4.1 Pyrex glass wool - heated in an oven at 450-500 *C for 8 hours minimum.
6.4.2 Glass funnel -125- to 250-mL.
6.4.3 Glass-fiber or quartz fiber filter paper - Whatman GF/D (or equivalent).
6.4.4 Drying column -15- to 20-mm ID Pyrex chromatographic column equipped with
coarse-glass ftit or glass-wool plug.
6.4.5 Pressure filtration SPE manifold, Supelco or equivalent.
Cleanup Apparatus
6.5.1 Pipets
6.5.1.1 Disposable, Pasteur, 150-mm long x 5-mm ID (Fisher Scientific 13-678-
6A, or equivalent).
6.5.1.2 Disposable, serological, 50-mL (8- to 10- mm ID).
6.5.2 Glass chromatographic columns
6.5.2.1 150-mm long * 8-mm ID, (Kontes K-420155, or equivalent) with
coarse-glass fht or glass-wool plug and 250-mL reservoir.
6.5.2.2 200-mm long * 15-mm ID, with coarse-glass frit or glass-wool plug and
250-mL reservoir.
6.5.2.3 300-mm long x 22-mm ID, with coarse-glass fiit, 300-mL reservoir, and
glass or fluoropolymer stopcock.
6.5.3 Oven - For baking and storage of adsorbents, capable of maintaining a constant
temperature (±5°C) in the range of 105-250°C.
-------
Concentration Apparatus
6.6.1 Rotaiy evaporator - Buchi/Brinkman-American Scientific No. E5045-10 or
equivalent, equipped with a variable temperature water bath.
6.6.1.1 Vacuum source for rotaiy evaporator equipped with shutoff valve at the
evaporator and vacuum gauge.
6.6.12 A recirculating water pump and chiller are recommended, as use of tap
water for cooling the evaporator wastes large volumes of water and can
lead to inconsistent performance as water temperatures and pressures
vary.
6.6.1.3 Round-bottom flask - 100-mL and 500-mL or larger, with ground-glass
fitting compatible with the rotary evaporator.
6.6.2 Kudema-Danish (K-D) concentrator
6.6.2.1 Concentrator tube - 10-mL, graduated (Kontes K-570050-1025, or
equivalent) with calibration verified. Ground-glass stopper (size 19/22
joint) is used to prevent evaporation of extracts.
6.6.2.2 Micro concentrator tube - 1.0-mL, graduated (Kontes K-570050-1000,
or equivalent) with calibration verified. Ground-glass stopper (size 19/22
joint) is used to prevent evaporation of extracts.
6.6.2.3 Evaporation flask - 500-mL (Kontes K-570001-0500, or equivalent),
attached to concentrator tube with springs (Kontes K-662750-0012 or
equivalent).
6.6.2.4 Snyder column - Three-ball macro (Kontes K-503000-0232, or
_ equivalent).
6.6.2.5 Boiling chips.
6.6.2.5.1 Glass or silicon carbide - Approximately 10/40 mesh,
extracted with methylene chloride and baked at 450 °C for 1
hour minimum
6.6.2.5.2 Fluoropolymer (optional) - Extracted with methylene
chloride.
6.6.2.6 Water bath - Heated, with concentric ring cover, capable of maintaining
a temperature within ±2°C, installed in a fume hood
10
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6.6.3 Nitrogen blowdown apparatus - Equipped with water bath controlled in the range
of 30 - 60°C (N-Evap, Organomation Associates, Inc., or equivalent), installed in
a fume hood.
6.6.4 TurboVap Nitrogen blowdown apparatus - Equipped with Turbotubes, and water
bath controlled in the range of 30 - 60°C (Turbo vap n, Zymark, or equivalent).
6.6.5 Sample vials
6.6.5.1 Amber glass, 2- to 5-mL with fluoropolymer-lined screw cap.
6.6.5.2 Glass, 0.3-mL, conical, with fluoropolymer-lined screw or crimp cap.
6.7 Gas Chromatograph - Shall have splitless or on-column injection port for capillary
column, temperature program with isothermal hold, and shall meet all of the performance
specifications in Section 10.
6.7.1 GC Columns - Each of the GC columns listed below is capable of resolving the
13 toxic PCB congeners analyzed for in this method. Other GC columns may be
used when resolution of the PCB congeners of concern from their most closely
eluting leading and trailing congeners can be demonstrated.
6.7.2 Column #1—50 m long x 0.25±0.02-mm ID; 0.25-nm film HT-8 (SGE, or
equivalent).
6.7.3 Column #2—60 m long * 0.25±0.02-mm ID; 0.25-jim film DBXLB (J&W, or
¦ equivalent).
6.8 High Resolution Mass Spectrometer - 28- to 40-eV electron impact ionization, shall be
capable of repetitively selectively monitoring 12 exact m/z's minimum at high resolution
10,000) during a period less than 1.5 seconds, and shall meet all of the performance
specifications in Section 10.
6.9 HRGC/HRMS Interface - The high resolution mass spectrometer (HRMS) shall be
interfaced to the high resolution gas chromatograph (HRGC) such that the end of the
capillary column terminates within 1 cm of the ion source but does not intercept the
electron or ion beams.
6.10 Data System - Capable of collecting, recording, and storing MS data.
11
M_ 1 -7 A
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7.0 REAGENTS AND STANDARDS
Note: unless otherwise stated, all reagents, water, and solvents must be pesticide grade (if
available) or equivalent.
7.1 Acid and Base Partitioning
7.1.1 Potassium hydroxide - Dissolve 20 g pesticide grade (if available) KOH in 100
mL reagent water.
7.1.2 Sulfuric acid - Pesticide grade (if available; specific gravity 1.84).
7.1.3 Hydrochloric acid - Pesticide grade (if available), 6N.
7.1.4 Sodium chloride - Pesticide grade (if available), prepare at 5% (w/v) solution in
reagent water.
7.2 Solution Drying and Evaporation
7.2.1 Solution drying - Sodium sulfate, reagent grade, granular, anhydrous (Baker
3375, or equivalent), rinsed with methylene chloride (20 mL/g), baked at 400°C
for 1 hour minimum, cooled in a desiccator, and stored in a pre-cleaned glass
bottle with screw-cap that prevents moisture from entering. If, after heating, the
sodium sulfate develops a noticeable grayish cast (due to the presence of carbon
in the crystal matrix), that batch of reagent is not suitable for use and should be
discarded. Extraction with methylene chloride (as opposed to simple rinsing) and
baking at a lower temperature may produce sodium sulfate that is suitable for use.
7.2.2 Prepurified nitrogen - 99.9995% purity.
7.2.3 Desiccant - EM Science silica gel Grade H Type IV Indicating (6-16 mesh).
7.3 Extraction
7.3.1 Solvents - Acetone, n-hexane, methanol, methylene chloride, and nonane;
distilled in glass, pesticide quality, lot-certified to be free of interferences,"
7.3.2 Water - Pesticide grade or equivalent, sold and stored in glass containers.
7.4 Adsorbents for Sample Cleanup
7.4.1 Silica gel
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7.411.1 Activated silica gel -100-200 mesh, Supelco 1-3651 (or equivalent),
rinsed with methylene chloride, baked at 180°C for a minimum of 1
hour, cooled in a desiccator, and stored in a precleaned glass bottle with
screw-cap that prevents mo-'sture from entering.
.» *
7.4.1.2 Add silica gel (30% w/w) - Thoroughly mix 44 g of concentrated
sulfuric acid with 100 g of activated silica gel in a clean container. Break
up aggregates with a stirring rod until a uniform mixture is obtained.
Store in a screw-capped bottle with fluoropolymer-lined cap.
7.4.1.3 Basic silica gel - Thoroughly mix 30 g of IN sodium hydroxide with
100 g of activated silica gel in a clean container. Break up aggregates
with a stirring rod until a uniform mixture is obtained. Store in a screw-
capped bottle with fluoropolymer-lined cap.
7.4.2 Carbon
7.4.2.1 Carbopak C - (Supelco 1-0258, or equivalent).
7.4.2.2- Cefite 545 - (Supelco 2-0199, or equivalent).
7.4.2.3 Thoroughly mix 18 g Carbopak C and 18 g Celite 545 to produce a 50%
w/w mixture. Activate the mixture at 130°C for a minimum of 6 hours.
Store in a desiccator.
7.5 Standard Solutions
Standards purchased as solutions or mixtures with certification to their purity,
concentration, and authenticity, or prepared from materials of known purity and
composition. If the chemical purity is 98 percent or greater, the weight may be used
without correction to compute the concentration of the standard. Standards should be
stored in the dark in a freezer at s0°C in screw-capped vials with fluoropolymer-lined
caps when not being used. A mark is placed on the vial at the level of the solution so that
solvent loss by evaporation can be detected. If solvent loss has occurred, or the shelf life
has expired, the solution should be replaced.
7.5.1 Stock Standard Solutions
7.5.1.1 Prepared in nonane per the steps below or purchase as dilute solutions
(Cambridge Isotope Laboratories/CIL, Wobum, MA, or equivalent).
Observe the safety precautions in Section 5.
7.5.12 An appropriate amount of assayed reference material is dissolved in
solvent For example, weigh 1 to 2 mg ofPCB 126 to three significant
figures in a 10-mL ground-glass-stoppered volumetric flask and fill to
13
N-i;.6
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the marie with nonane. After the PCB is completely dissolved, transfer
the solution to a clean 15-mL vial with fluoropolymer-lined cap.
7.5.1.3 Stock standard solutions should be checked for signs of degradation
prior tQ*the preparation of calibration or performance test standards.
Reference standards that can be used to determine the accuracy of
calibration standards are available from several vendors.
7.5.2 Precision and Recovery (PAR) Stock Solution
Using the solutions in Section 7.5, prepare the PAR stock solution to contain the
PCBs of interest at the concentrations shown in Table 3. When diluted, the
solution will become the PAR spiking solution (Section 7.5.7).
7.5.3 Internal Standard Solutions
7.5.3.1 Internal Standard Stock Solution
From stock standard solutions, or from purchased mixtures, prepare the
solution to contain the labeled internal standards in nonane at the stock
solution concentrations shown in Table 3. This solution is diluted with
acetone prior to use (Section 7.5.3.2).
7.5.3.2 Internal Standard Spiking Solution
Dilute a sufficient volume of the labeled internal standard stock solution
(Section 7.5.3.1) by a factor of 500 with acetone to prepare a diluted
spiking solution. Concentrations may be adjusted to compensate for
background levels. Each sample requires 1.0 mL of the diluted solution.
7.5.4 Cleanup Standard Spiking Solution
7.5.4.1 Prepare labeled PCBs'Sl and 111 in acetone at the level shown in
Table 3.
7.5.4.2 The cleanup standard is added to the scrubber water extract prior to
cleanup to measure the efficiency of the cleanup process.
7.5.5 Recovery Standard(s) Spiking Solution
Prepare the recovery standard spiking solution to contain labeled PCBs 52,101,
' ? and 178 in nonane af the level shown in Table 3-
7.5.6 Calibration Standards (CS1 through CSS)
14
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7.5;6.1 Combine the solutions in Sections 7.5.1 to produce the five calibration
solutions shown in Table 4 in nonane.
7.5.6.2 Calibration standards may also be purchased alreadv nreoared in nor ane
(CIL). <
7.5.6.3- These solutions permit the relative response factor (labeled to native) to
be measured as a function of concentration. The CS3 standard is used for
calibration verification (VER).
7.5.7 Precision and Recovery (PAR) Spiking Solution
7.5.7.1 Used for preparation of laboratory spike duplicate samples (Section 9.5).
7.5.7.2 Dilute 200 piL of the PAR stock solution (Section 7.5.2) to 10 mL with
acetone. Each laboratory spike QC sample requires 1.0 mL.
7.5.8 GC Retention Time Window Defining and Isomer Specificity Test Solution
7.5.8.1 This solution is used to define the beginning and ending retention times
for the PCB congeners and to demonstrate isomer specificity of the GC
columns.
7.5.8.2 The solution must contain the compounds listed in Table 8 (CEL. or
equivalent), at a minimum.
7.5.9 QC Check Sample
If available, a QC check sample should be obtained from a source independent of
the calibration standards. Ideally, this check sample would be a certified standard
reference material (SRM) containing the PCBs in known concentrations in a
sample matrix similar to the matrix being analyzed.
7.5.10 Solution Stability
7.5.10.1 Standard solutions used for quantitative purposes (Section 7.5.6) should
be analyzed periodically, and should be assayed against reference
standards before further use.
7.5.10.2 If the analysis yields standard concentrations that are not within 25% o f
the true value for any PCB, (he solutions will be replaced with solutions
that, when analyzed, yield concentrations that are within 25% of the
true value.
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8.0 SAMPLE COLLECTION, PRESERVATION, STORAGE, AND
HOLDING TIMES
8.1 Sample Collection
Scrabber water samples are collected as grab samples.
8.2 Pre-Treatment/Sterilization
Sample bottle must contain enough 1:1 HN03 to give 4% HN03 (v/v) for sterilization if
the scrubber water is not pre-treated with chlorine (minimum of 4 ppmv).
8.3 Sample Storage
Maintain aqueous samples in the dark at 4°C from the time of collection until receipt at
the laboratory.
8.4 Holding Times
8.4.1 Samples are stored in the dark at 4°C.
%
8.4.2 Sample extracts are stored in the dark at <-10°C until analyzed.
8.4.3 A maximum of 30 days between sample collection and extraction, and a
maximum of 45 days between extraction and analysis is recommended.
9.0 QUALITY ASSURANCE/QUALITY CONTROL
9.1 The minimum requirements of this method consist of spiking samples with labeled
compounds to evaluate and document analyte recovery, and preparation and analysis of
QC samples including blanks and duplicates. Laboratory performance is compared to
target performance criteria to establish the performance requirements of the method.
9.2 Labeled Compounds
The laboratory shall spike all samples with the labeled standard spiking solutions
(Sections 7.5.3.2 and 7.5.4) to assess method performance on the sample matrix.
Recovery of labeled standards from samples should be assessed and records should be
maintained.
0.2.1 Analyze each sample according to the procedures in Section 11. Compute the
percent recovery of the labeled standards as described in Section 12.2.3.
16
N-129
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9.2.2 The recovery of each labeled compound will be compared to the target limits in
Table 5. If the recovery of any compound falls outside of these linuu, the daa
will be flagged and impact on reported concentration will be discussed in the
reported results.
Laboratory Method Blanks
9.3.1 Prepare, extract, clean up, and concentrate a laboratory method blank with each
sample batch (samples of the same matrix started through the extraction process
on the same 12-hour shift, to a maximum of 20 samples).
9.3.2 If any native PCB analytes (Table 1) are found in the blank at greater than 20
percent of the concentration level found in the sample, the reported data should be
flaggged as potentially containing some contribution from laboratory procedures.
If method blank contamination is severe, sample preparation and analysis
procedures should be reviewed and reprocessing the sample set should be
considered depending on specific project requirements.
QC Check Sample
If available, analyze a QC check sample (Section 7.6.9) periodically to assuxe the
accuracy of calibration standards and the overall reliability of the analytical process. It is
suggested that the QC check sample be analyzed at least quarterly.
Laboratory Spike Duplicates
9.5.1 With each sample batch, spike duplicate scrubber water samples with PAR
spiking solution (Section 7.6.7) and process through extraction, cleanup, and
analysis procedures as the field samples.
9.5.2 Calculate precision for the duplicate laboratory spike samples as the relative
percent difference (RPD). The RPD should be < 50 percent.
9.5.3 Calculate accuracy for the laboratory spike samples by determining the perceru
recovery of spiked analytes. Accuracy should be within 40 -160 percent for
analytes spiked five times the background level of the scrubber water samples
Method Specifications
9.6.1 The specifications contained in this method can be met if the apparatus used is
calibrated properly and then maintained in a calibrated state.
9.6.2 The standards used for calibration (Section 7.6.6), calibration verification
(Section 7.6.6.3), and for laboratory spike samples (Section 7.6.7) should be
identical, so that the most precise results will be obtained.
17
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9.6.3 A HRGC/HRMS instrument will provide the most reproducible results if
dedicated to the settings and conditions required for the analyses of PCB analytes
by this method.
10.0 HRGC/HRMS CALIBRATION
10.1 Operating Conditions
Establish the operating conditions necessary to meet the minimum retention times for the
internal and recoveiy standards in Table 2.
10.1.1 Suggested HRGC Operating Conditions
Injector temperature: 290°C
Interface temperature: 290°C
Initial temperature: 150°C
Initial time: 2 min
Temperature program: 150 to 200°C at 10°C/min; 200 to 280°C at
2°C/min
NOTE: All portions of the column that connect the HRGC to the ion source shall
remain at or above the interface temperature specified above during analysis to
preclude condensation of less volatile compounds.
The HRGC conditions may be optimized for compound separation and sensitivity.
Once optimized, the same HRGC conditions must be used for the analysis of all
standards, blanks, and samples.
10 1.2 High Resolution Mass Spectrometer (HRMS) Resolution
10.1.2.1 Obtain a selected ion current profile (SICP) of each analyte listed in
Table 3 at the two exact m/z's specified in Table 6 and at * 10,000
resolving power by injecting an authentic standard of the PCBs either
singly or as part of a mixture in which there is no interference between
closely eluted components.
10.1.2.2 The analysis time for PCBs may exceed the long-term mass stability of
the mass spectrometer. Because the instrument is operated in the high-
resolution mode, mass drifts of a few ppm (e.g., 5 ppm in mass) can
have serious adverse effects on instrument performance. Therefore, a
mass-drift corr^tm?! mandatory and a IncJt-roass mlz from PFK is
used for drift correction. The lock-mass m/z is dependent on the exact
m/z's monitored within each descriptor, as shown in Table 6. The level
18
N-131
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ofPFK metered into the HRMS during analyses should be adjusted so
that the amplitude of the most intense selected lock-mass ziz s^gral
(regardless of the descriptor number) does not exceed 10 percent of the
full-scale deflection for a given set of detector parameters. Under those
conditions, sensitivity changes that might occur during me analysis can
be more effectively monitored.
NOTE: Excessive PFK (or any other reference substance) may cause
noise problems and contamination of the ion source necessitating
increased frequency of source cleaning. ,
10.1.2.3 If the HRMS has the capability to monitor resolution during the
analysis, it is acceptable to terminate the analysis when the resolution
falls below 10,000 to save reanalysis time.
10.1.2.4 Using a PFK molecular leak, tune the instrument to meet the minimum
required resolving power of 10,000 (10 percent valley) atm/z 3R0.9760.
For each descriptor (Table 6), monitor and record the resolution and
exact m/z's of three to five reference peaks covering the mass range of
the descriptor. The resolution must be greater than or equal to 10,000,
and the deviation between the exact m/z and the theoretical m/z
(Table 6) for each exact m/z monitored must be less than 5 ppm.
10.1.3 Ion Abundance Ratios, Minimum Levels, Signal-to-Noise Ratios, and Absolute
Retention Times
10.1.3.1 Choose an injection volume of either 1 - or 2-p.L, consistent with the
capability of the HRGC/HRMS instrument. Inject a 1- or 2-^L aliquot
of the CS1 calibration solution (Table 4) using the GC conditions from
Section 10.1.1.
10.1.3.2 Measure the SICP areas for each analyte, and compute the ion
abundance ratios at the exact m/z's specified in Table 6. Compare the
computed ratio to the theoretical ratio given in Table 7.
The exact m/z's to be monitored in each descriptor are shown in
Table 6. Each group or descriptor shall be monitored in succession as a
function of GC retention time to ensure that all of the toxic PCBs are
detected. Additional m/z's may be monitored in each descriptor, and the
m/z's may be divided among more than the descriptors listed in Table 6
provided that the laboratory is able to monitor the m/z's of all the PCBs
that may elute from the GC in a given retention-time window.
The mass spectrometer shall be operated in a mass-drift correction
mode, using PFK to provide lock m/z's. The lock mass for eac h group
19
N-32
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of m/z's is shown in Table 6. Each lock mass shall be monitored and
shall not vary by more than ±20 percent throughout its respective
retention time window. Variations of the lock mass by more than 20
percent indicate the presence of coeluting interferences that may
significantly reduce the sensitivity of the mass spectrometer.
Reinjection of another aliquot of the sample extract will not resolve the
problem. Additional cleanup of the extract may be required to remove
the interferences.
10.1.3.3 All PCB analytes and labeled compounds in the CS1 standard shall be
within the QC limits in Table 7 for their respective ion abundance
ratios; otherwise, the mass spectrometer shall be adjusted and this test
repeated until the m/z ratios fall within the limits specified. If" the
adjustment alters the resolution of the mass spectrometer, resolution
shall be verified (Section 10.1.2) prior to repeat of the test.
10.1.3.4 The peaks representing the PCBs and labeled compounds in the CS1
calibration standard must have signal-to-noise ratios (S/N) greater than
or equal to 10.0. Otherwise, the mass spectrometer shall be adjusted
and this test repeated until the peaks have S/N greater than or equal to
10.0.
10.1.3.5 Retention Time Windows - Analyze the GC retention time window
defining and isomer specificity test solution (Section 7.5.8) using the
optimized temperature program in Section 10.1.1. Table 2 gives the
elution order (first/last) of the window-defining compounds.
10.1.4 Isomer Specificity
10.1.4.1 From the analysis of the GC retention time -window and isomer
specificity test solution (Section 10.1.3.5), compute the percent valley
between the GC peaks for PCB 123 and PCB 118, and between the GC
peaks for PCB 156 and 157.
10.1.4.2 Verify that the height of the valley between these closely eluted isomers
is less than 25 percent. If the valley exceeds 25 percent, adjust the
analytical conditions and repeat the test or replace the GC column and
recalibrate.
10.2 Initial Calibration
1 C.2.1 Txcpare a calibration curve encompassing the concentration range for each
compound to be determined. Referring to Table 2, calculate the relative response
factors for unlabeled target analytes (RPJ relative to their appropriate internal
standard (Table 5) and the relative response factors for the l3Cu-labeled internal
20
N-133
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standards (RP^) using the four recovery standards (Table 5) according to the
following formulae:
yeO
¦(Aj+A,')x o.
g-
(aJ+aJ)
where:
A,2 and AB3 « sum of the integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for unlabeled PCBs,
A J and A^ m sum of the integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for the labeled internal standards,
A J and Aj - sum of the integrated ion abundances of the quantitation ions fTables 2,3 and
6) for the recovery standard,
gi, - quantity of the internal standard injected (pg),
Qm - quantity of the recovery standard injected (pg), and
Qm - quantity of the unlabeled PCB anatyte injected (pg).
MFm and the RF„ are dimensionless quantities; the units used to express Qu Q„ and Q,
must be the same.
10.2.2 Calculate the mean relative response factors and their respective percent relative
standard deviation (%RSD) for the five calibration solutions. If the mean relative
response factors between the analytes is not within 35% USD, the instrument must
be re-calibrated.
t ^.W
- RFn =
5
where n represents a particular PCB congener (n"l to 13; Table 3), andj is the
injection or calibration solution number; Qml to 5).
i j"7*®
where k represents a particular PCB internal standard (is ¦ 14 to 23; Table 3), andj
is the injection or calibration solution number; Q -1 to 5).
21
-------
10.3 Operation Verification
At the beginning of each 12-hour shift during which analyses are performed,
HRGC/HRMS system performance and calibration are verified for all native PCBs and
labeled compounds. Eor .these tests, analysis of the CS3 calibration verification (VER)
standard (Section 7.5.6,and Table 4) and the isomer specificity test solution (Section 7.5.8
and Table 8) shall be used to verify all performance criteria. Adjustment and/or _
recalibration (Section 10) shall be performed until all performance criteria are met. Only
after all performance criteria are met may samples and blanks be analyzed.
10.3.1 HRMS Resolution
A static resolving power of at least 10,000 (10 percent valley definition) must be
demonstrated at the appropriate m/z before any analysis is performed. Static
resolving power checks must be performed at the beginning and at the aid of each
analysis batch according to procedures in Section 10.1.2. Corrective actions must
be implemented whenever the resolving power does not meet the requirement.
10.3.2 Calibration Verification
10.3.2.1 Inject the VER standard using the procedure in Section 11.9.
10.3.2.2 The m/z abundance ratios for all PCBs shall be within the limits in
Table 7; otherwise, the mass spectrometer shall be adjusted until the
m/z abundance ratios fall within the limits specified, and the
verification test shall be repeated. If the adjustment alters the resolution
of the mass spectrometer, resolution shall be verified (Section 10.1.2)
prior to repeat of the verification test
10.3.2.3 The peaks representing each native PCB and labeled compound in the
VER standard must be present with a S/N of at least 10; otherwise, the
mass spectrometer shall be adjusted and the verification test repeated.
10.3.2.4 Calculate the relative response factors (RF) for unlabeled target
analytes [RF(D); n = 1 to 13 from Table 3] relative to their appropriate
internal standards (Table 2), and the RFy for the 13C12-labeled internal
standards [RF(ij); is = 14-23] relative to the recovery standards (Table 2)
using the equations shown in Section 10.2.1.
10.3.2.5 For each compound, compare the relative response factor with those
generated in the initial calibration. Relative response factors should be
within 35 percent of initial calibration results for 70% of the analytes
for the calibration to be verified. Once verified, analysis of standards
and sample extracts may proceed. If, however, fewer than 70% of the
response factors are within the 35% limit, the measurement system is
22
N-135
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not performing properly for those compounds. In this event, prepare a
fresh calibration standard or correct the problem causing the faii-ire and
repeat the resolution (Section 10.1.2) and calibration verification
(Section 10.3.2) tests, or recalibrate (Section 10). Per the analyst's
discretion, results may also be reported for these anaiyies using mc
average calibration verification response factors bracketing the samples
rather than the meanjesponse factor generated in the initial calibration
If this option is chosen, data reported using an average calibration
verification response factor should be flagged and discussed in the final
report. . .
10.3.3 Retention Times
The absolute retention times of the GC/MS internal standards in the calibration
verification shall be within ±15 seconds of the retention times obtained during
initial calibration.
10.3.4 HRGC Resolution
10.3.4.1 Inject the GC retention time window defining and isomer specificity
test solution (Section 7.5.S).
10.3.4.2 The valley height between PCBs 123 and 118 at m/z 325.8804 shall not
exceed 25 percent, and the valley height between PCBs 156 and 157
shall not exceed 25 percent at m/z 359.8415 on the GC columns.
10.3.4.3 If the absolute retention time of any compound is not within the limits
specified or if the congeners are not resolved, the GC is not performing
properly. In this event, adjust the GC and repeat the calibration
verification test or recalibrate, or replace the GC column and either
verify calibration or recalibrate.
10.4 Datastorage
MS data shall be collected, recorded, and stored.
10.4.1 Data Acquisition
The signal at each exact m/z shall be collected repetitively throughout the
monitoring period and stored on amass storage device.
23
N-136
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10.4.2 Response Factors and Multipoint Calibrations
The data system shall be used to record and maintain lists of response factors and
multipoint calibration curves. Computations of relative standard deviation
(coefficient of,variation) shall be used to test calibration linearity.
11.0 PROCEDURE
11.1 Sample preparation involves modifying the physical form of the sample so that the toxic
PCBs can be extracted efficiently. For samples known or expected to contain high levels
of the PCB analytes, the smallest sample size representative of the entire sample should
be used. The method provides directions for samples that have either *5% solids or for
samples that have >5% solids.
11.1.1 Scrubber water samples with 5% solids or less (visual estimate)
11.1.1.1 Shake or stir (with a clean glass rod) the sample for one minute to
obtain a representative water aliquot Transfer a 1-L aliquot to a clean
bottle.
11.1.1.2 Spike the internal standard spiking solution (Section 7.5.3.2) into the
bottle. Cap the bottle and mix the sample by shaking carefully. Allow
the sample to equilibrate for 30 minutes, with occasional shaking.
11.1.1.3 Add 5 mL of methanol to the sample. Cap and shake the sample to mix
thoroughly. Extract the sample using the SPE technique (Section
11.4,1), or an equivalent approved procedure.
11.1.2 Scrubber water with greater than 5% solids (visual estimate)
Determine percent solids according to Section 11.3.
Shake or stir (with a clean glass rod) the sample for one minute to
obtain a representative water aliquot. Transfer a 1-L aliquot to a clean
bottle.
Filter the aliquot and spike the filtrate with the internal standard spiking
solution (Section 7.5.3.2). Allow the filtrate to equilibrate for 30
minutes with occasional shaking. Add 5 mL of methanol to the filtrate.
Cap and shake the filtrate to mix thoroughly.
11.1.2.1
11.1.2.2
11.1.2.3
24
N-137
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11,1.2.4 Extract the filtrate using SPE as described in Section 11.4.1, or by using
an equivalent approved procedure. Extract the filter and collected
solids using Soxhlet techniques as described in Section 11.4.2.
11.2 Method Blank and Laboratory Spike Samples
11.2.1 With each sample set, a laboratory method blank and duplicate laboratory spike
samples must be processed through the same steps as the samples to check for
contamination and losses in the preparation processes.
11.2.2 For each sample or sample batch (to a maximum of 20 samples) to be extracted
during the same 12-hour shift, place three 1.0-L aliquots of reagent water in clean
sample bottles or flasks.
112.2.1 Spike two of these aliquots with PAR spiking solution (Section 7.5.7).
Iliese two PAR-spike aliquots will serve as the duplicate laboratory
spike samples (Section 9.5).
11.2.2.2 The unspiked aliquot will serve as the laboratory method blank.
11.2.2.3 Process the dupEcate laboratory spike samples and the laboratory
method blank according to procedures for scrubber water with 5%
solids or less (Section 11.1.1).
11.3 Percent Solids Determination
Note: This aliquot is used for determining the solids content of scrubber water samples
with visually >5% solids content, and not for determination of PCBs.
11.3.1 Weigh a weighing pan or beaker to three significant figures.
11.3.2 Transfer 10.0 ± 0.02 g of well-mixed sample to the pan or beaker.
11.3.3 Dry the sample for a mfaimum of 12 hours at 110 ± 5°C and cool in a desiccator
until the sample has equilibrated to room temperature. Weigh the dry sample plus
beaker.
11.3.4 Calculate percent solids as follows:
% solids * wei^ °f phis btaktr sfimr drying (g) - weight of beaker (g) x 1(J0
10 g
25
N-138
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11.4 Extraction and Concentration
11.4.1 Extraction procedures include solid phase (Section 11.4.1) for scrubber water with
a percent solids content of s5%.
11.4.2 A combination of solid phase (for the filtrate) and Soxhlet (for the solids)
extraction procedures are provided for scrubber water with a percent solids
content of >5%.
11.4.3 Solid Phase Extraction . .
11.4.3.1 SPE cartridge preparation
11.4.3.1.1 Place two SPE cartridges in the vacuum manifold.
11.4.3.1.2 Condition the cartridges with 15 mL aliquots of methylene
chloride, methanol, and deionized water. Do not allow the
cartridge to go dry from this point until the extraction is
completed.
11.4.3.2 Sample extraction
11.4.3.2.1 Allow the sample to equilibrate for 1-2 hours to settle the
suspended particles.
11.4.3.2.2 Allow a 1 L aliquot of the sample to be pulled through the
two SPE cartridges (approximately 500 mL in each).
11.4.3.2.3 Adjust the vacuum to complete the extraction in no less
than 15 minutes. An additional SPE cartridge may be used
if clogging prevents sufficient sample throughput.
11.4.3.2.4 Before all of the sample has been pulled through the
cartridge, add approximately 20 mL of reagent water to the
sample bottle, swirl to suspend the solids (if present), and
pour into the second reservoir. Pull through the SPE
cartridge. Use additional reagent water rinses until all solids
are removed.
11.4.3.2.5 Before all of the sample and rinses have been pulled
through the cartridge, rinse the sides of the reservoir with
small portions of reagent water.
11.4.3.2.6 Dry the cartridges under vacuum for 2 hours.
26
N-139
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11.4.3.3 Cartridge Elution
11.4.3.3.1 Release the vacuum, remove reservoir from the vacuum
manifold, and discard the extracted aqueous solution.
11.4.3.3.2 Insert two vials for eluant collection into the manifold.
Each vial should have sufficient capacity to contain the
total volume of the elution solvent (approximately 12 ml)
and should fit around the drip tip.
11.4.3.3.3 The drip tip should protrude into the vial to preclude loss of
sample from spattering when vacuum is applied.
Reassemble the vacuum manifold.
11.4.3.3.4 Wet each cartridge with 6 mL of acetone. Allow the solves:
to soak the C18 beads for 15-20 seconds. Pull all of the
solvent through the cartridges into the vials.
11.4.3.3.5 Wet each cartridge with 6 mL of methylene chloride. Allow
the solvent to soak the C18 beads for 15-20 seconds. Full all
of the solvent through the cartridge into the vial.
11.4.3.3.6 Release the vacuum, remove the vial containing the sample
solution.
11.4.3.3.7 Quantitatively transfer the solution to a 250-mL separator}'
fimnel (final volume is approximately 50 mL of hexane
extract).
11.4.3.3.8 If the percent solids content of the sample is s5%, proceec
to Section 11.5 for acid and base partitioning
11.4.3.3.9 If the percent solids content of the sample is > 5%, combine
the sample's filtrate extract with the solids extract, as
specified in Section 11.4.2.10.
11.4.4 Soxhlet Extraction
11.4.4.1 Place a clean extraction thimble (Section 6.3.3.2) in a clean
extractor.
11.4.4.2 Place 30 to 40 mL of methylene chloride in the receiver and 200 to
250 mL of methylene chloride in the flask.
11.4.4.3 Load the solids and filter into the thimble.
27
N-140
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11:4.4.4
Add approximately 5 g ofNa^O,, to the thimble.
Add a plug of clean glass wool to the thimble to prevent the filter
from floating on top of the extraction solvent.
Reassemble the Soxhlet apparatus, and apply power to the heating
mantle to begin extracting. Frequently check the apparatus for
foaming during the first 2 hours of extraction. If foaming occurs,
reduce the extraction rate until foaming subsides.
Extract the solids/filter for a total of 16 to 24 hours. Cool and
disassemble the apparatus.
Concentrate the extract to a final volume of 10 mL; transfer 5 mL of
the extract to a 10 mL storage vial with a PTFE-lined screw cap.
Label the extract and store at <0°C. Mark the liquid level on the vial
with a permanent marker to monitor solvent evaporation during
storage.
Solvent exchange the other half of the extract (5 mL) into hexane by
adding 10 mL of hexane, concentrating down to 1 mL using K-D
evaporation, adding 10 mL hexane, and concentrating down again to
2 mL. Transfer the extract with three aliquots (15 mL each) of
hexane into a 250-mL separatory funnel Proceed to Section 11.5 to
start cleanup procedures.
Combine the water filtrate extract from Section 11.4.3.3.9 with the
solids extract. Proceed to Section 11.5 to begin the cleanup
procedure.
11.5 Acid and Base Partitioning
11.5.1 Spike the cleanup standard (Section 7-5.4) into the separatory funnels containing
the sample extracts from Section 11.4.
11.5.2 Partition the extract against 50 mL of sulfuric acid (Section 7.1.2). Shake for 2
minutes with periodic venting into a hood. Remove and discard the aqueous
layer. Repeat the acid washing until no color is visible in the aqueous layer to a
maximum of four washings.
11.5.3 Partition the extract against 50 mL of sodium chloride solution (Section 7.1.4)
in the same way as with the acid. Discard the aqueous layer.
, 11.5.4 Partition the extract against 50 mL of potassium hydroxide solution
(Section 7.1.1) in the same way as with the acid. Repeat the base washing until
28
N-141
11.4.4.5
11.4.4.6
11.4.4.7
11.4.4.8
11.4.4.9
11.4.4.10
-------
no color is visible in the aqueous layer to a maximum of four washings.
Minimize contact time between the extract and the base to prevent
of the PCBs.
11.5.5 Repeat the partitioning against sodium chloride solution two more times, each
time discarding the aqueous layer.
11.5.6 Pour each extract through a drying column containing 7 to 10 cm of granular
anhydrous sodium sulfate (Section 7.2.1). Rinse the separator}' funnel with 30 to
50 mL of solvent, and pour through the drying column. Collect each extract in a
round-bottom flask.
11.5.7 Concentrate the extracts (Sections 11.6), and clean the extracts per Section 1 i .7.
11.6 Macro-Concentration - Extracts in methylene chloride or n-hexane are concentrated
using rotary evaporation, a Kudema-Danish, or Turbovap apparatus.
11.6.1 Rotary evaporation - Concentrate the extracts in separate round-bottom flasks.
Note: Improper use of the rotary evaporator may cause contamination of the
sample extract.
Assemble the rotary evaporator according to manufacturer's
instructions, and warm the water bath to 45 °C. On a daily basis,
preclean the rotary evaporator by concentrating 100 mL of clean
extraction solvent through the system. Archive both the concentrated
solvent and the solvent in the catch flask for a contamination check if
necessary. Between samples, use three 2- to 3-mL aliquots of
solvent to rinse the feed tube between samples. Collect waste in a
waste beaker.
Attach the round-bottom flask containing the sample extract to the
rotary evaporator. Slowly apply vacuum to the system, and begin
rotating the sample flask
Lower the flask into the water bath, and adjust the speed of rotation
and the temperature as required to complete concentration in 15 to
20 minutes. At the proper rate of concentration, the flow of solvent
into the receiving flask must be steady, with no bumping or visible
boiling of the extract occurring.
Note: If the rate of concentration is too fast, analyte loss may occur.
When the liquid in the concentration flask has reached an apparent
vol v- ' r f approximately 2 mL, remove the flask from the water bath
29
N-142
11.6.1.1
11.6.1.2
11.6.1.3
11.6.1.4
-------
and stop the rotation. Slowly and carefully admit air into the system.
Be sure not to open the valve so quickly that the sample is blown out
of the flask. Rinse the feed tube with approximately 2 mL of solvent.
11.6.2 Kuderoa-Danish (K-D)—Concentrate the extracts in separate 500-mL K-D
flasks equipped with 10-mL concentrator tubes. The K-D technique is used for
solvents such as methylene chloride and n-hexane.
11.6.2.1 Add 1 to 2 clean boiling chips to the receiver. Attach a three-ball
macro-Snyder column. Pre-wet the column by adding approximately
1 mL of solvent through the top. Place the K-D apparatus in a hot
water bath so that the entire lower rounded surface of the flask is
bathed with steam.
11.6.2.2 . Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 15 to 20
minutes. At the proper rate of distillation, the balls of the column
will actively chatter but the chambers will not flood.
When the liquid has reached an apparent volume of 1 mL, remove
the K-D apparatus from the bath and allow the solvent to drain and
cool for at least 10 minutes.
Remove the Snyder column and rinse the flask and its lower joint
into the concentrator tube with 1 to 2 mL of solvent. A 5-mL syringe
is recommended for this operation.
Remove the three-ball Snyder column, add a fresh boiling chip, and
attach a two-ball micro-Snyder column to the concentrator tube. Pre-
wet the column by adding approximately 0.5 mL of solvent through
the top. Place the apparatus in the hot water bath.
Adjust the vertical position and the water temperature as required to
complete the concentration in 5 to 10 minutes. At the proper rate of
distillation, the balls of the column will actively chatter but the
chambers will not flood.
When the liquid reaches an apparent volume of 0.5 mL, remove the
apparatus from the water bath and allow to drain and cool for at least
10 minutes.
11 6 ^ Turbovap - Concentrate the extracts in separate 250-mL Turbo tubes. The
Turbovap technique is used for solvents such as methylene chloride and n-
hexane.
30
11.6.2.3-
11.6.2.4
11.6,2.5
11.6.2.6
11.6.2.7
N-143
-------
11.7 Column Chromatography Cleanup
11.7.1 Silica Gel Cleanup
11.7.1.1 Place a glass-wool plug in a 15-mm ID chromatography column
(Section 6.5.2.2). Pack the column bottom to top with 1 g silica gel
(Section 7.4,1.1), 4 g basic silica gel (Section 7.4.1.3), 1 g silica ge;.
8 g acid silica gel (Section 7.4.1.2), 2 g silica gel, and 4 g granular
anhydrous sodium sulfate (Section 7.2.1). tap the column to settle
the adsorbents.
11.7.1.2 Pre-elute the column with 50 to 100 mL of n-bexane. Close the
stopcock when the n-hexane is within 1 mm of the sodium sulfate.
Discard the eluate. Check the column for channeling. If channeling is
present, discard the column and prepare another.
11.7.1.3 Apply the concentrated extract to the column. Open the stopcock
until the extract is within 1 mm of the sodium sulfate.
11.7.1.4 Rinse the receiver twice with 1-mL portions of n-hexane, and apply
separately to the column. Elute the PCBs with 75 mL of n-hexane
and collect the eluate.
11.7.1.5 Concentrate the eluate per Section 11.6 and proceed to Section
11.8.2 for carbon column cleanup.
11.7.1.6 For extracts of samples known to contain large quantities of other
organic compounds, it may be advisable to increase the capacity of
the silica gel column. This may be accomplished by increasing the
strengths of the acid and basic silica gels. The acid silica gel (Section
7.4.1.2) may be increased in strength to as much as 44% w/w (7.9 g
sulfuric acid added to 10 g silica gel). The basic silica gel (Section
7.4.1.3) may be increased in strength to as much as 33% w/w (50 mL
IN NaOH added to 100 g silica gel).
. 11.7.2 Carbon Column
11.7.2.1 Cut both ends from a 50-mL disposable serological pipet (Section
6.6.12) to produce a 20-cm column. Fire-polish both ends and flare
both ends if desired. Insert a glass-wool plug at one end, and pack
the column with 3.6 g of Carbopak/Celite (Section 7.4.2.3) to form
an adsorbent bed 20 cm long. Insert a glass-wool plug on top of the
bed to hold the adsorbent in place.
31
N-144
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11.7.2.2
Pre-elute the column with 20 mL each in succession of methylene
chloride, and n-hexane.
When the solvent is within 1 mm of the column packing, apply the
n-hexane sample extract to the column. Rinse the sample container
twice with 1-mL portions of n-hexane and apply separately to the
column. Apply 2 mL of n-hexane to complete the transfer.
Elute the column with 25 mL of n-hexane and collect the eluate.
This fraction will contain the mono- and di-ortho PCBs.
Elute the column with 15 mL of methanol and archive the eluate.
This second fraction will-contain residual lipids and other potential
interferents, if present.
Elute the column with 15 mL of toluene and collect the eluate. This
fraction will contain PCBs 77,126, and 169. Combine the first and
third fractions, and if carbon particles are present in the combined
eluate, filter through glass-fiber filter paper.
Concentrate the combined hexane and toluene fractions per Section
11.6 and proceed to Section 11.8 for final concentration.
11.8 Concentration to Final Volume
11.8.1 The extract is concentrated in a calibrated concentrator tube to a final
volume of 20 juL to 1 mL, per the analyst's discretion, under a gentle
stream of nitrogen.
11.5.2 Add 10 nL of the recovery standard solution (Section 7.5.5) to the
sample extract.
11.8.3 Proceed to Section 11.9 for HRGC/HRMS analysis.
11.9 HRGC/HRMS Analysis
11.9.1 Establish the operating conditions given in Section 10.1, perform initial
calibration if necessary (Section 10.2), or verify calibration (Section 10.3).
11.9.2 If an extract is to be reanalyzed and evaporation has occurred, do not add more
recovery standard solution. Instead, bring the extract back to its previous
volume (e.g., 19 nL, or 18 fiL if 2 ^L injections are used) with pure nonane.
11.7.2.3
11.7.2.4
11.7.2.5
11.7.2.6
11.7.2.7
32
N 145
-------
Inject 1.0 or 2.0 of the concentrated extract containing the recovery standard
solution, using on-column or splitless injection. The volume injected rai st b°
identical to the volume used for calibration (Section 10.1.3.1).
Start the HRGC column initial isothermal hold upon injection, start
data collection alter the solvent peak elutes. Stop the data collection after the
uC12-PCB 209 has eluted. Return the column to the initial temperature for
analysis of the next extract or standard.
12.0 DATA ANALYSIS AND CALCULATIONS
12.1 Qualitative Determination
A PCB analyte or labeled compound is identified in a standard, blank, or sample when
all of the criteria in Sections 12.1.1 through 12.1.4 are met. If the criteria for
identification in Sections 12.1.1-12.1.4 are not met, the PCB analyte has not been
positively identified. If interferences preclude identification, an estimated maximum
possible concentration (EMPC) can be reported (Section 12.2.5), or options for further
cleanup can be explored depending on specific project requirements. -
12.1.1 The signals for the two exact m/z's in Table 6 must be present and must
maximize within the same two seconds.
12.1.2 The signal-to-noise ratio (S/N) for the GC peak at each exact m!z must
be greater than or equal to 2.5 for each PCB detected in a sample extract
and greater than or equal to 10 for all PCBs in the calibration standard
(Section 7.5.6).
12.1.3 The ratio of the integrated areas of the two exact m/z's specified ir.
Table 6 must be within the limit in Table 7, or within ±10 percent of the
ratio in the midpoint (CS3) calibration or calibration verification (\T.R
whichever is most recent.
12.1.4 The relative retention time of the peak for a toxic PCB must be within
±15 seconds of the retention times obtained during calibration.
12.2 Quantitative Determination
12.2.1 For gas chromatographic peaks that have met the criteria outlined in
Section 12.1, calculate the concentration of the PCB compounds in the
extract, using the formula:
33
11.9.3
11.9.4
N-146
-------
c 4._xa.
Abx JLF„x V,
where:
m concentration of unlabeled PCS congeners in the sample (pg/L),
- sum of the integrated ion abundances of the quantitation ions (Tables 2,3 and
6) far unlabeled PCBs,
m sum of the integrated ion abundances of the quantitation ions (Tables 2, 3 and
6) for the labeled internal standards,
m quantity, in pg, of the internal standard added to the sample before extraction,
- calculated mean relative response factor for the anafyte ( MF, with nml to 13;
Section 10.2.1),
- volume of sample extracted (L).
Calculate the percent recovery of the eleven internal standards measured
in the sample extract, using the formula:
Percent recovery — ==— x 100
Qb*A„**Tis
where:
Ah - sum of the integrated ion abundances of the quantitation ions (Tables 2, 3
and 6) for the labeled internal standard,
A„ m sum of the integrated ion abundances of the quantitation ions (Tables 2, 3
and 6) for the labeled recovery standard,
Qm ¦ quantity, in ng, of the internal standard added to the sample before
extraction,
Q„ - quantity, in ng, of the recovery standard added to the cleaned-up sample
extract before HRGC/KRMS analysis, and
RFj, m calculated mean relative response factor for the labeled internal standard
relative to the appropriate recovery standard. This represents the mean
obtained in Section 10.2.2 (with is-14 to 23, Table 3),
The percent recovery of the cleanup standards is calculated similarly.
The percent recovery should meet the criteria shown in Table 5. If
recoveries are outside the limits of Table 5, the data should be flagged
and the impact on reported results discussed in the final report.
12.2.3 Outside Calibration Range
12.2.3.1 If the SICP area at either quantitation mlz for any compound exceeds
the calibration range of the system, the extract must be diluted and
re-analyzed.
C,
A,
A.
Q°
MF,
K
12.2.2
34
N-147
-------
12.2.3.2 Dilute the sample extract by a factor of 10, adjust the concentration
of the recovery standard to 100 pg/^iL in the extract, rxc analyze an
aliquot of this diluted extract.
12.2.4 EstimateQ Detection Limit (EDL)
2.5 (HI + H2 ) (Q,a)
f-i T% T ~ / * l ' J J * ' •'« '
(PS h (Hl„ + H2J (IF.) (VJ
where;
HI, and H2, m The heights of the noise where the primary and secondary m/z's for the
PCBs would elute.
Hlb and H2„ m The heights of the response of the primary and secondary m/z's for the
internal standard,
And Q„ RF„ and V, are as described in Section 112.1.
12.2.5 Estimated Maximum Possible Concentration (EMPC)
When the response of a signal having the same retention time as a toxic PCB
congener has a S/N in excess of 2.5 and does not meet all of the other
qualitative identification criteria listed in Section 12.1 calculate an Estimated
Maximum Possible Concentration (EMPC). The EMPC is calculated using the
equation in Section 12.2.1, except that A, should represent the sum of the area
under the smaller peak and of the other peak area calculated using the
theoretical chlorine isotope ratio. The value shall be noted as EMPC and the
results reported.
12.2.6 Results are reported to three significant figures for the PCBs and labeled
compounds found in all standards, blanks, and samples.
Note: Reported results will not be adjusted for field or laboratory blank levels.
12.2.6.1 Scrubber Water— results in pg/L (parts-per-quadrillion),
~ 12.2.6.2 Blanks—Report results above the EDL. Do not blank-correct results
If a blank accompanying a sample result shows contamination above
the EDL for the congener, flag the sample result and report the
results for the sample and the accompanying blank.
12.2.6.3 Dilutions (Section 12.2.3.2)
Results for PCB analytes in samples that have been diluted; for this
EPA project, both the undiluted and diluted PCB results are to be
35
N-148
-------
reported, whether or not all of the analytes are within the calibration
range.
12.2.7.4 Non-Detects
Note the non-detected PCB analytes as ND and report the estimated
detection limit established during the analysis.
13.0 METHOD PERFORMANCE
13.1 In a limited single laboratory demonstration of this method using scrubber water samples,
estimated detection limits of approximately 25 pg/L were achieved for PeCB; 5 pg/L for
HxCB; and 30 pg/L for HpCB.
13.2 Interlaboratory testing of this method to determine overall precision and bias has not been
performed.
14.0 POLLUTION PREVENTION
This method uses solid phase extraction (SPE) techniques for the extraction of PCBs
from liquid matrices. SPE uses much less solvent, about 1/100 as much, as traditional
liquid-liquid extraction techniques.
15.0 WASTE MANAGEMENT
PCB waste should be disposed of according to Toxic Substances Control Act (TSCA)
guidelines 40CFR 700-789, and hazardous waste should be disposed of according to
F.esource Conservation and Recovery Act (RCRA) guidelines 40CFR 260-269.
16.0 REFERENCES
1. Syhre, M., Hanschmann, G., and Heber, R.J. ofAOAC Inter., Vol. 81, No. 3,513- 517
(1998).
2. 'Toxic Polychlorinated Biphenyls by Isotope Dilution High Resolution Gas
Chrom atography/High Resolution Mass Spectrometry," U.S. EPA Method 1668, March,
lOOT
3. Obana, H., Kikuchi, K., Okihashi, M., and Shinjiro, H. Analyst, Vol. 122, 217-220 (1997).
36
N-149
-------
4. Loos, H, Vollmuth, S, and Niessner, R. Fres. J. Anal. Chem, 357(8), 1081-1087 (1997).
5. Ferrario, J., Byrne, C., and Dupuy, A.E. Jr. Organohalogen Compounds (Dioxin '96), 123-
• 127(1996).
6. Ahlborg, U.G., Becking, G.C., Bimbaum, L.S., Brouwer, A., Derks, Feeley, M.,
Golor, G., Hanberg, A., Larsen, J.C., Lion, A.K.D., Safe, S.H., Schlatter, C, Waem, F.,
Younes, M., and Yqanheikki, Chemosphere, Vol. 28, No. 6,1049-1067 (1994)
7. Strandell, M.E., Lexen, K.M., deWit, C.A., Jaemberg, U.G., Jansson, B., Kjeller, L-O.,
Kulp, S-E., Ljung, KL, Soederstroem, G., et al. Organohalogen Compounds (Dioxin '94),
363-366 (1994).
8. Ramos, L., Blanch, G.P., Hernandez, L., Gonzalez, M.J., J. Chromatography A, Vol. 690,
243-249 (1994).
9. Fitzgerald, E.F., Hwang, S.A., Brix, K., Bush, B., and Cook, K., Organohalogen
Compounds (Dioxin '94), 495-500 (1994),
10. Lazzari, L., Spemi,L., Salizzato, M., and Pavoni, B., Chemosphere, Vol. 38, No. 8,1925-
1935 (1999).
\
11. "Standard Guide for Good Laboratory Practices in Laboratories Engaged in Sampling and
Analysis of Water," ASTM D 3856,325-335,1995.
12. Sewart, A., Harrad, S.J., McLachlan, M.S., McGrath, S.P., and Jones, K.C., Chemosphere,
Vol. 30, No. 6,51-67(1995).
13. Dupont, G., Delteil, C., Camel, V., and Bennond, A., Analyst, Vol. 124,453-458 (1999).
14. "Standard Guide for General Planning of Waste Sampling," ASTM D 4687,48-55 (1995)
37
N-1E0
-------
17.0 TABLES AND FIGURES
Table 1. Toxic Polychlorinaled Biphenyls Determined by High Resolution Gas Chromatography
(HRGC)/High Resolution Mass Spectrometry (HRMS)
Native compound
IUPAC
PCBi
CAS Registry No.
No.3
Target Analytes
3,3',4,4'-TCB
32598-13-3
77
2,33',4,4-PeCB
32598-14-4
105
2,3,4,4',5-PeCB
74472-37-0
114
2,3',4,4',5-PeCB
31508-00-6
118
2',3,4,4',5-PeCB
65510-44-3
123
3,3',4,4',5-PeCB
57465-28-8
126
2,3,3',4,4',5-HxCB
38380-08-4
156
23,3,,4,4»,5'-HxCB
69782-90-7
157
2,3',4,4',5,5'-HxCB
52663-72-6
167
3,3',4,4',5,5-HxCB
32774-16-6
169
2f2,,3f3',4>4,^-HpCB
35065-30-6
170
2,2',3 4,4',5)5'-HpCB
35065-29-3
180
2,3,3',4,4',5,5'-HpCB
39635-31-9
189
Interned Standards
3,3',4,4'-TCB
160901-67-7
77L
2,3r3'f4,4'-PeCB
160901-70-2
105L
2,3,4,4',5-PeCB
160901-72-4
114L
2,3',4,4',5-PeCB
160901-73-5
118L
2',3,4,4',5-PeCB
160901-74-6
123L
3,3',4,4',5-PeCB
160901-75-7
126L
2,3,3',4,4',5-HxCB
160901-77-9
156L
2,3,3',4,4',5'-HxCB
160901-78-0
157L
2,3 ',4,4',5,5'-HxCB
161627-18-5
167L
S.S'.M'.S.S'-HxCB
160901-79-1
169L
2,2',2,3',4,4',5-HpCB
160901-80-4
170L
2,2',3,4,4',5,5'-HpCB
160901-82-6
180L
2,3,3 ',4,4',5,5 '-HpCB
160901-83-7
189L
Cleanup Standards
"Cir3,4,4',5-TCB
160901-68-8
81
uCV2-2,3,3',5,5,-PcCB
160901-71-3
HI
Recovery Standards
,3Cu-2^"',5,5'-TCB
" 160901-66-6
52
uCu-2^',4,4,5'-PeCB
160901-69-9
101
uCl2-2^,,3,4,4'^,-HxCB
160901-76-8
138
uCu-2,2',3,3 ',5,5',6-HpCB
160901-81-5
178
Final Eluter Standard
-
"C.-rDCB
160901-84-8
209
' Polychlorinated biphenyls:
TCB = Tetrachlorobiphrayl
PeCB = Pcntachlorobiphenyl
HxCB = Hexachlorobiphenyl
apwB = Heptachlorobipliei*/l
DCB = Decachlorobiphenyl
1 Suffix "L" designates a labeled compound.
38
N-151
-------
Table 2.
Retention Time (RT) References, Quantitation References, and Retention Times
(RTs) for the Toxic PCBs
IUFAC _ , IUPAC Retention time and PT5
No.1 PCB congener No.1 qaantitatioii reference (min)
52L 13012-2,2',5»5'-TOB - 13012-2,2',5,5'-TCB 28.56
81L 13012-3,4,4',5-TOB4 52L 13Cl2-2,2',5,5'-TOB 37.89
77L lSCUO^'.M'-TCB 52L 13012-2,2',S^'-TOB 38.85
77 3,3'.4,4'-TCB 77L 13012-3,3'A4'-TCB 38.85
101L 13012-2,2',4,5,5'-PeCB ~ 13012-2,2',4,5,5'-PeCB 35.02
111L 13012-2,3,3*,5,5'-PeOB4 101L UCn^'AS.S'-PeCB 37.13
123 2',3,4,4',5-PeCB 118L 13012-2,3',4,4',5-PeCB 39.90
118L 13C12-2,3',4,4',5-PeOB 101L 13012-2,2',4,5,5'-PeOB 40.17
118 2,3',4,4',5-PeCB 118L 13012-2,3',4,4',5-PeCB *0.17
114 2,3,4,4',5-PeCB 105L 13C12-2,3,3',4,4'-PeOB 40.79
105L 13012-2,3,SVM'-PeOB 101L 13012-2,2',4,5,5'-PeOB 42.22
105 2,3,3',4,4'-PeOB 105L 13012-2,3,3',4,4*-PeCB 42.22
126L 13012-3,3',4,4',5-PeCB 101L 13012-2,2',4,5,5*-PeOB 44.75
126 3,3',4.4',5-PcCB 126L 13012-3,3',4,4'.5-PcCB 44.75
138L 13012-2,2',3,4,4',5'-HxCB - 13012-2,2',4,5,5'-PeOB 43.23
167L 13C12-2,3»,4,4',5,5,-HxCB 138L 13C12-2^'^,4,4,f5,-HxCB 45.72
167 2,3',4,4',5,5'-HxCB 167L 13C12-2,3,I4l4,^,5'-HxCB 45.72
156L 13012-2,3,3',4,4',5-HxCB 138L 13C12-2^,4,4^'-HxCB 47.37
157L 13C12-2,3,3,,4,4,,5,-HxCB 138L 13012-2,2',3,4,4',5'-HxCB 47.79
156 2,3t3*,4,4',5-HxCB 156L 13012-2,3,3',4,4',5-HxCB 47.37
157 2,33',4,4',5,-HxCB 157L ncn^^'A^'-HxCB 47.79
169L 13C12-3,3',4,4't5,5,-HxCB 138L 13012-2,2',3,4,4*,5'-HxCB 50.25
169 3,3',4,4',5,5'-HxCB 169L 13C12-3,3',4,4',5,5'-HxCB 50.25
178L 13012-2,2',3,3',5,5',6-HpCB — UCn^'.W-PeCB 42.88
180L 13C12-2,2',3,4,4\5,5'-HpCB 178L 13012-2,2',3,3',5,5',6-HpCB 47.88
180 2,2',3,4,4',5,5'-HpCB 180L 13012-2^,3,4,4'^,5'-HpCB 47.88
170 2,2',3,3',4,4',5-HpCB 180L 13012-2^^,4,4',5, 5'-HpCB 49.90
189L 13C12-2,3,3',4,4',5,5,-HpCB 178L _ 13C12-W,3',5,5',6-HpCB 52,56
189 2,33*,4,4',5,5'-HpCB 189L 13C12-23,3',4,4*,5,5,-HpCB 52.56
209L 13C12-DCB5 178L 13012-2,2',3,3', 5,5', 6-HpCB 56.63
1 Suffix "L" indicates labeled compound.
3 Retention time data are for HT-8 column (per manufacturer).
3 Absolute recovery standards.
4 Cleanup standard
5 Final eluter.
39
N-152
-------
Table 3. Concentrations of Stock and Spiking Solutions Containing the Native PCBs and
Labeled Compounds
Spiking Spiking
mil Stock3 Solution2 Level
Cpd. No. Compound type (ng/mL) (ng/mL) (ng)
Precision and Recovery
Standards'
1
3,3',4,4-TCB
- 77
20
0.8
0.8
2
2,3,3',4,4-PeCB
105
1000
40
40
3
2,3,4,4',5-PeCB
114
1000
40
40
4
2,3',4,4',5-PeCB
118
1000
40
40
5
2',3,4,4',5-PeCB
123
1000
40
40
6
3,3',4,4',5-PeCB
126
100
4
4
7
2,3,3 ',4,4',5-HxCB
156
1000
40
40
8
2,3,3',4,4',5-HxCB
157
1000
40
40
9
2,3',4,4',5,5'-HxCB
167
1000
40
40
10
3f3',4,4,,5,5,-HxCB
169
200
8
8
11
2,2',3,3',4,4',5-HpCB
170
200
8
8
12
2,2',3,4,4',5,5-HpCB
180
1000
40
40
13
2,3,3 ',4,4',5,5-HpCB
Internal Standards4
189
200
8
8
14
13C12-33',4,4'-TCB
77L
1000
4
4
15
13 C12-2,3,3 ',4,4'-PeCB
105L
1000
4
4
16
13C 12-2,3',4,4',5-PeCB
118L
1000
4
4
17'
13 C12-3,3 ',4,4',5-PeCB
126L
1000
4
4
18
13C12-2,3,3',4,4',5-HxCB
156L
1000
4
4
19
13C12-2,3,3',4,4',5'-HxCB
157L
1000
4
4
20
13C12-2,3',4,4',5,5'-HxCB
167L
1000
4
4
21
13C12-3,3,,4,4\5,5,-HxCB
169L
1000
4
4
22
13 C12-2,2',3,4,4',5,5,-HpCB
180L
1000
4
4
23
13C12-2,3,3,,4,4',5,5,-HpCB
Cleanup Standards3
189L
1000
4
4
24
UCU'W,s-tcb
81L
200
1
1
25
13C12-2,3,3',5,5'-PeCB
Recovery Standards*
111L
1000
5
5
26
nC\2-2a\S,5'-7CB
52L
1000
200
2
27
13C 12-2,2',4,5,5-PeCB
101L
1000
200
2
28
13C12-2,2',3,4,4',5-HxCB
138L
1000
200
2
29
13012-2^,3,3',5,5',6-HpOB
Final Eluter
178L
1000
200
. 2
30
13C12-DCB
209L
2000
8
8
1 Section 7.5.7-prepared in nonane and diluted to prepare spiking solution.
* Sections 7.5.3.2, 7 5.4., 7.5.5,7.5.7-prepared in acetone from stock solution daily.
1 Section 7.5.1-prepared in nonane and diluted to prepare spiking solution. Concentrations are adjusted for
expected background levels.
* section 7..*).1.1-prepared in acetone from stock solution daily. Concentration* are adjusted for expected
background levels.
3 Section 7.5.4-prepsred in acetone; added to sample extracts before cleanup.
e Section 7.5.5-p'eyared in nonane; added to concentrated extract prior to injection.
40
N-153
-------
Table 4. Concentrations of PCBs in Calibration and Calibration Verification Solutions
IUPAC
CS1
CS2
CS3J
CS4
CS5
No.1
(ng/mL)
(ng/mL)
(ng/mT)
^pir/wT \
( « f?' rrj T
Precision and Recovery
Standards
3,3',4,4'-TCB
77
0.5
2
10
40
200
2,3,3',4,4'-PeCB
105
2.5
10
50
200
1000
2,3,4,4',5-PeCB
114
2.5
10
50
200
1000
2,3',4,4',5-PeCB
118
2.5
10
50
200
1000
2',3,4,4',5-PeCB
123
2.5
10
50
200
1000
33',4,4',5-PeCB
126
2.5
10
50
200
1000
2,3,3',4,4',5-HxCB
156
5
20
100
400
2000
2,3,3',4,4',5'-HxCB
157
5
20
100
400
2000
2,3,,4,4,,5t5l-HxCB
167
5
20
100
400
2000
3t3,,4,4'f5,5,-HxCB
169
5
20
100
400
2000
2,2',3,3',4,4',5-HpCB
170
5
20
100
400
2000
2,2,,3,4,4',5,5'-HpCB
180
5
20
100
400
2000
2,3,3',4,4',5,5-HpCB
189
5
20
.100
400
2000
Internal Standards
13C12-3,3',4,4'-TCB
77L
100
100
100
100
100
13C12-2,3,3,,4,4'-PeCB
105L
100
100
100
100
100
13C12-2,3',4,4',5-PeCB
118L
100
100
100
100
100
13C12-3,3',4f4',5-PeCB
126L
100
100
100
100
100
13C12-2,3,3',4,4',5-HxCB
156L
100
100
100
100
100
13C12-2,3,3',4,4',5'-HxCB
157L
100
100
100
100
100
13C12-2,3',4,4',5,5'-HxCB
167L
100
100
100
100
100
13C12-3,3',4,4',5,5'-HxCB
169L
100
100
100
100
100
13C12-2,2',3,4,4',5,5-HpCB
180L
100
100
100
100
100
13C12-2,3,3',4>4,,5,5,-HpCB
189L
100
100
100
100
100
Cleanup Standards
13C12-3,4,4',5-TCB
81L
0.5
2
10
40
200
13C12-2,3,3',5,5'-PeCB
111L
2.5
10
50
20C
100r.
Recovery Standards
13012-2,2',5,5-TCB
52L
100
100
100
100
100
13012-2,2',4,5,5'-PeCB
101L
100
100
100
100
100
13C12-2^'3»4>4'^'-HxCB
138L
100
100
100
100
100
13C12-2,2,,3,3,t5,5',6-HpCB
178L
100
100
100
100
100
Final Eluter
13C12-DCB
209L
200
200
200
200
200
1 Suffix "L" indicates labeled compound.
2 Sections 7,5,6, calibration verification solution.
N- V 4
-------
Table 5. Target Labeled Compound Recovery in Samples
Labeled PCB
IUPAC
No.
Test
cone
(iig/mL)!
Labeled compound
recovery
(ng/mL)
<%)
Internal Standards
13 C12-3,3 ',4,4'-TCB
77
100
20-160
20-160
13 C12-2,3,34,4-PeCB
105
100
20-160
20-160
13 CI 2-2,3 ',4,4',5-PeCB
118
100
20-160
*20-160
13C12-3,3',4,4',5-PeCB
126
100
20-160
20-160
13C!2-2^^,,4,4>HxCB
156
100
20-160
20-160
13 C12-2,3,3 ',4,4',5 '-HxCB
157
100
20-160
20-160
13C i2-2,3,,4,4',5,5'-HxCB
167
100
20-160
20-160
13C12-3,3',4,4',5,5'-HxCB
169
100
20-160
20-160
13C12-2,2',3,4,4',5,5'-HpCB
180
100
20-160
20-160
13C12-2,3,3 ',4,4',5,5-HpCB
189
100
20-160
20-160
Cleanup Standards
—
13C12-3,4,4',5-TCB
81
50
4-32
20-160
13C12-2,3,3',5,5'-PeCB
111
250
40-140
40-140
1 Based on 20 piL final extract volume.
42
N-1S5
-------
Table 6. Descriptors, Exact m/z's, m/z Types, and Elemental Compositions of the PCBs
Exact m/z
Descriptor m/z7 type Elemental composition Substance2
1. 289.9224 ' M C12 H6 35Q4 TCB
291.9194 M+2 C12 H6 35C13 37C1 TCB
301.9626 M 13C12 H6 35C14 TCBJ
303.9597 M+2 13C12 H6 35C13 37a TCBJ
318.9792 Lock Mass - FFK
325.8804 M+2 C12 H5 35C14 37C1 PeCB
327,8775 M+4 C12 H5 35C13 37C12 PcCB
330.9793 Lock Mass Check - PFK
337.9207 M+2 13C12 H5 35C14 37C1 PeCBJ
339.9178 M+4 13C12 H5 35C13 37C12 PeCBJ
2. 325.8804 M+2 C12 H5 35C14 37C1 PeCB
327.8775 M+4 C12 H5 35C13 37C12 PeCB
337.9207 M+2 13C12 H5 35C14 37C1 PeCBJ
339.9178 M+4 13C12 H5 35C13 37C12 PeCBJ
354.9792 Lock Mass - PFK
354.9792 Lock Mass Check - PFK
~ . 393.8025 M+2 C12 H3 35C16 37C1 HpCB
395.7996 M+4 C12 H3 35C15 37C12 HpCB
405.8428 M+2 . 13C12 H3 35C16 37C1 HpCBJ
407.8398 M+4 13C12 H3 35C15 37C12 HpCB'
3. 359.8415 M+2 C12 H4 35C15 37C1 HxCB
361.8385 M+4 C12 H4 35C14 37C12 HxCB
371.8817 M+2 13C12 H4 35C15 37C1 HxCBJ
373.8788 M+4 13C12 H4 35Q4 37C12 HxCB'
380.9760 Lock Mass - PFK
380.9760 Lock Mass Check - PFK
393.8025 M+2 C12 H3 35C16 37Q HpCB
395.7996 M+4 C12 H3 35C15 37C12 HpCB
405.8428 M+2 13C12 H3 35Q6 37Q HpCB"'
407.8398 M+4 -13C12 H3 "35C15 37C12 HpCBJ
4. 504.9696 Lock Mass - PFK
504.9696 Lock Mass Check - PFK
509.7229 M+4 - 13C12 35C18 37C12 DCBJ
511.7199 M+6 13C12 35C17 37Q3 DCBJ
1 Nuclldic masses used were:
H-1.007825 C-12.00000
13C-13.003355 . 35C1 - 34.968853 37C1 - 36.965903
1 TCB ¦ Tetrachlorobiphenyl
PeCB " Pentachlorobiphenyl
HxCB - Hexachlorobiphenyl
HpCB - Heptachlorobiphenyl
DCB - Decachlorobipheayi
1 13C labeled compound.
43
N-156
-------
Table 7. Theoretical Ion Abundance Ratios and QC Limits
Chlorine m/z's forming Theoretical QC Limit1
atoms ratio ratio —
Lower Upper
4 M/(M+2) 0,77 0.65 0.89
5 (M+2)/(M+4) 1.55 1.32 1.78
6 (M+2)/(M+4) 1-24 1.05 1.43
7 (M+2)/(M+4) 1.05 0.88 1.20
10 (M+4)/(M+6) 1.17 0.99 1.35
i- 1 ¦ i iibii i i =s===^=
1 QC limits represent +/-15 percent windows around the theoretical ion abundance ratio. These limits
are preliminary.
44
N 157
-------
Table 8. GC Retention Time Window Defining and Congener Specificity Test Solution1
(Section 7.5.8)
Congener
jr-ovp First e?ut«d Last eluted
TCB
54 ; •
2^2,6,6*
77
3,3',4,4'
PeCB
104
2,2',4,6,6'
126
3,3',4,4',5
HxCB
155
2,2',4,4', 6,6'
169
3,3',4,4',5,5'
JrlpCx?
188
2,2',3,4',5,6,6*
189 '
2,3,3',4,4',5,5'
Isomer snecificitv test ccmoonnds
123
2',3,4,4',5-PeCB
156
2,33',4,4',5-HxCB
118
2,3',4,4',5-PeCB
157
2,3,3',4,4',5'-HxCB
1 All compounds are at a concentration of 100 ng/mL in nonane.
45
N-158
-------
Archive 5 mL
Extract Using SPE
Samples with <= 5% Solids
Filter 1 L of Sample
Samples with > 5% Solids
Extract the
liquid Filtrate
Using SPE
Scrubber Water Sample
Spike with Cleanup Standard
Extract the
Solids using
Soxhlet
Technique
Spike Liquid
with Labeled
Internal
Standards
Spike 1 L of Sample with
Labeled Internal Standards
. Visually Estimate Percent
Solids Content of Sample
Combine Extracts from the
Solids and Liquid Sample
Concentrate Extract to 10 mL
Proceed to Sample Cleanup
Flow Diagram (Figure 2)
Solvent Exchange 5 mL of
Sample Extract to Hexane (50
mL)
Figure 1. Extraction Procedure for Scrubber Water Sample
46
N-159
-------
Silica Gel
Cleanup
* Repeat this step until the
aqueous layer is clear
Discardthe
Aqueous Layer
Discardthe
Aqueous Layer
Discardthe
Aqueous Layer
Add Recovery
Standard Solution
Cartxm Columns
Cleanup
Concentrate
to Final Volume
Extract Hexane Extract
with Sulfuric Acid*
Discard die
Aqueous Layer
Extract the Hexa&e
with
KOH Solution
Wash die Hexane
Layer with
NaCl Solution
Wash die Hexane
Layer with NaCl
Solution
See Figure 1 for
Description of
Sample Extraction
Figure 2. Cleanup Procedure for Scrubber Water Sample
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N-2
Battelle SOPs for D/F Analysis
N-161
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SOP0S02-02-01
Date Printed: 05.'14 99
Page 1 of5
Title: Standard Operating Procedure for Polychlorinated Dibenzo-p-
Dioxin/Polychlorinated Dibenzofuran (PCDD/PCDF) Sample Preparation
Using Modified Method 8290
Number; SOP0802-02-01
The attached Standard Operating Procedure is recommended for approval and commits the
laboratory to follow the elements described within.
This SOP is a controlled document which is maintained by the QA Coordinator and included in
appropriate Quality Assurance Project Plans, as required.
touwu
ichnical or Mana^gfotfnt Approval
JlUCMJ},
QA Coordinator Approval y
Date
Date
Distribution
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SOP0802-02-Q1
Date Printed: 05/14/99
Page 2 of 5
A. Procedure
Al. Scope and Applicability
This SOP describes routine procedures for preparing samples for PCDD/PCDF analysis. These
procedures follow general guidelines described in EPA Method 8290, with some minor
modifications/improvements.
A2. Summary of Method
The purpose of this SOP is to provide a description of PCDD/PCDF sample preparation activities
using modified Method 8290 procedures and covers the following:
¦ Sample collection, preservation, and handling
¦ Sample extraction and internal standard spiking
¦ Extract cleanup and
¦ Final concentration activities.
A3. Definitions
All references in this section are to SW846 Method 8290 unless otherwise indicated.
A4. Personnel Qualifications
Personnel assigned to laboratory activities meet the educational, work experience, and training
requirements for their positions. Records on personnel qualifications and training are maintained
in personnel files accessible for review during audit activities. Training is conducted in
accordance with standard operating procedures and is available to all laboratory personnel.
Employees must demonstrate proficiency at specific tasks and this capability is documented and
kept in a central file.
A5. Sample Collection
An. ?cmp)es are collected according to Section 6.2 or as required by the client.
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Page 3 of 5
A6. Handling and Preservation
All samples are handled according to Section 6.2 or as required by the client.
A7. Sample Preparation and Analysis
Samples are spiked with internal standard and extracted using the matrix-specific technique^
described in Section 7.0. Modifications to Section 7.0 include:
1, Fish Tissue (Section 7,2) - When a lipid determination is not required, a 10 g portion of the
fish sample and 250 mL of hexanermethylene chloride (1:1) are used for extraction. Whether or
not a lipid determination is required, the fish sample is mixed with 5 to 10 g Varian Hydromatrix
drying agent until free flowing. The remaining fish tissue extraction follows that described in the
method.
2. Soil/Sediment (Section 7.4.6) - The soil/sediment sample is mixed with 5 to 10 g ofVariar.
Hydromatrix drying agent until free flowing. Toluene is used as the extraction solvent without a
Dean Stark apparatus. The sample extract is typically not filtered through a glass fiber filter
unless a significant amount of solids are present in the extract.
Hydromatrix is used as a drying agent rather than sodium sulfate since the time required for the
sample-drying agent mixture to become free flowing is reduced when Hydromatrix is used
Samples prepared using Hydromatrix have yielded equivalent internal standard recoveries as
those prepared using sodium sulfate.
Prior to all extractions, the sample/Hydromatrix mixture is spiked with an internal standards
solution containing fifteen 13Ci2-labeied PCDD/PCDF, as called for in Method 1613, Table 3
rather than nine as stated in Method 8290. The additional labeled PCDD/PCDF allow all but two
of the isomers to be directly related to an internal standard for identification and quantification
purposes. Use of this complete range of internal standards provides better accuracy than
afforded by standard Method 8290.
PartjtiQn
The extracts are partitioned against acid and base solutions as described in Section 7.5.1 with the
following modifications: j
' \
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Date Prated: 05/14/99
Page 4 of 5
1. After the samples are transferred to the separatory funnels, the extracts are spiked with a
cleanup standard (2,3,7,8-TCDD-37CU) as called for in Method 1613, Section 7.11. This cleanup
standard is used to monitor the'recovery of the analytes through the cleanup process.
2. Instead of the 40-mL acid, base, and salt washes that are specified in Method 8290, Section
7.5.1, the samples are subject to one 30-mL acid wash, successive 20-mL acid washes as needed
to remove color, one 20 mL salt wash, onel5-mL base wash, and two 20 mL salt washes.
Reducing the volume of acid, base and salt solutions has proven non-deleterious to internal
standard recoveries.
Silica/Alumina Column Cleanup
The extracts are put through silica and alumina columns in a manner similar to that called for in
Section 7.5.2 with the following modifications:
Although the silica column is prepared as described in the method, the alumina column is
prepared using 6 g of Sigma basic alumina. Both silica and alumina columns are rinsed
independently with 20 mL of hexane. The columns are then stacked with the silica on top of the
alumina and the sample extract is applied to the silica column. The stacked columns are rinsed
with 100 mL of hexane which is discarded. The columns are separated so that 40 mL of
hexane:methylene chloride (1:1) may be passed through the alumina column. The
hexane:methylene chloride eluant is collected and concentrated to 1 mL for processing through a
carbon column.
Utilizing this stacked column approach has proven non-deleterious to internal standard
recoveries but has decreased sample preparation time and solvent usage. Procedures for the use
of basic alumina are taken from Method 1613, Section 13.4.
Carbon Column Cleanup
The sample extracts are processed through a carbon column as described in Section 7.5.3 with
the following modifications:
The carbon mixture that is used to pack the column consists of a 20% (w/w) mixture of
Carbopack-C/Celite 545. Method 1613, Section 13.5 suggests the use of an 18%
Carbopack/Celite mixture. A 20% Carbopack/Celite mixture was chosen in order to remove
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Date Printed: 05/14/99
Page 5 of 5
more interferences from the sample extracts and to improve internal standard recoveries. When
the column is packed, only glass wool, 0.55 g of the carbon mixture, and more glass wool arc
used. The additional plugs of Celite are not used.
The elution scheme is essentially the same as specified in Method 1613, Section 13.5 v,ith the
exception that the carbon columns are back-eluted with 30-mL toluene rather than 20 ml as
specified in Section 13.5.5.
The final concentration and reconstitution of the sample extracts is significantly different than
that described in Section 7.5.3.6 to accommodate transfer of the extract to GC autosampier vials:
20 :L of nonane is pipetted into muffled, methylene chloride-rinsed concentrator tubes. The
tubes are lightly tapped to remove any air bubbles present and the meniscus is maiked. 200 ;I of
hexane is pipetted into the tubes and the meniscus is marked. Leaving the solvents in the tubes,
the sample extracts are transferred from round bottom flasks to tubes using 3 x 1 mL hexane
rinses. The extracts are blown down to approximately 200 :L. The round bottom flasks are
rinsed with 1 mL of methylene chloride which is transferred to the tubes and again concentrated
to approximately 200 :L. The round bottom flasks are rinsed with 0.5 mL of methylene chloride
which is transferred to the tubes and again concentrated to 200 :L. The extracts are spiked with
10 :L of the nonane recovery spiking solution and vortexed for 30 seconds. The extracts are
blown down to the 20 :L meniscus level and then transferred to a GC vial for analysis.
The above procedure has been proven as an effective and efficient method of concentrating the
sample extracts for analysis.
B. References
1. SW-846, Method 8290. Polychlorinated Dibenzodioxins (PCDDs) and Polychionnated
Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-Resolution Mass
Spectrometry (HRCG/HRMS), Revision 0,1994.
2. EPA Method 1613: Tetra-Through Octa-Chlorinated Dioxins and Furans by Isotope Dilution
HRGC/HRMS, Revision B, 1994, EPA 821-B-94-005.
-------
SOP0802-01-01
Date Printed: 05/24/99
Page 1 of 5
Title: Standard Operating Procedure For The Analysis of Polychlorinated
Dibenzo-p-Dioxin/Polychlorinated Dibenzofiiran (PCDD/PCDF) Using
High Resolution Gas Chromatography/High Resolution Mass Spectrometry
(HRGC/HRMS) Using Modified Method 8290
Number: SQP0802-01-01
The attached Standard Operating Procedure is recommended for approval and commits the
laboratory to follow the elements described within.
Distribution
This SOP is a controlled document which is maintained by the QA Coordinator and included in
appropriate Quality Assurance Project Plans, as required.
arfmical or Man^ge^nt Approval
UU'Mi 4-"
QA Coordinator Approval
s/u/rr
Date
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SOP0802-01-01
Date Printed: 05/14/99
Page 2 of 5
A. Procedure
Al. Scope and Applicability .
This SOP describes routine procedures for HRGC/ HRMS analysis of samples for PCDD PCDF
These analyses follow general guidelines described in EPA Method 8290, with some minor
modifications/improvements.
A2. Summary of Method
The purpose of this SOP is to provide a description ofPCDD/PCDF sample analysis activities
using modified Method 8290 procedures and covers the following:
¦ Chromatographic/Mass Spectrometry conditions and data acquisition parameters
¦ Calibration
¦ jAnalysis
¦ Calculations and
¦ System performance criteria.
A3. Definitions
VG, Fisons, and Micromass all refer to the same company, and may be used interchangeably
A4. Personnel Qualifications
Personnel assigned to laboratory activities meet the educational, work experience, and training
requirements for their positions. Records on personnel qualifications and training are maintained
in personnel files accessible for review during audit activities. Training is conducted in
accordance with standard operating procedures and is available to all laboratory personnel.
Employees must demonstrate proficiency at specific tasks and this capability is documented and
kept in a central file.
AS. Apparatus and Materials
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Date Printed; 05/14/99
Page 3 of 5
All calibration, column performance, window defining, recovery standards, internal standards
spiking solutions, PARs, SRMs, etc. are obtained from commercial sources such as Cambridge
Isotope Labs.
A6. Instrument or Method Calibration
The GC/HRMS instrumentation is calibrated at levels specified in Method 1613, Table 4 with
one additional calibration standard at concentrations equivalent to Vi the level of Method 1613's
lowest calibration point The Method 1613 calibration solutions represent an expanded
calibration concentration range compared to the calibration range in Method 8290.
Using the option in Method 1613, Section 10.2, only 1 ul of calibration solution or sample
extract is injected per run, rather than 2 ul as specified in Method E290, Section 7.7. The
samples are injected on-column, rather than split-splitless as stated in Method 8290, Section 7.6.
For DB-5 continuing calibration analyses, a combination solution made by Cambridge Isotope
Labs, composed cf Calibration solution 3, window defining mixture, and tetra dioxin GC column
performance mixture, is injected at the beginning and end of each 12 hour run period. The
response factors are checked against the mean RRF from the initial calibration, and must fall
within the +/- 20% RRF window for natives, and the +/- 30% window for I3C-lableled
compounds, unless otherwise specified by the client. This allows determination of calibration
and column performance in a single run.
A7. Sample Preparation and Analysis
A.7.1 Sample Preparation
For sample preparation procedures, see SOP for Poly chlorinated Dibenzo-p-
dioxin/Polychlorinated Dibenzofuran (PCDD/PCDF) Sample Preparation Using Modified
*/¦ , * . i n r*
,w b* — _ W -
A.7.2 Sample Analysis
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SOP0802-01-01
Date Printed: 05/14/99
Page 4 of 5
The GC/MS parameters listed in Method 3290, section 7.6 are followed with the follo wing
exception:. The GC :chr^ LSv~d Id X»lvt-fcAWsl SJ+.S v wuSC d, but the temperatuxc, iioo a
*» *
different initial temperature (140 C) to allow the solvent peak to elute slowly enough to not trip
the source ion gauge. The upper temperature of the ramp is held to 320 C rather than 330 C to
accommodate the upper temperature limit of the column.
All five groups (Tetra through Octa) are monitored separately. The mass for the cleanup
standard 37Cl4-2,3,7,8-TCDD, ;s also monitored per Method 1613, Table 8. Analysis is carried
out as stated in Method 8290, Section 7.8.
A8. Data Acquisition, Calculations, and Data Reduction
Calculations are carried out using Opusquan, a software program designed for dioxin/furan
analysis by VG/Micromass Co. Ltd. These calculations are the same as specified in Method
8290, Section 7.9. Estimated detection limit is calculated by measuring the sum of the heights of
a native peak at the predicted retention time, times 2.5, divided by the total area of its internal
standard ions, using the equation:
MDL = (F * Ni * Si * A/H * Qs) / (RJRF *As * S)
Where
F = the user factor (dl_factor) in the form "fullrun"
Ni = the sum of the noise level of the analyte ions
Si = the sum of the "min_sig_to_noise" keyword value for each of the analyte ions
A/H = the mean area: height ratio of all ions of this analyte's internal standard
Qs = the internal standard amount
RRF = the mean relative response factor of the analyte
As = the total area of all internal standard ion peaks
S = the weight of the sample
A method blank is analyzed and processed using Opusquan in the "blank" mode. The noise
factor for the natives in this blank run is then subtracted from subsequent runs, which are j
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Date Printed: 05/14/99
Page 5 of5
processed in the "quantitation" mode to obtain an accurate detection limit for each analyte in
each run.
A9. Computer Hardware and Software
Calculations are earned out using Opusquan, a software program designed for dioxin/furan
analysis by VG/Micromass Co. Ltd.
B. Quality Coutrol and Quality Assurance
B.l. System Performance Criteria
A combination calibration solution 3/window defining mixture/column performance mixture is
injected at the beginning and end of each twelve-hour period. This is to ensure adequate
resolution of the isomeric peaks, to ascertain that the windows are set correctly to see all the
isomqrs in each congener group, and to verify that the HUMS is adequately tuned. A PFK
resolution check is also hard-copied at the beginning and end of each GC/HRMS analysis batch
to verify mass resolution.
C. References
1. SW-846, Method 8290. Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated
Dibetizofurans (PCDFs) by High Resolution Gas Chromatography/High Resolution Mass
Spectrometry (HRGC/HRMS), Revision 0,1994.
2. EPA Method 1613: Tetra-Through Octa-Chlorinated Dioxins and Furans by Isotope Dilution
HRGC/HRMS, Revision B, 1994, EPA 821-B-94-005.
3. VG Opusquan 2.0 Reference Manual, Issue 4, March 1995
4. Private communication from John Bill, Fisons Instruments, 04-20-95
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N-3
PAH Protocols
N-172
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California Environmental Protection Agency
®j§Air Resources Board
Method 429
Determination of Poly cyclic Aromatic
Hydrocarbon (PAH) Emissions
from Stationary Sources
Adopted: September 12, 1989
Amended: July 28, 1997
N-173
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TABLE OF CONTENTS
Page
1 INTRODUCTION 1
1.1 APPLICABILITY ...1
1.2 PRINCIPLE 1
1.3 DEFINITIONS AND ABBREVIATIONS 1
2 THE PRE-TEST PROTOCOL 4
2.1 RESPONSIBILITIES OF THE END USER, TESTER, AND ANALYST 4
2.2 PRE-TEST REQUIREMENTS 5
2.3 REQUIRED PRELIMINARY ANALYTICAL DATA 6
2.4 EXPECTED RANGE IN TARGET PAH CONCENTRATIONS
OF INDIVIDUAL PAHs.: - 7
2.5 1 SAMPLING RUNS, TIME, AND VOLUME 7
%
3 INTERFERENCES 10
4 SAMPLING APPARATUS, MATERIALS, AND REAGENTS 11
4.1 SAMPLING APPARATUS 11
4.2 SAMPLING MATERIALS AND REAGENTS 14
4.3 PRE-TEST PREPARATION 1?
4.4 SAMPLE COLLECTION 20
4.5 CALCULATIONS ...... 26
4.6 ISOKINETIC CRITERIA 30
5 SAMPLE RECOVERY 30
5.1 SAMPLE RECOVERY APPARATUS 30
5.2 SAMPLE RECOVERY REAGENTS 31
5 ?. SAMPLE RECOVERY PROCEDURE 32
July 28, 19; ' M-429Pa}y. "
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5.4 SAMPLE PRESERVATION AND HANDLING 33
6 ANALYTICAL PREPARATION 34
6.1 SAFETY 34
6.2 CLEANING OF LABORATORY GLASSWARE 34
6.3 APPARATUS 34
6.4 SAMPLE PREPARATION: REAGENTS 35
6.5 SAMPLE EXTRACTION 36
6.6 COLUMN CLEANUP 37
7 GC/MS ANALYSIS 41
7.1 APPARATUS 41
7.2 REAGENTS.., 42
7.3 INITIAL CALIBRATION ' • 45
7.4 CONTINUING CALIBRATION 47
7.3 GC/MS ANALYSIS ! 48
7.6 QUALITATIVE ANALYSIS 49
7.7 QUANTITATIVE ANALYSIS 49
8 QUALITY ASSURANCE/QUALITY CONTROL 51
8.1 QA SAMPLES 51
8.2 ACCEPTANCE CRITERIA 53
8.3 ESTIMATION OF THE METHOD DETECTION LIMIT (MDL)58
AND PRACTICAL QUANTITATION LIMIT (PQL) 55
8.4 LABORATORY PERFORMANCE 55
9. CALCULATIONS 56
9.1 ANALYSTS CALCULATIONS 56
9.2 TESTER'S CALCULATIONS 60
July 28, 1997 M-429 Page ii
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10 REPORTING REQUIREMENTS 63
10.1 PRE-TEST PROTOCOL 63
10.2 LABORATORY REPORT 64
10.3 EMISSIONS TEST REPORT r 67
11 BIBLIOGRAPHY.... 69
TABLES
1 Method 429 Target Analytes 70
2 Practical Quantitation Limits for Target PAHs 71
3 PAH Analysis by HRMS of Different Lots.
of Cleaned Resin 72
4 Composition of the Sample Spiking Solutions 73
4A Composition of Alternative Sample Spiking Solutions 74
5 Concentrations of PAHs in Working GC/MS Calibration
Standard Solutions for Low Resolution Mass Spectrometry 75
6 Concentrations of PAHs in Working GC/MS Calibration
Standard Solutions for High Rjesolution Mass Spectrometry 77
6A Concentrations of PAHs in Alternative Working GC/MS Calibration
Standard Solutions for High Resolution Mass Spectrometry 79
7 Spike Levels for Labelled Standards 8 j
7 A Spike Levels for Labelled Standards for Alternative
HRMS Spiking Scheme 82
8" Target Concentrations for Labelled Standards in Sample Extract 83
8A Target Concentrations for Labelled Standards in Sample Extract
Obtained with Alternative HRMS Spiking Scheme 84
9 Concentrations of compounds in Laboratory Control Spike Sample 8:
10 Recommended Gas Chromatographic Operating Conditions
for PAH Analysis 86
July 28,1997 M-429 Page
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11 Assignments of Internal Standards for Calculation of RRFs
and Quantitation of Target PAHs and Surrogate Standards 87
11A Assignments of Interna] Standards for Calculation of RRFs
and Quantitation of Target PAHs and Surrogate
Standards Using Alternative HRMS Spiking Scheme 88
12 Assignments of Recovery Standards for Determination of Percent
Recoveries of Internal Standards and the Alternate Standard 89
12A Assignments of Recovery Standards for Determination of
Percent Recoveries of Internal Standards and the Alternate Standard
Using Alternative HRMS Spiking Scheme 90
13 Quantitation and Confirmation Ions for Selected
Ion Monitoring of PAHs by HRGC/LRMS 91
14 Mass Descriptors Used for Selected Ion Monitoring
of PAHs by HRGC/HRMS 93
FIGURES
1 Method 429 Flowchart 95
2 PAH Sampling Train 96
3 Condenser and Sorbent Trap for Collection of Gaseous PAH 97
4 XAD-2 Fluidized Bed Drying Apparatus 9E
5 Method 429 Field Data Record *. 99
6 Recovery of PAH Sampling Train 100
7 Flowchart for Sampling, Extraction and Cleanup for
Determination of PAH in a Split Sample 101
8 Flowchart for Sampling, Extraction and Cleanup for
Determination PAH in a Composite Sample 102
9 Example of Pre-Test Calculations 103
10 CARB Method 429 (PAHs) Sampling Train Setup Record 104
11 CARB Method 429 (PAHs) Sunpling Train Recovery Record 105
12 Chain of Custody Sample Record 106
July 28, 1997 M-429 Page iv
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13 Chain of Custody Log Record 107
14A Example of GC/MS Summary Report (HRMS) for
Initial Calibration Solution #1 108
14B Example of Initial Calibration (ICAL) Summary 109
14C Example of Continuing Calibration Summary 110
15A Example of Summary Report of LCS Results Ill
15B LCS Recoveries for Benzo(a)pyrcne 112
16A Example GC/MS Summary Report (HRMS) for Sample Run #32 113
16B Example Laboratory Report of PAH Results for Sample Run #32 114
17A Example of Tester's Summary of Laboratory Reports 115
17B Field Data Summary for PAH Emissions Test 116
17C Example of Emissions Test Report 117
APPENDIX A
Determination of the Method Detection Limit 118
July 28,
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Method 429
Determination of Polycyclic Aromatic Hydrocarbon (PAH)
Emissions From Stationary Sources
1 INTRODUCTION
1.1 APPLICABILITY
This method applies to the determination of nineteen polycyclic aromatic hydrocarbons (PAH) in
emissions from stationary sources. These are listed in Table 1. The sensitivity which can ultimately
be achieved for a given sample will depend upon the types and concentrations of other chemical
compounds in the sample as well as the original sample size and instrument sensitivity.
Any modification of this method beyond those expressly permitted shall be considered a major
modification subject to approval by the Executive Officer of the California Air Resources Board or
his or her authorized representative.
1.2 PRINCIPLE
Particulate and gaseous phase PAH are extracted isokineticaliy from the stack and collected on
XAD-2 resin, in impingers, or in upstream sampling train components (filter, probe, nozzle). Only
fee total amounts of each PAH in fee stack emissions can be determined with this method. It has not
been demonstrated that the partitioning in the different parts of fee sampling train is representative of
the partitioning in the stack gas sample for particulate and gaseous PAH.
The required analytical method is isotope dilution mass spectrometry combined with high resolution
gas chromatography. This entails the addition of internal standards to all samples in known
quantities, matrix-specific extraction of the sample wife appropriate organic solvents, preliminary
fractionation and cleanup of extracts and analysis of fee processed extract for PAH using high-
resolution capillary column gas chromatography coupled with either low resolution mass
spectrometry (HRGC/LRMS), or high resolution mass spectrometry (HRGC/HRMS). To ensure
comparable results, the same MS method must be used for samples collected at all tested locations at
those sources where more than one location is tested.
Minimum performance criteria are specified herein which must be satisfied to ensure the quality of
fee sampling and analytical data.
1.3 DEFINITIONS AND ABBREVIATIONS
.3.1 Internal Standard
An internal standard is a 2H-labelled PAH which is added to all field samples, blanks and other
quality control samples before extraction. It is also present in fee calibration solutions. Internal
standards are used to measure fee concentration of fee analyte and surrogate compounds. There
is one internal standard assigned to each of fee target analytes and surrogates.
July 28, 1997 M-429Page
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1.3.2 Surrogate Standard
A surrogate standard is a labelled compound added in a known amount to fee XAD-2 resin of the
sampling train, and allowed to equilibrate with the matrix before the gaseous emissions are
sampled. The suirogate'standard has to be a component that can be completely resolved, is not
present in die sample, tad does not have any interference effects. Its measured concentration in
the extract is an indication of the how effectively the sampling train retains-PAH collected on the
XAD-2 resin. The recovery of the surrogate standards in die field blanks can be used to
determine whether there are arty matrix effects caused by time or conditions under which the
sample is transported and stored prior to analysis.
1.3.3 Alternate Standard
An alternate standard is a H-labelled PAH compound which is added to the impinger contents
prior to extraction to estimate the extraction efficiency for PAHs in die impinger sample
1.3.4 Recoveiy Standard
A recovery standard is a 2H-labelled PAH compound which is added to the extracts of all field
samples, blanks, and quality control samples before HRGC/MS analysis. It is also present in the
calibration solution. - The response of the internal standards relative to the recovery standard is
^ used to estimate the recovery of the internal standards. The internal standard recovery is an
indicator of the overall performance of the analysis.
1.3 5 Relative Response Factor
The relative response factor is the response of the mass spectrometer to a known amount of an
analyte or labelled compound (internal standard or surrogate standard) relative to a known
amount of an internal standard or another labelled compound (recoveiy standard or internal
standard).
1.3.6 Performance Standard
A performance standard is a mixture of known amounts of selected standard compounds It i>
used to demonstrate continued acceptable performance of the GC/MS system. These checks
include system performance checks, calibration checks, quality checks, matrix recovery , and
surrogate recoveries.
1.3.7 Performance Evaluation Sample
A performance evaluation sample is one prepared by EPA or other laboratories that contains
known concentrations of method analytes, and has been analyzed by multiple laboratories to
determine statistically the accuracy and precision that can be expected when a method is
performed by a competent analyst. Concentrations must be in the same range as typical field
samples. Analyte concentrations are not known by the analyst
July 28, 1997 M-429 P-.,
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1.3.8
Laboratory Control Sample
A laboratory control sample is one that contains known concentrations of method analvtes that is
analyzed by a laboratory to demonstrate that it can obtain acceptable ider*i^""'~:'-"-
measurements with procedures to be used to analyze field samples containing the same analytes.
Analyte concentrations' are known by the analyst The laboratory must prepare the control
sample from stock standards prepared independently from those used for calibration.
1.3.9 End User
The regulating agency shall be considered the end user if this test method is conducted for
regulatory purposes, or the regulating agency shall designate the end user for the purposes of this
method. Otherwise the end user shall be the parly who defrays the cost of performing this test
method. In any case, the pre-test protocol (Section 2) must identify the end user.
1.3.10 Tester
Usually the tester is a contract engineering firm that performs the sampling procedures and
delegates responsibility for specific analytical procedures to an analytical group (usually part of a
subcontracting laboratory firm). In some cases, the tester may be part of the regulating agency.
The tester shall be the party ultimately responsible for the performance of this test method
whether directly or indirectly through the co-ordination of the efforts of the analytical group and
the efforts of the sampling group.
1.3.11 Analyst
This term refers to the analytical group that performs the analytical procedures to generate the
required analytical data.
1.3.12 Source T arget Concentration
This is the target concentration for each emitted PAH of interest specified by the end user of the
test results. The target concentration shall be expressed in units of mass of target substance per
volume of emissions; typical units are nanograms per dry standard cubic meter or micrograms
per dry standard cubic meter (ng/dscm or jag/dscm)
1.3.13 The Method Detection Limit
The method detection limit (MDL) is based on the precision of detection of the analyte
concentration near the detection limit It is the product of the standard deviation of seven
replicate analyses of resin samples spiked with low concentrations of the analyte and Student's t
value for 6 degrees of freedom at a confidence level of 99%.
1.3.14 The Practical Quantitation Limit
The practical quantitation limit (PQL) is a limit for each compound at or below which data must
not be reported. It is the minimum sample mass that must be collected in the sampling train to
allow detection during routine laboratory operation within the precision limits established by the
July 28, 199? M-429 Page 3
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MDL determination. The PQLs will be estimated at 5 times the MDL for those PAH that are not
contaminants of the resin. The PQL for the remainder will be estimated at 5 times the blank
XAD-2 resin level.
2 THE SOURCE TEST PROTOCOL
Every performance of this test method shall have an identified operator of the source to be tested, an
identified end user of the test method results, and an identified tester who performs this test methoa.
Figure 1 is a summary of the responsibilities of the parties Involved is the coordination and performance
of the source test The protocol for the entire test procedure should be understood and agreed upon by
the responsible parties prior to the start of the test.
2.1 RESPONSIBILITIES OF THE END USER AND THE TESTER
2.1.1 Hie End User
Before testing may begin, the end user of the test results (1.3.9) shall specify a source target
concentration for each of the PAH to be determined by this method using the guidelines of
Section 2.2.1.
The end user shall approve the source test protocol only after reviewing the document and
determining that the minimum pre-test requirements (Sections 2.2 to 2.5) have been met
2.1.2 The Tester
The tester (1.3.10) shall have fee primaiy responsibility for the performance of the test method,
and shall co-ordinate die efforts of the analytical group and the efforts of the sampling group
The tester shall be responsible for the selection of an analyst with documented experience in the
satisfactory performance of the method. The tester shall obtain from the analyst all of the
analytical data (Section 2.3) that are required for pre-test calculations of sampling parameters
Before performing the rest of this method, the tester shall develop and write a source test
protocol (Section 2.2) to help ensure that useful test method results are obtained The tester shal!
plan the test based on the information provided by the end user, the results of pre-test surveys of
the source, and the tester's calculations of target source testing parameters (Section 2,2).
The tester shall be responsible for ensuring that all of the sampling and analytical reporting
requirements (Section 10) are met
2.1.3 The Analyst
Hie analyst shall be responsible for performing all of the required analytical procedures
described in this test method and reporting the results as required by Sections 2.3,4.2 1, 4.2.2,
lu.i.i, 10.1.2, 10.1.3, and 10.2).
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2.2 PRE-TEST REQUIREMENTS
The source test protocol shall specify the test performance criteria of the end user and all
assumptions, required data and calculated targets for thi following testing parirr.
(1) source target concentration of each emitted PAH of interest (2.2.1),
(2) preliminary analytical data (2.3) for each target PAH, and
(3) planned sampling parameters (2.5.4,2.5.5, and 2.5.6).
The protocol must demonstrate that the testing parameters calculated by the tester will meet the
needs of the end user. The source test protocol shall describe the procedures for all aspects of the
source test including information on supplies, logistics, personnel and other resources necessary for
an efficient and coordinated test
The source test protocol shall identify the end user of the results, the tester, the analytical group, and
the sampling group, and the protocol shall be signed by the end user of the results and the tester.
The tester shall not proceed with the performance of the remainder of this method unless the snurce
test protocol is signed by the tester and the end user.
s
2.2,1 Source Target Concentration (STC)
The tester shall not proceed with the test unless a target concentration has been chosen. This will
be the primary reporting objective of the emissions test The end user shall select a basis for
determining each target concentration from: a) regulatory limits, b) environmental risk
assessments, aad (c) the interests of the end user, the tester, and the stationary source.
2.2.1.1 Regulatory Limits
The regulatory limit shall be the basis for determining a target concentration for stationary
source emissions in those cases where the purpose of the Emissions test is to demonstrate
compliance with the established regulatory limit
2.2.1.2 Environmental Risk Assessments
In some cases testing is conducted for an environmental risk assessment A pre-test estimate
of the permissible risk shall then be used to determine the target concentration for stationary
source emissions.
Note that some risk assessment methodologies will assume that a PAH is present at the
detection limit or one half of die detection limit even when the compound is not detected.
This is inappropriate for planning for the performance of the test method because by
definition a substance cannot be detected at one half of its detection limit In such cases, the
target sampling parameter must be the maximum practical sample volume.
July 28, 1997 M-429 Page 5
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2.2.1.3 Interests of the Bad User, the Tester and the Stationary Source
In cases where the emissions test is not being performed to demonstrate compliance with a
regulation, nor is it required for a risk assessment, the end user may use emissions results
from previous tests bf die facility or from similar facilities.
If estimates of the emissions are not available, the tester must conduct a preliminary 4est at
each emissions point of interest This target concentration is necessary for the calculation of
the target sampling parameters required by Section 2.5. Therefore, the emissions measured
during the preliminary test must be representative of source operation. The tester must
document operating conditions, and know from historical data, the extent to which the
results of this preliminary run are representative of emissions from the source. This will
require documentation of operating conditions during the preliminary test, and a knowledge
of the potential variability in emissions with differences in source operation.
As an alternative to conducting a preliminary test, die end user may specify, as a sampling
target, the longest practical sampling time so as to obtain the lowest practically achievable
source reporting limit (Section 2.5.6).
2.3 REQUIRED PRELIMINARY ANALYTICAL DATA
2.3.1 Results of Blank Contamination Checks
The tester must obtain from the analyst the results of the PAH contamination checks The
analytical report must satisfy the reporting requirements of Sections 10 and 10.1.
The analyst shall use the procedures described in Sections 4.2.1 and 4.2.2 to clean the sampling
media (filters and XAD-2 resin) and check for PAH contamination.
Table 3 shows the results of analyses of different lots of re-cleaned XAD-2 resin The purpose
of this table is to show typical variability. Actual results may vary from one test to another
2.3.2 The Method Detection Limit
The method detection limit (MDL) must be determined by the same analyst (1.3.11) that w:li
perform the analyses subsequent to sampling. Before estimating the method detection limit
(MDL), the analyst shall identify those PAH that are contaminants of die XAD-2 resin using the
procedures described in Sections 4.2.2.1 to 4.2.2.4. The analyst shall determine the MDL as
described in Section 8.3 and Appendix A.
2.3.3 The Practical Quantitation Limit
The analyst shall calculate the practical quantitation limits (PQLs) for the target PAH. This
value will be 5 times die MDL or 5 times the XAD-2 background level for those compounds that
have been identified by the analyst as contaminants.
July 28,1997 M429 P..
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Table 2 lists practical quantitation limits obtained during ARB's development of this method
The values for the PQLs will van- with the performance of individual laboratories. I herefore,
die tester must obtain PQL values for all of die target analytes from the analyst.
2.4 EXPECTED RANGE IN TARGET CONCENTRATIONS OF INDIVIDUAL PAHs
The PAH compounds in a source test sample-can show large differences in concentrations. A sample
that might provide sufficient analyte for the detection and quantitation of the lowest concentration
PAH could contain levels of other PAHs that exceed the upper limit of the method.
In some cases the solution is two GC/MS injections - first with the undiluted extract, and then again
after appropriate dilution of the extract At other times the required minimum dilution might be so
large as to result in the reduction of the internal standard response below the minimum required by
the method. With prior notification of expected levels of the target analytes, the analyst can modify
the preparation of the samples so that useful results might be obtained. All major modifications must
be approved by the Executive Officer.
2.5 SAMPLING RUNS, TIME, AND VOLUME
2.5.1 Sampling Runs
A test shall include at least three sampling runs in series and a blank sampling train.
2.5.2 Minimum Sample Volume (MSV)
This is the minimum sample volume that must be collected in the sampling train to provide the
minimum reportable mass of PAH for quantitation. It must be based on a) the practical
quantitation limit (2.3.3), b) the source target concentration (2.2.1), and c) sampling limitations.
Use Equation 429-1 to calculate the target MSV for each PAH analyte.
MSV(dscm) = PQL x _L 429-1
STC
— Where:
PQL = The practical quantitation limit, ng/sample (Section 2.3.3)
STC = The source target concentration, ng/dscm (Section 2.2.1)
July 28, 1997 M-429Page?
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2,5.3
Minimum Sampling Time (MST)
This is the minimum time required to collect the minimum sample volume at die expected
average volumetric sampling rate (VSR), Use Equation 429-2 to calculate the minimum
sampling time (MSI) required to collect the minimum sample volume calculated in Section
2.52. The tester must use an average volumetric sampling rate (VSR) appropriate for the source
to be tested.
MST(hours) = —' -Y * * — 429*2
VSR 0.028317 60
Where:
VSR ¦ Expected average volumetric sampling rate, dscfm
60 - Factor to convert minutes to hours
0.028317 = Factor to convert dscf to dscm
The end user must decide whether the MSTs are all practically feasible and whether they can be
increased to allow for any deviation from the sampling and analytical conditions assumed by the
\ test plan. Based on this decision, the tester must use either Section 2.5.4 (a) or 2.5.4 (b) to
| calculate a planned sample volume (PSV).
2.5.4 Planned Sample Volume (PSV)
This is die volume of emissions that must be sampled to provide the target anaiytes at levels
between the PQL and the limit of linearity. The planned sample volume is the primary sampling
target whenever practically feasible. The PSV is calculated according to either 2.5.4 (a) or
2.5.4 (b).
(a) If the end user has decided that the MSTs can be increased, die tester must use Equation
429-3 to calculate the PSV using die largest of the 19 MSV values calculated in Section
2.5.2. and the largest value for F that will give a practically achievable sample volume that
provides the target anaiytes at levels between die PQL and the limit of linearity. Use this
PSV to calculate the planned sampling time (Section 2.5.5 a) and Equation 429-6
(b) If the MSTs are not all practically achievable, the tester and die end user must agree on a
maximum practical sampling time (Section 2.5.5b). This value must then be used for the
PST in Equation 429-4 to calculate the PSV. Hie tester must identify in the source test
protocol the target anaiytes for which the PSV is lower than the MSV. The primary
reporting objective of fee test cannot be achieved for those anaiytes. If the primary reporting
objective cannot be achieved for all of the target anaiytes, it must be discussed in die
nmtnrol and the alternative reporting objective (Section 2.5.6) must be approved by the end
user of the results.
The volu.-' r' ¦; that is actually collected will be determined by practical sampling
limitat-.rjtnc.. of the data and the level of uncertainty that the end user car.
July 28,1997 M429Pag.- '
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tolerate in the measurement of the target concentrations. This uncertainty will d:crease as
the value of F (Equation 429-5) increases.
PSV(dscm) = MSV * F
429-3
PSV(dscm) = PST * VSR
429-4
PSV
MSV
429-5
Where:
PST = Planned sampling time from Section 2.5.5
F = A safety factor (>1) that allows for deviation from ideal sampling and
analytical conditions
2.5.5 Planned Sampling Time (PST)
Two options are available for calculating the planned sampling time depending on whether the
primary objective can be achieved for all of the target anaJytes.
(a) The planned sampling time (PST) shall be long enough to I) collect the planned sample
volume with reportable levels of the target analytes and 2) sample representative operating
conditions of the source. If the average sampling rate (VSR) used to estimate the planned
sampling time cannot be achieved in fee field (Section 4.4.4.1), the sampling time must be
recalculated using the actual VSR and the target PSV in equation 429-6.
(b) The planned sampling time shall be a practical maximum approved by the end user and it
shall be long enough to sample representative operating conditions of the source.
PST (hours) = x
VSR
1
60
429-6
x
0.028317
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2.5.6 Preliminary Estimate of Source Reporting Limit (SRL)
Before the test proceeds, the end user and the tester shall agree on a preliminary estimate of the
source reporting limit for each target PAH. The SRL shall be calculated using Equation 429-7.
The planned sample volume will contain reportable levels of a given analyte if that anahte is
present in the emissions at a concentration that is equal to or greater than die calculated SRL
SRL(ng/dscm) = St 429-7
Where:
SRL « Preliminary estimate of source reporting limit, ng/dscm
PQL = Practical quantitation limit, ng
PSV ¦= Planned sample volume, dscm
2.5.7 Example Calculations
Figure 9 B is an example of the minimum required calculations of sampling parameters for the
source test protocol.
3 INTERFERENCES
Interferences may be caused by contaminants in solvents, reagents, sorbents, glassware, and other sample
processing hardware that lead to discrete artifacts and/or elevated backgrounds at the ions monitored All
of these materials must be routinely demonstrated to be free from interferences under the conditions of
the analysis by running laboratory reagent blanks as described in Section 6.1.1.
The use of high purity reagents and solvents helps to minimira interference problems Purification of
solvents by distillation in all-glass systems may be required.
Transformation of PAH and the formation of artifacts can occur in the-sampling train. PAH degradation
and transformation on sampling train filters have been demonstrated. Certain reactive PAH such as
benzo[a]pyrene, benzo[a]anthracene, and fluoranthene when trapped on filters can readily react with
stack gases. These PAH are transformed by reaction with low levels of nitric acid and higher levels of
nitrogen oxides, ozone, and sulfur oxides-
PAH degradation may be of even greater concern when they are trapped in the impingers When stack
gases such as sulfur oxides and nitrogen oxides come in contact with die impinger water they are
converted into sulfuric acid and nitric acid respectively. There is evidence that under such conditions
certain PAH will be degraded. It is recommended that die PAH levels in the impingers be used as a
tool 'o determine if breakthrough has occurred in die resin.
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4
SAMPLING APPARATUS, MATERIALS AND REAGENTS
4,1 SAMPLING APPARATUS
The sampling train components listed below are required. All surfaces which may come in contact
with the sample or recovery solvents shall be of quartz, borosiicate glass or Teflon. The tester may
use an alternative to the required sampling apparatus only it after review by the Executive Officer, it
is deemed equivalent for the purposes of this test method
Mention of trade names or specific products does not constitute endorsement by the California Air
Resources Board. In all cases, equivalent items from other suppliers may be used.
A schematic of the sampling train is shown in Figure 2. The train consists of nozzle, probe , heated
particulate filter, condenser, and sorbent module followed by three impingers and a silica gel drying
cartridge. An in-stack filter may not be used because at the in-stack temperatures the filter material
must be of a material other than the Teflon required by the method. A cyclone or similar device in
the heated filter box may be used for sources emitting a large amount of particulate matter.
For sources with a high moisture content, a water trap may be placed between the heated filter and
die sorbent module. Additional impingers may also be placed after the sorbent module. If any of
these options are used, details must be provided in the test report The train may be constructed by
adaptation of an ARB Method 5 train. Descriptions of the train components are contained in the
following sections.
4.1.1 Probe Nozzle
Quartz, or borosilicate glass with sharp, tapered leading edge. The angle of taper shall be 30°
and the taper shall be on the outside to preserve a constant internal diameter. The probe nozzle
shall be of the button-hook or elbow design, unless otherwise approved by the Executive Officer.
A range of sizes suitable for isokinetic sampling should be available, e.g., 0.32 to 1.27 cm
(1/8 to 1/2 in.) - or larger if higher volume sampling trains are used - inside diameter (ID)
nozzles in increments of 0.16 cm (1/16 in.). Each nozzle shall be calibrated according to the
procedures outlined in Section 5.1 of ARB method 5.
4.1.2 Probe
The probe must be lined or made of Teflon, quartz, or borosilicate glass. Other inert materials
may be used only if they have been approved by the Executive Officer. The liner or probe
extends past the retaining nut into the stack. A temperature-controlled jacket provides protection i
of the liner or probe. The liner shall be equipped with a connecting fitting that is capable of
forming a leak-free, vacuum tight connection without the use of sealing greases.
4.1.3 Preseparator
A cyclone, a high capacity impactor or other device may be used if necessary to remove the j
majority of the particles before the gas stream is filtered. This catch must be used for any I
July 28, 1997
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i
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subsequent analysis. The device shall be constructed of quartz or borosilicate glass. Other inert
materials may be used subject to approval by the Executive Officer.
4.1.4 Filter Holder
The filter holder shall be constructed of borosilicate glass, with a Teflon frit or Teflon coated
wire support and glass-to-glass seal or Teflon gasket The holder design shall provide a positive
seal against leakage from the outside or around the filter. The holder shall be attached
immediately at the outlet of the probe, cyclone, or nozzle depending on the configuration used.
Whenever "O" ring seals are used, they shall be of Teflon or Teflon coated material Other inert
holder and gasket materials may be used subject to approval by the Executive Officer
4,1.5 Sample Transfer Line
The sample transfer line shall be Teflon (1/4 in. O.D. x 1/32 in. wall) with connecting fittings
that are capable of forming leak-free, vacuum tight connections without using sealing greases
The line should be as short as possible.
4.1.6 Condenser
The condenser shall be constructed of borosilicate glass and shall be designed to allow the
cooling of the gas stream to at least 20°C before it enters the sorbent module. Design for the
normal range of stack gas conditions is shown in Figure 3.
4.1.7 Sorbent Module
The sorbent module shall be made of glass with connecting fittings that are able to form leak-
free, vacuum tight seals without the use of sealant greases (Figure 3). The vertical resin trap is
preceded by a coil-type condenser, also oriented vertically, with circulating cold water. Gas
entering the sorbent module must have been cooled to 20°C (68°F) or less. The gas temperature
shall be monitored by a thermocouple placed either at fee inlet or exit of the sorbent trap The
. sorbent bed must be firmly packed and secured in place to prevent settling or channeling during
sample collection. Ground glass caps (or equivalent) must be provided to seal the sorbent-filled
trap both prior to and following sampling. All sorbent modules must be maintained in the
vertical position during sampling.
4.1.8 Impinger Train
Connect three or more impingers in series with ground glass fittings able to form leak-free,
vacuum tight seals without sealant greases. Whenever "O" ring seals are used, they shall be of
Teflon or Teflon coated material. All impingers shall be of the Greenburg-Smith design
modified by replacing the tip with a 1.3 cm (1/2 in.) ID. glass tube extending to 1.3 cm
(1/2 in.)from the bottom of the flask.
The first impinger may be oversized for sampling high moisture streams. The first and second
impingers shall contain 100 mL of 3 mM sodium bicarbonate (NaHC03) and 2.4 mM sodium
carbonate (Na2C03) (Section 4.2.5). This is intended to neutralize any acids that might form in
1997 M-429 Pag
i
I
July 28,
i
N-1S0
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the impingers. The third impinger shall be empty. Silica gel shall be added to the fo'irth
impinger.
A thermometer which measures temperatures to within 1°C (2°F), shall be placed at the outlet of
the third impinger. .*
4.1.9 Silica Gel Cartridge
This may be used instead of a fourth impinger. It shall be sized to hold 200 to 300 gm of silica
gel-
4.1.10 PitotTube
Type S, as described in Section 2.1 of ARB Method 2 or other devices approved by the
Executive Officer. The pitot tube shall be attached to the probe extension to allow constant
monitoring of the stack gas velocity as required by Section 2.1.3 of ARB Method 5. When the
pitot tube occurs with other sampling components as part of an assembly, the arrangements must
meet the specifications required by Section 4.1.1 of ARB Method 2. Interference-free
arrangements are illustrated in Figures 2-6 through 2-8 of ARB Method 2 for Type S pitot tubes
having external tubing diameters between 0.48 and 0.95 cm (3/16 and 3/8 in.).
Source-sampling assemblies that do not meet these minimum spacing requirements (or the
equivalent of these requirements) may be used only if the pitot tube coefficients of such
assemblies have been determined by calibration procedures approved by the Executive Officer.
4.1.11 Differential Pressure Gauge
Two inclined manometers or equivalent devices, as described in Section 2.2 of ARB Method 2.
One manometer shall be used for velocity head (AP) readings and the other for orifice differential
pressure readings.
4.1.12 Metering System
Vacuum gauge, leak-free pump, thermometers accurate to within 3°C (5.4°F), dry gas meter
capable of measuring volume to within 2 percent, and related equipment, as shown in Figure 2.
Other metering systems must meet the requirements stated in Section 2.1.8 of ARB Method 5.
4.1.13 Barometer
Mercury, aneroid, or other barometer capable of measuring atmospheric pressure to within
2.5 mm Hg (0.1 in. Hg). In many cases, the barometric reading may be obtained from a nearby
national weather service station, in which case the station value (which is die absolute barometric
pressure) shall be requested and an adjustment for elevation differences between the weather
station and sampling point shall be applied at a rate of minus 2.5 mm Hg (0.1 in. Hg) per 30 m
(100 ft) elevation increase or vice versa for elevation decrease.
July 28, 1997 M429Pagel3
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4,1.14 Gas Density Determination Equipment
Temperature sensor and pressure gauge, as described in Section 2.3 and 2.4 of Method 2, and
gas analyzer, if necessary, as described in Method 3. The preferred configuration and alternative
arrangements of the temperature sensor shall be die same as those described in Section 2.1.10 of
ARB Method 5.
4.1.15 Filter Heating System
The heating system must be capable of maintaining a temperature around the filter holder during
sampling of (120±14°C) (248±25°F). A temperature gauge capable of measuring temperature
to within 3°C (5.4°F) shall be installed so that the temperature around die filter holder can be
regulated and monitored during sampling.
4.1.16 Balance
To weigh the impingers and silica gel cartridge to within 0.5 g.
4.2 SAMPLING MATERIALS AND REAGENTS
4.2.1 Filters
: The filters shall be Teflon coated glass fiber filters without organic binders, or Teflon membrane
filters, and shall exhibit at least 99.95 percent efficiency (0.05 percent penetration) on 0.3
micron dioctyl phthalate smoke particles. The filter efficiency test shall be conducted in
accordance with ASTM standard Method D 2986-71 (Reapproved 1978). Test data from the
supplier's quality control program are sufficient for this purpose. Record the manufacturer's lot
number.
4,2.1.1 Contamination Check of Filter
The tester must have the filters cleaned by the analyst and checked for contamination prior to
use in the field. The contamination check must confirm that there are no PAH contaminants
present that will interfere with the analysis of the sample PAHs of interest at the target
reporting limits. The analyst must record the date the filter was cleaned.
The filters shall be cleaned in batches not to exceed 50 filters. To clean the filters, shake for
one hour in methylene chloride in a glass dish that has been cleaned according to Section 6 2
After extraction, remove the filters and dry them under a clean N2 stream. Analyze one filter
using the same extraction, clean-up and analysis procedures to be used for the field samples
(Sections 6.5.1,2,6,6, and 7.5).
Dloiik value _ Total mass (ng) of analyte 429-8
per filter " No. filters extracted
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The acceptance criteria for filter cleanliness depends on 1) the method reportirg limit. ?.*! '.he
expected field sample volume and 3) the desired reporting limit for the sampled emissions
stream. Filters with PAH levels equal to or greater than the target reporting limit for the
analyte(s) cf concern shall be rejected for field use.
If the filter does not pass the contamination check, re-extract the batch and analyze a clean
filter from the re-extracted batch. Repeat the re-extraction and analysis until an acceptably
low background level is achieved. Store the remainder tightly wrapped in clean hexane-
rinsed aluminum foil as described in Section 4.3.3.
Record the date of the last cleaning of the filters and the date of the PAH analysis, and
prepare a laboratory report of the analytical results that includes all of the information
required by Section 10,2.
The tester shall obtain this laboratory report with the date of cleaning of the filters, and the
date of the filter contamination check from the analyst, and report them in the source test
protocol and the test report as required by Sections 10.1 and 10.3.
The XAD-2 resin must be purchased precleaned and then cleaned again as described below
before use in the sampling train.
This procedure must be carried out in a Soxhlet extractor which will hold enough XAD-2 for
several sorbent traps, method blanks and QC samples. Use an all glass thimble containing
an extra coarse frit for extraction of the XAD-2. The frit is recessed 10 to 15 mm above a
crenelated ring at the bottom of the thimble to facilitate drainage. The resin must be
carefully retained in the extractor cup with a glass wool plug and stainless steel screen to
prevent floating on the methylene chloride.
Clean the resin by two sequential 24 hour Soxhlet extractions with methylene chloride.
Replace with fresh methylene chloride after the first 24 hour period.
The adsorbent must be dried with clean inert gas. Liquid nitrogen from a standard
commercial liquid nitrogen cylinder has proven to be a reliable source of large volumes of
gas free from organic contaminants. A 10.2 cm ED Pyrex pipe 0.6 m long with suitable
retainers as shown in Figure 4 will serve as a satisfactory column. Connect the liquid
nitrogen cylinder to the column by a length of cleaned 0.95 cm ID copper tubing, coiled to
pass through a heat source. A convenient heat source is a water bath heated from a steam
line. The final nitrogen temperature should only be warm to the touch and not over 40°C.
Continue the flow of nitrogen through the adsorbent until all the residual solvent is removed.
The rate of flow should be high enough that the particles are gently agitated but not so high
as to cause die particles to break up.
4.2.2 Amberlite XAD-2 Resin
4.2.2.1
Cleaning XAD-2 Resin
4.2.2.2
Drying Cleaned XAD-2 Resin
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4.2.2.3 Residual Methylene Chloride Check.
Weigh a 1.0 g sample of dried resin into a small vial, add 3 mL of hexane.
cap the vial and shake it well.
Inject a 2 mL sample of the extract into a gas chromatograph operated under
the following conditions:
6 ftx 1/8 in stainless steel containing 10% OV-101 on 100/120
Supelcoport
Helium at a rate of 30 tnL/min.
Flame ionization detector operated at a sensitivity of 4 X 10"n A/mV.
250°C.
Detector
Temperature: 305°C.
Oven
Temperature: 30°C for 4 min; programmed to rise at 40°C per min until it reaches 250°C;
return to 30°C after 1000 seconds.
Compare the results of the analysis to the results from a reference solution prepared by
adding 2.5 pL of methylene chloride into 100 mL of hexane. This corresponds to 100 jig of
methylene chloride per g of adsorbent The maximum acceptable concentration is 1000 ug'j:
of adsorbent If the methylene chloride in the adsorbent exceeds this level, drying must be
continued until the excess methylene chloride is removed.
4.2.2.4 Contamination Check of XAD-2 Resin
The cleaned, dried XAD-2 resin must be checked for PAH contamination. Analyze a sample
of the resin equivalent in size to the amount required to charge one sorbent cartridge for a
sampling train. The extraction, concentration, cleanup and GC/MS analytical procedures
shall be the same for this sample as for the field samples (Sections 6.5.1.2,6.6, and 7.5;
Extraction:
Analysis:
Column:
Carrier Gas:
Detector:
Injection Port
Temperature:
The acceptance limit will depend on die PQL, fee expected concentration in the sampled gas
stream, and the planned sample volume. The contamination level must be less than the PQL
or no more than 20 percent of the expected sample level.
If the cleaned resin yields a value for a target analyte which is not acceptable for the end
lua-'s intended application of the test results, repeat the extraction unless the analy st has
historical data that demonstrate that re-extraction cannot reasonably be expected to further
reduce the contamination levels. The tester must obtain these data from the analyst and
include them in both the source test protocol and the emissions test report
July 28,1997 M-429Pagc
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The contamination check shall be repeated if the analyst does not have such historical data
The analyst shall reclean and dry the resin (4.2.2,1,4,2.2.2, and 4,2.2,3) and repeat the PAH
analysis of the re-cleaned resin. If the repeat analysis yields a similar result to the first,
record Ac contamination level for both die initial cleaning and the re-clwiin®
The analyst shall record the dates of die cleaning and extraction of die resin, and prepare a
laboratory report of the analytical results that includes all of the information required by
Section 10.2.
The tester shall obtain the dates of cleaning and the laboratory report of the results of the
contamination check from the analyst, and report them in both the source test protocol and
the emissions test report as required by Sections 10.1 and 10.3.
The tester shall identify the analytes for which the PQLs will be based on a blank
contamination value, and calculate die PQLs as required by Section 2.3.3.
4.2.2.5 Storage ofXAD-2 Resin
After cleaning, the resin may be stored in a wide mouth amber glass container with a Teflon-
lined cap, or placed in one of the glass adsorbent modules wrapped in aluminum foil and
capped or tightly sealed with Teflon film at each end. The containers and modules shall then
s be stored away from light at temperatures 4°C or lower until the resin is used in the sampling
; train.
The adsorbent must be used within twenty one (21) days of cleaning. If the adsorbent is not
used within 21 days, it must be re-checked for contamination before use.
4.2.3 Silica Gel
Indicating type, 6 to 16 mesh. If previously used, dry at 175°C (350°F) for 2 hours. New silica
gel may be used as received. Alternatively, other desiccants (equivalent or better) may be used,
subject to approval by the Executive Officer.
4.2.4 Reagent Water
Deionized, then glass-distilled, and stored in hexane- and methylene chloride-rinsed glass
containers with TFE-lined screw caps.
4.2.5 Impinger Solution
Sodium bicarbonate 3 mM, and sodium carbonate 2.4 mM Dissolve 1.0081 g sodium
bicarbonate (NaHC03) and 1.0176 g of sodium carbonate (NajCQ^) in reagent water (4.2.4),
and dilute to 4 liters.
4.2,6 Crushed Ice
Place crushed ice in the water bath around the impingers.
July 28, 1997 M-429 Page 17
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4.2.7 Glass Wool
Clean by methylene chloride soxhlet extraction for 16 hours. Air dry in a clean container in a
clean hood. Store in methylene chloride washed glass jar with TFE-lined screw cap
4.2.S Chromic Acid Cleaning Solution
Dissolve 200 g of sodium dichrornate in 15 mL of reagent water, and then carefully add 400 mL
of concentrated sulfuric acid.
4.3 PRE-TEST PREPARATION
The positive identification and quantitation of PAH in an emissions test of stationary sources are
strongly dependent on the integrity of the samples received and the precision and accuracy of all
analytical procedures employed. The QA procedures described in Sections 4.3.7 and 8 are to be used
to monitor the performance of the sampling methods, identify problems, and take corrective action.
4.3.1 Calibration
AH sampling train components shall be maintained and calibrated according to the procedure
described in APTD-0576 (Section 11.7), unless otherwise specified herein. The tester shall
maintain a record of all calibration data.
4.3.1.1 Probe Nozzle
Probe nozzles shall be calibrated according to the procedure described in ARB Method 5.
4.3.1.2 PitotTube
Calibrate the Type S pitot tube assembly according to the procedure described in Section 4
of ARB Method 2.
4.3.1.3 Metering System
Calibrate the metering system before and after use according to the requirements of Section
5.3 of ARB Method 5.
4.3.1.4 Temperature Gauges
Use the procedure in Section 4.3 of ARB Method 2 to calibrate in-stack temperature gauges
Dial thermometers, such as those used for the dry gas meter and condenser outlet, shall be
calibrated against mercury-in-glass thermometers.
4.3.1.5 Leak-Check of Metering System Shown in Figure 1
The tester shall use the procedure described in Section 5.6 of ARB Method 5
July 28', 1997 M-429Pag' S
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4.3.1.6 Barometer
Calibrate against a mercury barometer.
4.3.2 Cleaning Glassware for Sampling and Recovery
All glass parts of the train upstream of and including the sorbent module and the first impingers
shall be cleaned as described in Section 3 A of the 1974 issue of Manual of Analytical Methods
for Analysis of Pesticide Residues in Human and Environmental Samples (Reference 11.4).
Take special care to remove residual silicone grease sealants on ground glass connections of used
glassware. These greasy residues shall be removed by soaking several hours in a chromic acid
cleaning solution (4.2.8) prior to routine cleaning as described above. Other cleaning procedures
may be used as long as acceptable blanks are obtained. Acceptance criteria for blanks are stated
in Section 8.2.
Rinse all glassware with acetone, hexane, and methylene chloride prior to use in the PAH
sampling train.
Glassware used in sample recovery procedures must be rinsed as soon as possible after use with
the last solvent used in it This must be followed by detergent washing with hot water, and rinses
with tap water, deionized water, acetone, hexane, and methylene chloride. Other cleaning
procedures may be used as long as acceptable blanks are obtained. Acceptance criteria for
blanks are stated in Section 8.2.
4.3.3 Preparation of Filter
The clean dry filter (4.2.1) must be kept tightly wrapped in hexane-rinsed aluminum foil and
stored at 0 to 4°C in a container away from light until sampling. Before inserting the filter in the
sampling train, check visually against light for irregularities and flaws or pinhole leaks.
4.3.4 Preparation of Sorbent Cartridge, Method Blank, and
Laboratory Control Samples
Sorbent Cartridge —
Use a sufficient amount (at least 30 gms or 5 gms/m3 of stack gas to be sampled) of cleaned
resin to completely fill the glass sorbent cartridge which has been thoroughly cleaned as
prescribed (4.2.2).
Add the required surrogate standards (Table 7) to the sorbent cartridges for all of the sampling
and blank trains for each series of test runs. Follow the resin with hexane-rinsed glass wool, cap
both ends, and wrap the cartridge in aluminum foil. Store the prepared cartridges as required by
Section 4.3.5.
The sorbent cartridges must be loaded, and die surrogate standards must be added to the resin in
a clean area in the laboratory. There must be no turnaround of a used cartridge m the field
July 28, 1997 M^29Pagel9
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The analyst shall record the date that the surrogate standards were added to the resin and the
amount of each compound. The tester shall obtain these data from the analyst and report them in
the source test protocol and the test report
The appropriate levels for the surrogate standards are given in Table 7 which shows the spiking
plan for surrogate standards, internal standards, alternate standards, and recovery standards. All
of these required compounds are generally available. Additional labelled PAH may also be used
if available. The labelled compounds used as surrogate standards must be different from the
internal standards used for quantitation, and from the alternate and recovery standards. If the
spiking scheme (Table 7) is modified, the tester must demonstrate that the proposed modification
will generate data of satisfactory quality. Table 7A shows an approved modification that has
been used in ARB's method development. All modifications must be approved by the Executive
Officer before fee emissions test is performed.
Laboratory Method Blank
Take a sample of XAD-2 resin from the same batch used to prepare fee sampling cartridge. This
will serve as the laboratory meftod blank (Section 8.1.1). The mass of this sample must be the
same as feat used in the sampling train. Spike with the same surrogate standards at the same
levels used in the sampling cartridges.
Laboratory Control Sample
\
; Set aside two samples of XAD-2 resin from fee same batch used to prepare fee sampling
cartridge. These will serve as the laboratory control samples. (Section 8.1.3). The mass of each
sample must be fee same as that used in fee sampling train.
4.3.5 Storage of Prepared Cartridges, Method Blank and Laboratory Control Sample
Store fee aluminum foil wrapped sorbent cartridges away from light at 4°C or lower until they
are fitted into the sampling trains. Do not remove fee caps before the setup of the sampling
train.
The maximum storage time from cleaning of the resin to sampling wife fee spiked resin cartridge
must not exceed 21 days (4.2.2.5).
Store fee laboratory method blank and laboratory control samples in amber glass jars wife
Teflon-lined lids at temperatures no higher than 4°C.
4.4 SAMPLE COLLECTION
Because of the complexity of this method, testers must be experienced wife the test procedures in
order to ensure reliable results.
* i Field Determinations
Select the sampling site and the minimum number of sampling points according to ARB Method
I or as specified by fee Executive Officer.
July 28, ! 9?? M-429 Page 2>
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Determine the stack pressure, temperature, and die range of velocity heads usinc A R3 Meiod 2,
Conduct a leak-check of the pitot lines according to ARB Method 2, Section 3.1.
Determine die moisture content using ARB Method 4 or its alternative ::
making isokinetic sampling rate settings.
Determine the stack gas dry molecular weight, as described in ARB Method 2, Section 3.6. if
integrated sampling (ARB Method 3) is used for molecular weight determination, the integrated
bag sample shall be taken simultaneously with, and for the same total length of time as, the
sample run.
Select a nozzle size based on the range of velocity heads, such that it is not necessary to change
die nozzle size in order to maintain isokinetic sampling rates. Do not change the nozzle size
during the run. Ensure that the proper differential pressure gauge is chosen for the range of
velocity heads encountered (see Section 2.2 of ARB Method 2).
Select a probe extension length such that all traverse points can be sampled. For large stacks,
consider sampling from opposite sides of the stack to reduce die length of probes.
The target sample volume and sampling time must already have been calculated for the source
test protocol and approved by the end user as required by Sections 2.2 and 2.5. The total
sampling time must be such that (1) the sampling time per point is not less than 2 minutes
(or some greater time interval as specified by the Executive Officer), and (2) the total gas sample
volume collected (corrected to standard conditions) will not be less than the target value
calculated for the source test protocol (Section 2.5.5).
To avoid timekeeping errors, the number of minutes sampled at each point should be an integer
or an integer plus one-half minute.
4.4.2 Preparation of Collection Train
Keep all openings where contamination can occur covered until just prior to assembly or until
sampling is about to begin.
Caution: Do not use sealant greases in assembling the sampling train.
Record the performance of the setup procedures for the sampling train. Figure 10 is an example
of a form for recording the sampling train setup data. The tester must record all of the routine
information indicated on this form as well as any additional data which are necessary for
documenting the quality of any reported results.
Place 100 ml of the impinger solution (4.2.5) in die first impinger and weigh- Record the total
weight Repeat the procedure for the second impinger. Leave the third impinger empty. Weigh
the empty third impinger and record the weight
Weigh 200 to 300 g of silica gel to die nearest 0.5 g directly into a tared impinger or silica gel
cartridge just prior to assembly of the sampling train. The tester may optionally measure and
record in advance of test time the weights of several portions of silica gel in air-tight containers.
July 28, 1997 M-429Page21
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One portion of the preweighed silica gel must then be transferred from its container to the silica
gel cartridge or fourth impingcr. Place the container in a clean place for later use in the sample
recovery.
Using tweezers or clean'disposable surgical gloves, place a filter in the filter holder. Be sure that
die filter is property centered and the gasket properly placed so as to prevent the sample gas
stream from circumventing the filter. Check the filter for tears after assembly of the filter holder
is completed.
Mark the probe extension with heat resistant tape or by some other method to denote die proper
distance into the stack or duct for each sampling point
Assemble the train as in Figure 2. Place crushed ice around the impingers.
4.4.3 Leak-Check Procedures
4.4.3.1 Pretest Leak-Check
After the sampling train has been assembled, turn on and set the filter and probe heating
systems at the desired operating temperatures. Allow time for die temperature to stabilize
Leak-check die train at die sampling site by plugging the nozzle with a TFE plug and pulling
a vacuum of at least 380 mm Hg (15 in. Hg).
Note: A lower vacuum may be used, provided that it is not exceeded during the test
The following leak-check instructions for the sampling train are described in Section 4.1.4.1
of ARB Method 5. Start the pump with by-pass valve fully open and coarse adjust valve
completely closed. Partially open the coarse adjust valve and slowly close the by-pass valve
until the desired vacuum is reached. Do not reverse the direction of the by-pass valve This
will cause water to back up into the filter holder. If the desired vacuum is exceeded either
leak-check at this higher vacuum or end the leak-check as described below and start over.
Determine the leakage rate. A leakage rate in excess of 4 percent of the average sampling
rate or 0,00057 m3 per min. (0.02 cfm), whichever is less, is unacceptable Repeat the leak-
check procedure until an acceptable leakage rate is obtained. Record the leakage rate on the
field data sheet (Figure 5).
When the leak-check is completed, first slowly remove the plug from die inlet to the probe
\ nozzle and immediately turn off die vacuum pump. This prevents water from being forced
backward and keeps silica gel from being entrained backward.
4.4.3.2 Leak-Checks During Sample Run
I£ during the sampling run, it becomes necessary to change a component (e.g., filter
assembly or impingcr), a leak-check shall be conducted immediately before chc cam^ is
made. The leak-check shall be done according to the procedure described in Section 4 4 3 .1
above, except that it shall be done at a vacuum equal to or greater than the maximum value
recorded up to that point in the test If the leakage rate is found to be no greater than
July 28, 1997 M-429 Pag- .•
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0.00057 m3/min (0,02 cfm) or 4 percent of the average sampling rate (whicheve r is lessl th-
results are acceptable, and no correction will need to be applied to the total volume of dry
gas metered. If, however, a higher leakage rate is obtained, the tester shall either (1) record
the leakage rate and correct the volume of gas sampled since the last d-d. ^ L:
Section 4.4,3,4 below, or (2) void the sampling run. Record the leakage rate.
Immediately after component changes, leak-checks must be conducted according to the
procedure outlined in Section 4.4.3.1 above. Record the leakage rate oc the field data sheet
(Figure 5).
4.4.3.3 Post Test Leak-Check
A leak-check is mandatory at the conclusion of each sampling ran. The leak-check shall be
done in accordance with the procedures outlined in Section 4.4.3.1 except that it shall be
conducted at a vacuum equal to or greater than the maximum value recorded during the
sampling run. Record the leakage rate on die field data sheet (Figure 5). If the leakage rate
is found to be no greater than 0.00057 m3/min (0.02 cfin) or 4 percent of the average
sampling rate (whichever is less), the results are acceptable, and no correction need be
applied to the total volume of dry gas metered. If, however, a higher leakage rate is
obtained, the tester shall either, (1) record the leakage rate and correct the sample volume as
shown in Section 4.4.3.4 below, or (2) void the sampling run.
*
4.4.3.4 ' Correcting for Excessive Leakage Rates
If the leakage rate observed during any leak-check after fee start of a test exceeds the
maximum leakage rate Lt (see definition below), replace Vffl in Equation 429-9 with die
following expression.
V„ - i (Li - L.)6S - (Lp - L.)0P 429-9
i = l
Where:
Vffl = Volume of gas sampled as measured by the dry gas meter (dscf).
La « Maximum acceptable leakage rate equal to 0.00057 m3/min
t0.02 frVmin) or 4% of the average sampling rate, whichever is
smaller.
Lp = Leakage rate observed during the post-test leak-check, m3/min
(ft'/min).
Li
e,
July 28,1997
= Leakage rate observed during the leak-check performed prior to the
"ith" leakcheck (i - l,2,3...n), m3/min (tf/min).
= Sampling time interval between two successive leak-checks beginning
with the interval between the first and second leak-checks, min.
M-429 Page 23
N-201
J
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0p » Sampling time interval between the last (n4) leak-check and the end of
the test, min.
Substitute only for those leakage rates (Lj or Lp) which exceed Lg.
Train Operation
No smoking is allowed.
Sampling Train
During the sampling ran maintain a sampling rate within 10 percent of true isokinetic, unless
otherwise specified or approved by the Executive Officer. The actual sampling rate must be
at or above the VSR (Equation 429-4) to collect the target sample mass in the estimated
sampling time. If the target sampling rate cannot be achieved, adjust the planned sampling
time to achieve the target sample volume (PSV).
For each ran, record die data required on the sample data sheet shown in Figure 5. Hie
operator must record the dry gas meter reading at the beginning of the test, at the beginning
and end of each sampling time increment, when changes in flow rates are made, before and
after each leak-check, and when sampling is halted.
Record other readings required by Figure 5 at least once at each sample point during each
time increment and additional readings when significant changes (20 percent variation in
velocity head readings) necessitate additional adjustments in flow rate.
Level and zero the manometer. Because the manometer level and zero may drift due to
vibrations and temperature changes, make periodic checks during the traverse
Clean the portholes prior to the test run to minimize the chance of sampling the deposited
material. To begin sampling, remove the nozzle cap and verify that the pitot tube and probe
extension are properly positioned. Position the nozzle at the first traverse point with the tip
pointing directly into the gas stream.
Immediately start the pump and adjust the flow to isokinetic conditions. Nomographs are
available, which aid in the rapid adjustment of die isokinetic sampling rate without excessive
computations. These nomographs are designed for use when the Type S pitot tube
coefficient (C^) is 0.85±0.02, and the stack gas equivalent density (dry molecular weight)
(Md) is equal to 2S±4. APTD-0576 (Reference 11.7) details the procedure for using the
nomographs. If Cp and Mj are outside the above stated ranges, do not use the nomographs
unless appropriate steps (see Reference 11.8) are taken to compensate for the deviations
When the stack is under significant negative pressure (height of impinger stem), take care to
close the coarse adjust valve before inserting die probe extension assembly into the stack to
prevent water from being forced backward. If necessary, die pump may be turned on with
the coarse adjust valve closed.
M-429Pag • 24
N-202
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When the probe is in position, block off the openings around the probe and porthole ro
prevent unrepresentative dilution of the gas stream.
Turn ca tic recirculating p'inp fc""^"""bent module and the cond«*"c?r spH hperip
monitoring the temperature of the gas entering the adsorbent trap. Ensure that the
temperature of thegas is 20°C or lower before sampling is started.
Traverse the stack cross section, as required by ARB Method 1 or as specified by the
Executive Officer, being careful not to bump the probe nozzle into the stack walls when
sampling near the walls or when removing or inserting the probe extension through the
portholes. This minimizes the chance of extracting deposited material.
During the test ran, take appropriate steps (e.g., adding crushed ice to the impinger ice bath)
to maintain the temperature at the condenser outlet below 20°C (68°F). Also, periodically
check the level and zero of the manometer.
If the pressure drop across the filter becomes too high, making isokinetic sampling difficult
to maintain, fee filter may be replaced during a sample run. Another complete filter
assembly must be used rather than changing the filter itself Before a new filter assembly is
installed, conduct a leak-check as outlined in Section 4.4.3.2. The total PAH analysis shall
include the combined catches of all filter assemblies.
A single train shall be used for the entire sample run, except in cases where simultaneous
sampling is required in two or more separate ducts or at two or more different locations
within the same duct, or, in cases where equipment failure necessitates a change of trains. In
all other situations, the use of two or more trains will be subject to approval by the Executive
Officer.
Note that when two or more trains are used, a separate analysis of each train shall be
performed, unless identical nozzle sizes were used on all trains, in which case the catches
from the individual trains may be combined and a single analysis performed.
At the end of the sample run, turn off the pump, remove the probe extension assembly from
the stack, and record die final dry gas meter reading. Perform a leak-check, as outlined in
Section 4.4.3.3. Also, leak-check the pi tot lines as described in ARB Method 2; the lines
must pass this leak-check, in order to validate the velocity head data. Record leakage rates.
Record any unusual events during the sampling period.
4.4.4.2 Blank Train
There shall be at least one blank tram for each series of three or fewer test runs. For those
sources at which emissions are sampled at more than one sampling location, there shall be at
least one blank train assembled at each location for each set of three or fewer runs.
Prepare and set up die blank train in a manner identical to that described above for the
sampling trains. The blank train shall be taken through all of die sampling train preparation
steps including the leak-check without actual sampling of the gas stream. Recover the blank
July 28, 1997 M-429Page25
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train as described in Section 5.3. Follow all subsequent steps specified for the sampling
train including extraction, analysis, and data reporting.
4.4.5 Calculation of Percent Isokinetic
Calculate percent isokinetic (Section 4.5.7) to determine whether the run should be repeated. If
there was difficulty in maintaining isokinetic rates because of source conditions, consult with the
Executive Officer for possible variance on the isokinetic rates.
4.5 CALCULATIONS
Cany out calculations retaining at least one extra decimal figure beyond that of the acquired data.
Round off figures after die final calculation.
4.5.1 Nomenclature
A * Cross-sectional area of stack, ft2.
A,j « Cross-sectional area of nozzle, ft2.
Bm ¦= Water vapor in the gas stream, proportion by volume.
1 Cs = Concentration of PAH in stack gas, ng/dscm, corrected to standard conditions
~ of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) on diy basis.
Gs = Total mass of PAH in stack gas sample, ng.
AH = Average pressure differential across the orifice meter, mm H20 (in, H20)
I = Percent isokinetic sampling.
La = Maximum acceptable leakage rate for either a pretest leak-check or for a leak-
check following a component change; equal to 0.00057 m3/min (0.02 cfm) or 4
percent of the average sampling rate, whichever is less.
Lj = Individual leakage rate observed during die leak-check conducted prior to the
"ith" component change (i ¦ 1,2,3, ...n), m3/min (cfin).
Lp = Leakage rate observed during the post-test leak-check, m3/min (cfin)
Md = Molecular weight of stack gas, diy basis, lb/lb-mole (g/g-mole).
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-mole)
Ms = Molecular weight of stack gas, wet basis, lb/lb-mole (g/g-mole)
Pbv = Barometric pressure at the sampling site, mm Hg (in. Hg).
?s = Absolute stack gas pressure, mm Hg (in Hg).
July 28, 15"* M-429 Page ?,
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= Standard absolute pressure, 760 mm Hg (29.92 in, Hg).
Qyjjj = Dry volumetric stack gas flow rate corrected to standard conditions, dscj}min
(dscm/min).
pw = Density of water, 0.9982 g/mL (0.002201 lb/mL).
R = Ideal gas constant 0,06236 mm Hg-m3/°K-g-mole (21.83 in Hg-tf/R-lb-mole).
Tm = Absolute average dry gas meter temperature, °K (°R).
Ts = Absolute average stack gas temperature °K (°R).
= Standard absolute temperature, 293°K (528°R).
Vle = Total volume of liquid collected in impingers and silica gel, mL.
Vm = Volume of gas sample as measured by dry gas meter, dcm (dcf).
^o(std) = Volume of gas sample measured by the dry gas meter, corrected to standard
conditions, dscm (dscf).
V^std) = Volume of water vapor in the gas sample, corrected to standard conditions,
dscm (dscf).
vs = Stack gas velocity, calculated by ARB Method 2, Equation 2-9, ft/sec (m/sec).
Y = Dry gas meter calibration factor,
0 = Total sampling time, min.
0! = Sampling time interval, from the beginning of a run until the first component
change, min.
0; = Sampling time interval between two successive component changes, beginning
with the interval between the first and second changes, min.
0p = Sampling time interval,- from the final (n4) component change until the end of
the sampling run, min.
-------
4.5.2
Average Dry Gas Meter Temperature and Average Orifice Pressure Drop
See sampling run record (Figure 5).
4.5.3 Dry Gas Volume < /
Use Equation 429-10 to correct the sample volume measured by the dry gas meter to standard
conditions (20°C, 760 mm Hg or 68°F, 29.92 in Hg).
V ¦ VV ± hdUl • K V Y tidSl
m(std) m -p p 1 m >p
1 m *td 1 m
Where:
"^std
Kj = -= 0.3858 °K/mm Hg for metric units
^Std
= 17.65 °R/m Hg for English units
NOTE: Equation 429-10 may be used as written unless the leakage rate observed during any of
the mandatory leak-checks (i.e., the post-test leak-check or leak-checks conducted prior to
component changes) exceeds La. If L or L; exceeds Lt, Vm in Equation 429-10 must be
modified as described in Section 4,4.3.4,
4.5.4 Average Stack Gas Velocity
Calculate the average stack gas velocity, v$, as specified in ARB Method 2, Section 5.2
4.5.5 Volume of Water Vapor
Calculate the volume of water vapor using Equation 429-11 and the weight of the liquid
collected during sampling (Sections 5.3.6 and 5.3.8).
V - V P* RT*» = V V 429-11
M*d) vlc T7~ "5 ^ vlc
mw «td
wnere:
K2 » 0.001333 m3/mL for metric units, or
= 0.04707 f^/raL for English units.
July 28, 1997 ' M429 Pag •
fi
-------
4.5.6 Moisture Content
Calculate the moisture content of the gas, BOT
"" V,
B = w(std) 429-12
V + V
m(std) w(std)
NOTE: In saturated or water-droplet laden streams, the procedure for determining the
moisture content is given in the note to Section 1.2 of Method 4. For the purpose of
this method, the average stack-gas temperature from Figure 5 may be used for this
determination, provided that the accuracy of the in-stack temperature sensor is ±1°C
(2°F)
4.5.7 Isokinetic Variation
4.5.7.1 Calculation from Raw Data
100TS
I =
K,VU ~
m \ /
60 6 v Ps A
S 3 0
Where:
K3 = 0,003454 mm Hg-m3/mL-°K for metric units
= 0.002669 in Hg-ft3/mL-°R for English units
4.5.7.2 Calculation from Intermediate Values
, = _ 100T, Vn(std)
v, 6 A„ P, 60 (1 - B„)
T V
_ jr s m(jtd)
P, v, 0 A (1 - B„)
sa n v ws'
Where:
429-13
429-14
July 28, 1997 M-429Page29
N-207
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K4 = 4.320 for metric units.
- 0.09450 for English units.
4.5.8 Average stack gas dry volumetric flow rale
Use Equation 429-15 to calculate the average dry volumetric flow rate of the gas.
Qstd = 60 K, (1 - B ) V A
( \
P
«/
429-15
Where.
-
l*td
' nd
= 0.3858 °KAnm Hg for metric units
•= 17.65 °R/in Hg for English units
4.6 ISOKINETIC CRITERIA
If 90 percent < I < 110 percent, the isokinetic results are acceptable. If there is a bias to the results
because I < 90 percent or I > 110 percent, then the results must be rejected and the test repeated,
unless the test results are accepted by the Executive Officer.
5 SAMPLE RECOVERY
5.1 SAMPLE RECOVERY APPARATUS
5.1,1 Probe Nozzle Brush
Teflon brush with Teflon handle. The brush shall be properly sized and shaped to brush out the
probe nozzle.
5.1.2
5.1.3
Wash Bottles
Teflon wash bottles are required; Teflon FEP^.
Glass Sample Storage Containers
Precleaned narrow mouth amber glass bottles, 500 mL or 1000 mL. Screw cap liners shall be
Teflon.
July 28,1997
M-429 Page if
N-208
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5.1.4 Filter Storage Containers
Sealed filter holder or precieaned, wide-mouth amber glass containers with Teflon-lined screw
caps.
5.1.5 Balance
To measure condensed water to within 0.5 g.
5.1.6 Silica Gel Storage Containers
Air tight metal containers to store silica gel.
5.1.7 Funnel and Rubber Policeman
To aid in transfer of silica gel to container; not necessary if silica gel is weighed in the field
5.1.8 Funnel
To aid in sample recovery. Glass or Teflon® must be used.
5.1.9 Ground Glass Caps or Hexane Rinsed Aluminum Foil
To cap off adsorbent tube and die other sample-exposed portions of the aluminum foil.
5.1.10 Aluminum Foil
Heavy-duty, precieaned with methylene chloride.
5.2 SAMPLE RECOVERY REAGENTS
5.2.1 Reagent Water
Deiomzed (DI), then glass distilled, and stored in hexane and methylene chloride-rinsed glass
containers with TFE-lined screw caps.
5.2.2 Acetone
Nanograde quality. "Distilled in Glass" or equivalent, stored in original containers. A blank
must be screened by the analytical detection method.
5.2.3 Hexane
Nanograde quality. "Distilled in Glass" or equivalent, stored in original containers. A blank
must be screened by die analytical detection method.
July 28, 1997 M429Page31
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5,2.4 Methylene Chloride
Nanograde quality or equivalent A blank must be screened by the analytical detection method
5.3 SAMPLE RECOVERY PROCEDURE
No smoking is allowed.
Proper cleanup procedure begins as soon as the probe is removed from the stack at the end of the
sampling period and a post test leak-check has been performed (4.4.3.3). Allow the probe to cool.
When the probe can be safely handled, wipe off all external particulate matter near the tip of the
probe nozzle. Conduct the post test leak-check as described in Section 4.4.3.3. Remove the probe
from the train and close off both ends of the probe with precleaned aluminum foil (5.1.10). Seal off
the inlet to the train with a ground glass cup or precleaned aluminum foil.
Transfer the probe and impinger assembly to the cleanup area. This area must be clean, and enclosed
so that the chances of contaminating the sample will be minimized.
Inspect the train prior to and during disassembly and note any abnormal conditions, broken filters,
color of the impinger liquid, etc. Figure 6 summarizes the recovery procedure described in Sections
4 5.3.1 to 5.3.S.
' Figure 11 is an example of a form for recording the performance of the sample recovery procedure.
The tester must record all of the routine information indicated on this form as well as any additional
data which are necessary for documenting die quality of any reported results.
5.3.1 Sample Container No. 1 (front half rinses)
Quantitatively recover material deposited in the nozzle, probe, the front half of the filter holder,
and the cyclone, if used, first by brushing and then by sequentially rinsing with acetone, hexane.
and methylene chloride three times each. Place all these rinses in Container No 1 Mark the
liquid level.
5.3.2 Cyclone Catch
If the optional cyclone is used, quantitatively recover the particulate matter by sequentially
rinsing the cyclone with acetone, hexane, and methylene chloride. Store in a clean sample
container and cap.
5.3.3 Sample Container No. 2 (filter)
Carefully remove the filter from the filter holder and place it in its identified container Use a
pair of precleaned tweezers to handle the filter. Do not wrap the filter in aluminum foil. If it is
necessary to fold the filter, make sure that the particulate cake is inside the fold. Carefully
transfer to the container any particulate matter and/or filter fibers which adhere to the filter
holder gasket by using a diy inert bristle brush and/or a sbaip-edged blade. Seal the container
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5.3.4
Sorbent Module
Remove the sorbent module from the train and cap it
5.3.5 Sample Container No. 3 (back half rinses)
Rinse the back half of die filter holder, the transfer line between the filter and the condenser, and
the condenser (if using the separate condenser-sorbent trap) three times each with acetcne,
hexane and methylene chloride, and collect all rinses in Container No. 3. If using the combined
condenser/sorbent trap, the rinse of the condenser shall be performed in the laboratory alter
removal of the XAD-2 portion. If the optional water knockout trap has been employed, the
contents and rinses shall be placed in Container No. 3. Rinse it three times each with acetone,
hexane, and methylene chloride. Mark the liquid level.
The back half rinses may also be combined in a single container with the front half rinses
(Section 5.3.1).
5.3.6 Sample Container No. 4 (Impinger contents)
Wipe off the outside of each of the first three impingers to remove excess water and other
material. Weigh the impingers and contents to the nearest ±0.5 gusing a balance. Record the
weight Calculate and then record the weight of liquid collected during sampling. Use this
weight and the weight of liquid collected in the silica gel (Section 5.3.8) to calculate the moisture
content of the effluent gas (Sections 4.5.5 and 4.5.6). Pour the impinger catch directly into
Container No. 4. Mark the liquid level.
5.3.7 Sample Container No. 5 (Impinger rinses)
Rinse each impinger sequentially three times with acetone, hexane, and methylene chloride and
pour rinses into Container No. 5. Mark the liquid level. These rinses may be combined with the
previously weighed impinger contents in Container No. 4.
5.3.8 Weighing Silica Gel
Weigh the spent silica gel to the nearest 0.5 g using a balance. Record the weight Calculate and
then record the weight of liquid collected during sampling. Use this weight and the weight of
liquid collected in die impingers (Section 5.3.6) to calculate the moisture content of the effluent
gas (Sections 4.5.5 and 4.5.6)..
5.4 SAMPLE PRESERVATION AND HANDLING
From the time of collection to extraction, maintain all samples (Sections 5.3.1 to 5.3.7) at 4°C or
lower and protect from light All samples must be extracted as soon as practically feasible, but
within 21 days of collection; and all extracts must be analyzed as soon as practically feasible, but
within 40 days of extraction. Success in meeting the holding time requirement will depend on pre-
test planning by the tester and die laboratory.
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6 ANALYTICAL PREPARATION
This method is restricted to use only by or under the supervision of analysts experienced in the use of
capillary column gas chromatography/mass spectrometry and skilled in Ac interpretation of mass spectra
Each analyst must demonstrate the ability to generate acceptable results with this method using die
procedures described in Sections 7.3,8.2.6, and 8.3.1.
6.1 SAFETY
The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined.
Nevertheless, each chemical compound should be treated as a potential health hazard and exposure to
these chemicals must be reduced to fee lowest possible level by whatever means available. Tie
laboratory is responsible for maintaining a current file of OSHA regulations regarding the safe
handling of the chemicals specified in this method. A reference file of material safety data sheets
should also be made available to all personnel involved in the chemical analysis. Reference 11.9
describes procedures for handling hazardous chemicals in laboratories.
The following method analytes have been classified as known or suspected human or mammalian
carcinogens: benzo(a)anthracene and dibenzo- (ajh,)anthracene. A guideline for the safe handling of
carcinogens can be found in Section 5209 of Title 8 of fee California Administrative Code.
6.2 t CLEANING OF LABORATORY GLASSWARE
~ Glassware used in the analytical procedures (including the Soxhlet apparatus and disposable bottles)
must be cleaned as soon as possible after use by rinsing with fee last solvent used in it This must be
followed by detergent washing wife hot water, and rinses wife tap water, deionized water, acetone,
hexane, and methylene chloride. Other cleaning procedures may be used as long as acceptable blanks
are obtained. Acceptance criteria for blanks are given in Section 8.2.
Clean aluminum foil with acetone followed by hexane and methylene chloride.
6.3 APPARATUS
6.3. i Grab Sample Bottle
Amber glass, 125-mL and 250-mL, fitted with screw caps lined wife Teflon. The bottle and cap-
liner must be acid washed and solvent rinsed wife acetone and methylene chloride, and dried
before use.
6.3.2 Concentrator Tube, Kudema-Danish
10-mL, graduated (Kontes-K-570050-1025 or equivalent). Calibration must be checked at the
volumes employed in the test A ground glass stopper must be used to prevent evaporation of
extracts.
6.3.3 Evaporation Flask, Kudema-Danish
SOO-mL (Kontes K-570001-0500 or equivalent). (Attached to concentrator tube with springs).
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6.3.4 Snyder Column, Kudema-Danish
Three-ball macro (Kontes K-569001-0121 or equivalent).
6.3.5 Snyder Column, Kudema-Danish
Two-ball micro (Kontes K-569001-0219 or equivalent).
6.3.6 Minivials
1.0 mL vials; cone-shaped to facilitate removal of very small samples; heavy wall borosilicate
glass; with Teflon-faced rubber septa and screw caps.
6.3.7 Soxhlet Apparatus
1 liter receiver, 1 heating mantle, condenser, Soxhlet extractor.
6.3.8 Rotary Evaporator
Rotovap R (or equivalent), Brinkmann Instruments, Westbury, NY.
6.3.9 Nitrogen Slowdown Apparatus
N-Evap Analytical Evaporator Model 111 (or equivalent), Organomation Associates Inc.,
North borough, MA.
6.3.10 Analytical Balance
Analytical. Capable of accurately weighing to the nearest 0.0001 g.
6.3.11 Disposable Pipet
5 3/4 inch x 7,0 mm OD.,
6.4 SAMPLE PREPARATION REAGENTS
6.4.1 Reagent water
Same as 5.2.1.
6.4.2 Acetone
Same as 5.2.2.
6.4.3 Hexane
Same as 5,2.3.
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6.4.4
Methylene Chloride
Same as 5.2.4.
Sulfuric Acid .*
ACS. Reagent grade. Concentrated, sp. gr. 1.84.
Sodium Sulfate
ACS. Reagent grade. Granular, anhydrous. Purify prior to use by extracting with methylene
chloride and oven drying for 4 or more hours in a shallow tray. Place the cleaned material in a
glass container with a Teflon-lined screw cap, and store in a desiccator.
Silica Gel
For column chromatography, type 60, EM reagent, 100-200 mesh, or equivalent Soxhlet extract
with methylene chloride, and activate by heating in a foil covered glass container for longer than
16 hours at 130 °C, then store in a desiccator. The storage period shall not exceed two days.
NOTE: The performance of silica gel in the column cleanup procedure varies with
manufacturers and with the method of storage. He analyst shall establish a procedure
that satisfies the performance criteria of Section 6.6.1.
Alumina: Acidic
Soxhlet extract with methylene chloride, and activate in a foil covered glass container for 24
hours at 190 °C.
NOTE: The performance of alumina in the column cleanup procedure varies with
manufacturers and with the method of storage. The analyst shall establish a procedure
that meets the performance criteria of Section 6.6.1.
6.4.9 Nitrogen
Obtained from bleed from liquid nitrogen tank.
6.5 SAMPLE EXTRACTION
WARNING: Stack sampling will yield both liquid and solid samples for PAH analysis. Samples
must not be split prior to extraction even when they appear homogeneous as in the
case of single liquid phase samples. Solid samples such as the resin are not
homogeneous and particulate matter may not be uniformly distributed on the filter. In
addition, filter samples are generally so small that the desired detection limit might not
be achieved if the sample were split
6,4.5
6.4.6
6.4.7
6.4.8
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The recovered samples may be combined as follows:
1) Particulate filter and particulate matter collected on the filter (Section 5,3.3), cyclone catch
(Section. 5,3.2) zzd :unpl: ccr.tci-crXT? 1 (c"c*ion 5.3.1).
2) Sample container No. 3 (Section 5.3.5), resin (Section 5.3.4) and rinse of resin cartridge.
3) Sample container No.4 (Section 5.3.6) and sample container No.5 (Section 5.3,7)
Two schemes for sample preparation are described in Sections 6.5.1 and 6.5.2 below. One of these
must be used.
Section 6.5.1 describes sample preparation procedures for separate GC/MS analyses of impingers
and the remainder of the sampling train. Figure 7 is a flowchart of the extraction and cleanup
procedures.
Section 6.5.2 describes sample preparation procedures for GC/MS analysis of a single composite
extract from each sampling train. The recovered samples are combined as shown in Figure 8.
6.5.1 Separate Analysis of Impingers
A separate analysis of the impingers can be used to determine whether there has been
breakthrough ofPAHs past the resin.
6.5.1.1 Extraction of Liquid Samples
A. Sample Container No, 1 (Front half rinses)
Concentrate the contents of sample container No. 1 (Section 5.3.1) to a volume of about
1-5 mL using the nitrogen blowdown apparatus. Rinse the sample container three times
with small amounts of methylene chloride and aid these rinses to the concentrated
solution. Concentrate further to about 1-5 mL. This residue will likely contain
particulate matter which was removed in the rinses of the probe and nozzle. Transfer
the residue (along with three rinses of the final sample vessel) to the Soxhlet apparatus
with the filter and particulate catch and proceed as described under Section 6.5 .1.2
below.
B. Sample Container No. 3 (Back half rinses)
Concentrate the contents of sample container No. 3 (Section 5.3.5) to a volume of about
1-5 mL using the nitrogen blowdown apparatus. Rinse the sample container three times
with small amounts of methylene chloride and add these rinses to the concentrated
solution. Concentrate further to about 1-5 mL. Combine this residue (along with three
rinses of the final sample vessel) in the Soxhlet apparatus with the resin sample, and
proceed as described under Section 6.5.1.2 below.
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C. Containers No. 4 and No. 5 (Impinger contents and rinses)
Place the contents of Sample Containers No. 4 and No. 5 (Sections 5.4.6 and 5.4.7) in a
separatory funnel. Add the appropriate amount of2H-labeBed alternate standard
solution (Section 7 and Table 7 or 7A) to achieve the final extract concentrations
indicated in Table 8 or 8A. The amounts required by Section 7.2.4 are based on a final
volume of 500 nL for analysis (450 pL of sample extract and 50 nL of recovery
standard solution). Extract the sample three times with 60 mL aliquots of methylene
chloride. Combine the organic fractions. Divide the extract in two: one half to be
archived, and the other for cleanup and GC/MS analysis. Store die archive sample at
4°C away from light
Pour the remaining extract through Na2S04 into a round bottom flask. Add 60 to 100
mL hexane and evaporate to about 10 mL. Repeat tee times or less if the methylene
chloride can be removed with less hexane. Add the appropriate amount of alternate
standard (Section 7.2.7) to achieve the final extract concentrations shown in Table 6 or
6A. This standard must be used to monitor the efficiency of the cleanup procedure
Concentrate the remaining sample to 2 mL with a Kudema-Danish concentrator or
rotary evaporator, then transfer the extract to a 8 mL test tube with hexane. Proceed
with sample cleanup procedures below (Section 6.6).
6.5.1.2 Extraction of Solid Samples
Filter, Particulate matter, and Resin
The Soxhlet apparatus must be large enough to allow extraction of the sample in a single
batch. Clean the Soxhlet apparatus by a 4 to 8 hr Soxhlet with methylene chloride at a
cycling rate of 3 cycles per hour. Discard the solvent. Add 20 g Na^C^ to the thimble
Combine the filter, resin, glass wool, and concentrated front and back half rinses (6.5.1.1A
and 6.5.1. IB) and place on top of the NajSO^ Add the appropriate amount of internal
standard (Section 7.2.4 and Table 7) to achieve the final extract concentrations indicated in
Table 8.
Place the thimble in the Soxhlet apparatus, and add about 700 mL of methylene chloride to
the receiver. Assemble the Soxhlet, turn on the heating controls and cooling water, and
allow to reflux for 16 hours at a rate of 3 cycles per hour. After extraction, allow the
Soxhlet to cool. Divide the sample in two: one half to be archived, and the other for cleanup
and GC/MS analysis. Store the archive sample at 4°C away from light
Exchange the remaining extract to hexane. Add 60 to 100 mL hexane and evaporate to
about 10 mL. Repeat three times or as necessary to remove the methylene chloride. Add the
appropriate amount of alternate standard (Section 7.2.7 and Table 7 or 7A) to achieve the
final extract concentrations shown in Table 8 or 8A. This alternate standard must be used to
the efficiency of the cleanup procedure when the impingers are analyzed separately
from the remainder of the sampling train.
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Concentrate the remaining sample to about 2 mL with a Kuderna-Danish concentrator c
rotoevaporator, then transfer the extract to a 8-mL test tube with hexaie. Proceed with
sample cleanup procedures below (Section 6,6).
6.5.2 Single Composite Extract For Analysis
6.5.2.1 Extraction of Aqueous Samples
Containers No, 4 and No. 5 (Impinger contents and rinses)
Pour the contents of Sample Containers No, 4 and No. 5 (Sections 5.3.6 and 5.3.7) into an
appropriate size separately funnel. Do not add internal standards. Instead, add die
appropriate amount of alternate standard spiking solution (Section 7 and Table 7 or 7 A) to
achieve the final extract concentrations indicated in Table 8 or 8A.
Extract the sample three times with 60 mL aliquots of methylene chloride. Combine the
organic fractions with the solid samples and concentrated rinses (6.5.2.2) in a Soxhlet
extractor.
6.5.2.2 Extraction of Solid Samples
Concentrate the front and back half rinses as described in Sections 6.5.1.1 A and 6 5.1.IB.
Clean the Soxhlet apparatus as in Section 6.5.1.2. Place the filter and resin in the Soxhlet
apparatus along with the concentrated front and back half rinses and the impinger extract
Add the internal standards, extract the sample, and concentrate the extract as described in
Section 6.5.1.2. Divide the extract into two equal portions. Store one of these, the archive
sample, at 4 °C away from light The remaining extract must be exchanged to hexane as
described in Section 6,5.1.2. Do not add the alternate standard to this composite extract It
has already been added to the impinger sample (6.5,2,1).
Concentrate the extract to 2 mL with a Kuderna-Danish concentrator or rotary evaporator,
then transfer to a 8-mL test tube with hexane or equivalent non-polar solvent such as
isooctane. Proceed with sample cleanup procedures below (Section 6.6)
6.6 COLUMN CLEANUP
Several column chromatographic cleanup options are available. Either of the two described below
may be sufficient Before using a procedure for the cleanup of sample extracts, the analyst must
demonstrate that the requirements of Sections 8.1.3.1 and 8.2.6 can be met using die cleanup
procedure. Acceptable alternative cleanup procedures may also be used provided that the analyst can
demonstrate that the performance requirements of Sections 8.1.3.1 and 8.2.6 can be met
Compliance with the requirements of Sections 8.1.1.1 and 8.2.6 must also be demonstrated whenever
there is a change in the column cleanup procedure used for the initial demonstration.
The sample extract obtained as described in Sections 6.5.1C and 6.5.1.2 or 6.5.2.2 is concentrated to
a volume of about 1 mL using the nitrogen blowdown apparatus, and this is transferred quantitatively
with hexane rinsings to at least one of the columns described below.
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6.6.1 Column Preparation
A, Silica Gel Column
Pack a glass gravity-column (250 mm x 10 mm) in the following manner:
Insert a clean glass wool plug (Section 4.2,7) into die bottom of the column and add 10
grams of activated silica gel (Section 6.4.7) in methylene chloride. Tap the column to settle
the silica gel, and then add a 1 cm layer of anhydrous sodium sulfate (Section 6 4.6)
Variations among batches of silica gel may affect the elution volume of the various PAH.
Therefore, the volume of solvent required to completely elute all of die PAH must be verified
by the analyst The weight of the silica gel can then be adjusted accordingly. Satisfactory
recovery (as defined in Section 6.6) of each native PAH in the LCS (8.1.3) must be
demonstrated whenever there is a change in the method of preparing the silica ge! columns
B. Acid Alumina Column
Pack a 250 mm x 10 mm glass gravity column as follows:
- Insert a clean glass wool plug (Section 4.2.7) into the bottom of the column. Add 6 g of acid
alumina prepared as described in Section 6.4.8. Tap the column gently to settle the alumina.
' and add 1 cm of anhydrous sodium sulfate to the top.
~
Satisfactory recoveiy (as defined in Section 6.6) of each native PAH in the LCS (8.1.3) must
be demonstrated whenever there is a change in the method of preparing the acid alumina
columns.
6.6.2 Column Chromatography Procedure
A. Silica Gel Column
Elute the column with 40 mL of hexane. The rate for all elutions should be about 2 mL/mir.
Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, transfer
the 1 mL sample extract onto the column using two additional 2 mL rinses of hexane to
complete die transfer. Just prior to exposure of the sodium sulfate layer to the air, begin
elution of the column with 25 mL of hexane followed by 25 mL of methylene
chloride/hexane (2:3Xv/v). Collect the entire eluate. Concentrate the collected fraction to
about 5 mL using die K-D apparatus or a rotary evaporator. Do not allow the extract to go
to dryness.
Transfer to a minivial using a hexane rinse and concentrate to 450 pL using a gentle stream
of nitrogen. Store the extracts in a refrigerator at 4 °C or lower away from light until
GC/MS analysis (Section 7).
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B. Alumina Column
Elute the column with 50 mL of hexane. Let the solvent flow through the column until the
head of the liquid in the column is just above the sodium sulfate layer. Close the stopcock to
stop solvent flow. .*
Transfer 1 mL of the sample extract onto the column. Rinse out extract vial with two 1 inL
rinses of hexane and add it to the top of the column immediately. To avoid overloading the
column, it is suggested that no more than 300 mg of extractable organics be placed on the
column.
Just prior to exposure of the sodium sulfate to the air, elute the column with a total of 15 mL
of hexane. If the extract is in 1 mL of hexane, and if 2 mL of hexane was used as a rinse,
then 12 mL of additional hexane should be used. Collect the effluent and concentrate to
about 2 mL using the K-D apparatus or a rotary evaporator.
Transfer to a minivial using a hexane rinse and concentrate to 450 joL using a gentle stream
of nitrogen. Store the extracts at 4°C or lower away from light until GC/MS analysis.
7 GC/MS ANALYSIS
7.1, APPARATUS
7.1.1 Gas Chromatograph
An analytical system complete with a temperature programmable gas chromatograph and all
required accessories including syringes, analytical columns, and gases. The GC injection port
must be designed for capillary columns. Splitless injection is recommended.
7.1.2 Column
Fused silica columns are required.
A. 30 M long x 0.32 mm ID fused silica capillary column coated with a cross linked phenyl
methyl silicone such as DB-5.
B. Any column equivalent to the DB-5 column may be used as long as it has the same
separation capabilities as the DB-5.
7.1.3 Mass Spectrometer
7.1.3.1 Low Resolution
A low resolution mass spectrometer (LRMS) equipped with a 70 eV (nominal) ion source
operated in the electron impact ionization mode, and capable of monitoring all of the ions in
each Selected Ion Monitoring (SIM) group (Table 13) with a total cycle time of 1 second or
less.
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7.1.3.2
High Resolution
The high resolution mass spectrometer (HRMS) must be capable of operation in the SIM
mode at a resolving power of 8,000. Electron impact ionization must be used. The mass
spectrometer mutt be capable of monitoring all of the ions listed in each of the three SIM
descriptors (Table 14) with a total cycle time of 1 second or less.
7.1.4 GC/MS Interface
Any gas chromatograph to mass spectrometer interface may be used as long as it gives
acceptable calibration response for each analyte of interest at the desired concentration and
achieves the required timing performance criteria (Sections 7.3.5 and 7,3.6). All components of
the interface must be glass or glass-lined materials. To achieve maximum sensitivity, the exit
end of the capillary column should be placed in the mass spectrometer ion source without being
exposed to the ionizing electron beam.
7.1.5 Data Acquisition System
A computer system must be interfaced to the mass spectrometer. The system must allow the
continuous acquisition and storage on machine-readable media of all data obtained throughout
the duration of the chromatographic program. The computer must have software that can search
any GC/MS data file for ions of a specific mass and plot a Selected Ion Current Profile or SICP
(a plot of the abundances of the selected ions versus time or scan number). Software must also
be able to integrate, in any SICP, the abundance between specified time or scan-number limits
The data system must provide hard copies of individual ion chromatograms for selected gas
chromatographic time intervals.
The data system must also be able to provide hard copies of a summary report of toe results of
the GC/MS runs. Figures 14A to 14C show the minimum data that the system must be available
to provide.
7.2 REAGENTS
7.2.1 Stock Standard Solution (1.00 pg/jjJL)
Standard solutions can be prepared from pure standard materials or purchased as certified
solutions.
7.2.2 Preparation of Stock Solutions
A. Calibration standards. Prepare stock calibration standard solutions of each of the PAH
analytes by accurately weighing the required amount of pure material. Dissolve the materia!
in isooctane and dilute to volume. When compound purity is assayed to be 96% or greater,
the weight may be used without correction to calculate the concentration of the stock
standard.
July 28, 1997 M-429 Page 42
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Cominercially prepared stock standards may be used at any concentration if they are certified
by the manufacturer or by an independent source.
B. Internal standards. Prepare stock solutions in i so octane of the fourteen internal standards
listed in Table 4 or 4A at concentrations of 1000 ng/^L.
C. Recovery standards. Prepare stock solutions in isooctane of the three recovery standards
listed in Table 4 or 4A at concentrations of 1000 ng/^L.
D. Alternate standard. Prepare a stock solution in isooctane of the alternate standard listed in
Table 4 or 4A at a concentration of 1000 ng/|iL.
E. Surrogate standards. Prepare stock solutions in isooctane of the surrogate standards listed in
Table 4 or 4A at a concentration of 1000 ng/pL.
Store stock standard solutions in Teflon®-seaIed screw-cap bottles at 4°C and protect from
light Stock standard solutions must be checked frequently for signs of degradation or
evaporation, especially just before using them to prepare calibration standard solutions or
spiking solutions.
Replace stock standard solutions every 12 months or more frequently if comparison with
quality control check samples according to Section 7.4.1 indicates a problem.
7.2.3 Calibration Standards
Prepare calibration standards at a minimum of five concentration levels. One of the calibration
standards should be at a concentration near, but above, the method detection limit. The others
should include the range of concentrations found in real samples but should not exceed the linear
range of the GC/MS system.
Prepare calibration working standard solutions by combining appropriate volumes of individual
or mixed calibration standards with internal standard, recovery standards, and alternate standard
spiking solution and making up to volume with hexane to obtain the solution concentrations
given in Tables 5, 6, and 6A. The suggested ranges are 0.25 ng/^L to 5.0 ng/^L for LRMS and
10 pg/pL to 500 pg/nL for HRMS.
All standards must be stored at 4°C or lower and must be freshly prepared if the check according
to Section 7.4.1 indicates a problem.
7.2.4 Internal Standard (IS) Spiking Solution
The concentration of internal standard in the IS spiking solution must be such that the amount of
solution added to the calibration standard solution and the sample is at least 2 mL.
Prepare the internal standard spiking solution by using appropriate volumes of stock solutions of
Section 7.2.2B to give die concentrations shown in Table 4 or 4A. A volume of 2 mL of either
the LRMS or HRMS spiking solution will provide die amount of the internal standards that
must be added to the sample (Table 7 or 7A) before extraction to achieve, in a final volume of
July 28, 1997 M-429 Page 43
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500 yL, the sample extract concentrations shown in Table 8 for LRMS and Table 8 or 8A for
HRMS analysis. The target concentrations in Tables 8 and 8A are based on a final volume of
500 yL and 100 percent recovery of the internal standards added to the sample.
Recovery Standard Spiking Solution
Hie concentration of recovery standard in this spiking solution must be such that the amount of
solution added to the concentrated sample extract is 50 yL to give a final extract volume of 500
ml.
Use an appropriate volume of stock solution of Section 7.2.2C to prepare a recovery standard
spiking solution with the concentrations shown in Table 4 or 4A, Store at 4 °C or lower
A volume of 50 pL of the recovery standard spiking solution shown in Table 4 or 4A will
provide the amount of each recovery standard required by Table 7 or 7A to achieve the target
sample concentration of Table 8 or 8A. Final volumes, may be adjusted depending on the target
detection limit
Surrogate Standard Spiking Solution
The concentration of surrogate standard in this spiking solution must be such that the amount of
solution added to the calibration standard solution and the sorbent module is at least 2 mL.
Prepare the surrogate standard spiking solution by using the appropriate volume of stock
solution of Section 7.2.2E to give the concentration shown in Table 4 or 4A. A volume of 2 mL
of either the LRMS or HRMS spiking solution will provide the amount of the surrogate
standards that must be added to the sample (Table 7 or 7A) before sampling to achieve the
sample extract concentrations shown in Table 8 or 8A in a final sample volume of 500 pL
Alternate Standard Spiking Solution
The concentration of alternate standard in this spiking solution must be such that the amount of
solution added to the calibration standard solution and the sample extracts is at least 2 mL
Prepare the alternate standard spiking solution by using the appropriate" volume of stock solution
of Section 7.2.2D to give the concentration shown in Table 4 or 4A. A volume of 2 mL of eithe?
the LRMS or HRMS spiking solution will provide the amount of the alternate standard that
must be added to the sample (Table 7 or 7A) before extraction to achieve the sample extract
concentrations shown in Table 8 or 8A in a final sample volume of500 yL.
Calibration Check Standard
The calibration check standard shall be used for column performance checks, and for continuing
calibration checks. Solution #3 from Table 5 shall be the calibration check standard for LRMS,
cation #3 from Table 6 or 6A shall be the calibration ch»*ck standard for HRMS.
M-429 Pag- V.
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7.3 INITIAL CALIBRATION
An acceptable initial calibration (7.3.8) is required before any samples are an ah zed, and then
intermittently throughout sample analyses as dictated by results of the continuing calibration
procedures described in Section 7.4. The GC/MS system must be properly calibrated and the
performance documented during the initial calibration.
7.3.1 Retention Time Windows
Before sample analysts, determine the retention time windows during which the selected ions will
be monitored. Determine Relative Retention Time (RRTs) for each analyte by using the
corresponding 2H - labelled standard.
7.3.2 GC Operating Conditions
The GC column performance (Section 7.3.5) must be documented during the initial calibration.
Table 10 summarizes GC operating conditions known to produce acceptable results with the
column listed. The GC conditions must be established by"each analyst for the particular
instrumentation by injecting aliquots of the calibration check standard (7.2.8). It may be
necessary to adjust the operating conditions slightly based on observations from analysis of these ..
solutions. Other columns and/or conditions may be used as long as column performance criteria
of Section 7.3.5 are satisfied.
Thereafter the calibration check standard must be analyzed daily to verify the performance of the
system (Section 7.4).
7.3.3 GC/MS Tuning Criteria
A. Low Resolution Mass Spectrometry
Use a compound such perfluorotributylamine (PFTBA) to verify that the intensity of the
peaks is acceptable. If PFTBA is used, mass spectral peak profiles for m/z 69, 219 and 264
must be recorded, plotted, and reported. The scan should include a minimum of +/- two
peaks (i.e, m/z 67-71 for the m/z 69 profile).
B. High Resolution Mass Spectrometry
Tune the instrument to meet the minimum required resolving power of 8,000 at 192.9888 or
any other PFK reference signal close to 128.0626 (naphthalene). Use peak matching and the
chosen PFK reference peak to verify that the exact mass of m/z 242.9856 is within 5 ppm of
die required value. The selection of the low and high mass ions must be such that they
provide the largest voltage jump performed in any of the three mass descriptors.
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'1
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7,3.4 MS Operating Conditions
A. Low Resolution Mass Spectrometry
Analyze standards mid samples with the mass spectrometer operating in the Selected Ion
Monitoring (SIM) mode with a total cycle time of 1 second or less.
B. High Resolution Mass Spectrometry
Analyze standards and samples with the mass spectrometer operating in the SIM mode with
a total cycle time (including the voltage reset time) of one second or less.
A reference compound such as Perfluorokerosene (PFK) must be used to calibrate the SIM
mass range. One PFK ion per mass descriptor is used as a lock-mass ion to correct for mass
drifts that occur during the analysis. In addition to the lock-mass ion, several ions
characteristic of PFK are monitored as QC check ions (Table 13).
7.3.5 - GC Column Performance Criteria
A. The height of the valley between anthracene and phenanthrene at m/z 178 or the 2H-analogs
at m/z 188 shall not exceed 50 percent of the taller of the two peaks.
x B. The height of the valley between benzo(b)fluoranthene and benzo(k)£luoranthene shall not
! exceed 60 percent of the taller of the two peaks.
*
If these criteria are not met and normal column maintenance procedures are not successful, the
column must be replaced and the initial calibration repeated.
7.3.6 Mass Spectrometer Performance
A. Low Resolution Mass Spectrometry
Verify acceptable sensitivity during initial calibration. Demonstrate that the instrument wir
achieve a minimum signal-to-noise ratio of 10:1 for the quantitation and confirmation ions
when the calibration standard with the lowest concentration is injected into the GC/MS
system.
B. High Resolution Mass Spectrometry
Record the peak profile of fee high mass reference signal (m/z 242.9856) obtained during
peak matching by using the low-mass PFK ion at m/z 192.9888 (or lower in mass) as a
reference. The minimum resolving power of 8,000 must be demonstrated on the high-mass
ion while it is transmitted at a lower accelerating voltage than the low-mass reference ion.
which is transmitted at lull sensitivity.
The format of the peak profile representation must allow manual determination of the
resolution, that is, the horizontal axis must be a calibrated mass scale (arcu or ppra per
division).
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The peak width of the high mass ion at 5 percent of the peak height must not exceed 125
PPm in mass.
7.3.7 Calibration Procedure
Using stock standards, prepare at least five calibration standard solutions, using the same solvent
that was used in fee final sample extract Keep the recovery standards and the internal standards
at fixed concentrations. Adjust the concentrations recommended in Tables 5 and 6, if necessary,
to ensure that the sample analyte concentration falls within the calibration range. The calibration
curve must be described within the linear range of the method.
Calibrate the mass spectrometer response using a 2 jiL aliquot of each calibration solution.
Analyze each solution once.
Calculate:
A. fee relative response factors (RRFs) for each analyte as described in Sections
7.7.1.1,7.7.1.2, and 7.7.1.3.
B. fee mean RRFs as required by Section 7.7.1.4.
C. the standard deviation (SD) and relative standard deviation (RSD) as required
s by Section 7.7.2.
Report all results as required by Section 10.2.
7.3.8 Criteria for Acceptable Initial Calibration
An acceptable initial calibration must satisfy fee following performance criteria:
A. The requirements of Sections 7.3.5 and 7.4.6 must be met
B. The signal to noise ratio (S/N) for fee GC signals present in every selected ion current
profile (SICP) must be > 10:1 for the labelled standards and unlabelled analytes.
C. The percent relative standard deviation for the mean relative response factors must be no
greater than 30 percent for both fee unlabelled analytes and internal standards
(Section 7.7.2). Otherwise, take corrective action as required by Section 7.7.2.
7.4 CONTINUING CALIBRATION
The continuing calibration consists of an analysis of the calibration check standard (Section 7,2.8)
once during each 12-hour shift as described in Section 7.4.1.
The criteria for acceptable continuing calibration are given in Section 7.4.2. These must be satisfied
or else corrective action must be taken as required by Section 7.4.2,
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7.4.1 Calibration Check
The calibration check standard (Section 7.2.8) must be analyzed at the beginning and end of each
analysis period, or at tike beginning of every 12-hour shift if the laboratory operates during
consecutive 12 hour shifts.
«* *
Inject a 2-pL aliquot of the calibration check standard (Section 7.2.8) into the GC/MS. Use the
same data acquisition parameters as those used during the initial calibration.
Check the retention time windows for each of the compounds. They must satisfy the criterion of
Section 7.4.2C
Check for GC resolution and peak shape. Document acceptable column performance as
described in Section 7.3.5. If these criteria are not met, and normal column maintenance
procedures are unsuccessful, the column must be replaced and the calibration repeated
Calculate die continuing RRF and ARRF, die relative percent difference (RFD) between the daih
RRF and the initial calibration mean RRF as described in Section 7,7.1.5.
Report the results as required by Section 10.2.
7.4.2 Continuing Calibration Performance Criteria
An acceptable continuing calibration must satisfy die following performance criteria:
A. Hie signal to noise ratio (S/N) for the GC signals present in the selected ion current profile
(SICP) for all labelled and unlabelled standards must be i 10:1.
B. The measured RRFs of all analytes (labelled and unlabelled) must be within 30 percent of
the mean values established during the initial calibration. If this criterion is not satisfied, a
new initial calibration curve must be established before sample extracts can be analyzed
C. The retention time for any internal standard must not change by more than 30 seconds from
the most recent calibration check. Otherwise, inspect the chromatographic system for
m?lfimctions and make the necessary corrections. Document acceptable performance with &
new initial calibration curve.
7.5 GC/MS ANALYSIS
The laboratory may proceed with the analysis of samples and blanks only after demonstrating
acceptable performance as specified in Sections 7.3 and 7.4.
Analyze standards, field samples and QA samples (Section 8.1) with die gas chromatograph and
mass spectrometer operating under the conditions recommended in Sections 7.3.2 and 7.3.4
Approximately 1 hr before HRGC/LRMS or HRGC/HRMS analysis, adjust the sample exiract
volume to approximately 500 nL. This is done by adding 50 jiL of the recovery standard spike
solution (Section 7.2.5, and Table 4 or 4A) to the 450 |iL final volume (Section 6.6.2) of die
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concentrated sample extract give the sample extract concentration required by Table 8 or 8 A. If the
sample volume must be changed to achieve a desired detection limit, the recovery spike solutim
concentration must be adjusted accordingly to achieve the target concentrations of Tabic 8 cr 8A.
LJcct a 2 |iL aliquot if the ramplc c:."tract C--cr: 6.6.2) on to the DB-5 colun-1 T T~ '•"*"*
volume as that used during calibration. Recommended GC/MS operating conditions are described in
Section 7,3,
The presence of a given PAH is qualitatively confirmed if the criteria of Section 7.6.1 are satisfied.
The response for any quantitation or confirmation ion in the sample extract must not exceed the
response of the highest concentration calibration standard.
Collect, record, and store the data for die calculations required by Sections 9.1.7,9.1.8,9.1.9, and
9.1.10. Report the results as required by Section 10.2.
7.6 QUALITATIVE ANALYSIS
7.6.1 Identification Criteria
7.6.1.1 Ion Criteria
For LRMS analysis, all quantitation and confirmation ions (Table 13) must be present
7.6.1.2 Relative Retention Time (RRT) Criteria
The relative retention time (RRT) of the analyte compared to the RRT for the 2H-standards
must be within ±0.008 RRT units of the relative retention times obtained from the
continuing calibration (or initial calibration if this applies).
7.6.1.3 Signal to Noise Ratio
The signal to mean noise ratio must be 10:1 for the internal standards. This ratio for the
unlabelled compounds must be greater than 2.5 to 1 for the quantitation ions for HRMS and
for both quantitation and confirmation ions for LRMS.
If broad background interference restricts the sensitivity of the GC/MS analysis, the analyst
must employ additional cleanup on the archive sample and reanalyze.
7.7 QUANTITATIVE ANALYSIS
7.7.1 Relative Response Factors (RRFs)
7.7.1.1 RRF for Unlabelled PAH and Surrogate Standards
from Initial Calibration Data
Use the results of the calibration and Equation 429-13 to calculate the relative response
factors (RRFs) for each calibration compound and surrogate standard in each calibration
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solution (Tables 5 or 5A). Table 11 shows the assignments of the internal standards for
calculation of the RRFs for the calibration solution shown in Table 5. Table 11A shows the
assignments of the internal standards for calculation of the RRFs for the calibration solution
shown in Table 5A. Report the results as required by Section 10.2.
7.7.1.2 RRF for Determining Internal Standard Recovery
Use the results of the calibration in Equation 429-18 to calculate fee relative response factor
for each internal standard relative to an appropriate recovery standard. Table 11 shows the
assignments of the recovery standards for calculating internal standard recoveries for the
calibration solution shown in Table 5. Table 11A shows the assignments of the recover}
standards for calculating internal standard recoveries for the calibration solution shown in
Table 5A. Report the results as required by Section 10.2.
7.7.1.3 RRF for Determining Alternate Standard Recoveiy
Use the calibration results and Equation 429-19 to calculate the response factor for the
alternate standard relative to the appropriate recoveiy standard. Table 11 shows the
assignment of the recovery standards for calculating alternate standard recovery for the
calibration solution shown in Table 5. for the calibration solution shown in Table 5 Report
the results as required by Section 10.2.
7.7.1.4 Mean Relative Response Factor
Use Equation 429-20 to calculate the mean RRF for each compound (unlabelled calibration
standards, surrogate standards, internal standards mid alternate standard). This is the
average of the five RRFs calculated for each compound (one RRF calculated for each
calibration solution). The mean RRF may be used if the linearity criterion of Section 7.7.2 is
satisfied.
Report the results as required by Section 10.2.
7.7.1.5 RRF from Continuing Calibration Data
Analyze one or more calibration standards (one must be the medium level standard) on each
work shift of 12 hours or less. Use Equations 429-17,429-18, and 429-19 to calculate the
RRFs for each analyte. Use Equation 429-22 to calculate ARRF, the relative percent
difference between the daily RRF and the mean RRF calculated during initial calibration
Check whether the performance criterion of Section 7.4.2B is satisfied. Report the results as
required by Section 10.2.
7.7.2 Relative Standard Deviation of Relative Response Factors
For each analyte, calculate (he sample standard deviation (SD) of die RRFs used to calculate the
?PF Use Equation 429-21 to calculate thi percent relative standard deviation (%RSD)
for each analyte. The analyst may use fee mean RRF if the percent relative standard deviation of
the RRFs is 30% or less. If the RSD requirement is not satisfied, analyze additional aliquots of
appropriate calibration solutions to obtain an acceptable RSD of RRFs over the entire
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concentration range, or take action to improve GC/MS performance. Otherwise, use the
complete five point calibration curve for that compound.
8 QUALITY ASSURANCE/QUALITY CONTROL
Each laboratory that uses this method is required to operate a formal quality control program. The
minimum quality control requirements of this program consists of an initial demonstration of laboratory
capability (according to Sections 7.3 and 8.1,3,1), and periodic analysis of blanks and spiked samples as
required in Sections 8.1.1 and 8.1.3.2 as a continuing check on performance.
The laboratory must maintain performance records to document the quality of data that are generated.
The results of the data quality checks must be compared with the method performance criteria to
determine if the analytical results meet the performance requirements of the method. The laboratory must
generate accuracy statements as described in Section 8.4.1.
8.1 QA SAMPLES
8.1.1 Laboratory Method Blank
The analyst must run a laboratory method blank with each set of 15 or fewer samples. The
method blank must be a resin sample from the same batch used to prepare the sampling cartridge .
and the laboratory control samples. The method blank must be prepared and stored as described
in Sections 4.3.4 and 4.3.5.
The analyst shall perform all of the same procedures on the method blank as are performed on
the solid samples (Section 6.5.2.1) from the beginning of sample extraction through to the end of
the GC/MS analytical procedures.
8.1.2 Performance Evaluation Samples
The laboratory should analyze performance evaluation samples quarterly when these samples
become available. These samples must be prepared and analyzed by the same methods used for
the field samples. Performance for the most recent quarter should be reported with the results of
the sample analysis.
8.1.3 Laboratory Control Sample (LCS)
8.1.3.1 Initial Demonstration of Laboratory Capability
Before performing sample analyses for the first time, the analyst shall demonstrate the
ability to generate results of acceptable precision and accuracy by using the following
procedures.
Prepare spiking solutions from stock standards prepared independently from those used for
calibration. Spike at least four resin samples cleaned as described in Section 4.2.2 with each
of the target unlabelled analytes as indicated in Table 9. Blank resin contamination levels
must be no greater than 10 percent of the levels of the spiked analytes. Add the amounts of
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internal standards required by Table 7 or 7A. Add the alternate standard to the extract to
monitor the efficiency of the cleanup procedure.
The LCS spikes shall undergo all of the same procedures as are performed on the solid
samples (Section 6.5.1.2) from the beginning of sample extraction through to the end of the
GC/MS analytical procedures.
Calculate:
(A) percent recoveries for the internal standards and alternate standard,
(B) flie mass of each target analyte in pg/sample or ng/sampie,
(C) the average of the results for the four analyses in pg/sample or
ng/sample,
(D) the average recovery (R) as a percentage of the amount added, and
(E) the relative standard deviation SR.
Report the results as required by Section 10.2.4.
If all the acceptance criteria of Section 8.2.6 are satisfied for all of the target PAH, the
analyst may begin analysis of blanks and samples. Otherwise, corrective action must be
taken as required by Section 8.2.6.
8.1.3.2 Ongoing Analysis of LCS
The analyst must run two laboratory control samples with each set of 15 or fewer samples
The resin for the LCS must be taken from the same batch used to prepare the sampling
cartridge and the laboratory method blank. The LCS resin must be prepared and stored as
described in Sections 4,3.4 and 4.3.5.
Prepare spiking solutions from stock standards prepared independently from those used for
calibration. Spike each resin sample with each of the target unlabelled analytes as indicated
in Table 9. Blank resin contamination levels must be no greater than 10 percent of the levels
of the spiked analytes. Add die amounts of internal standards required by Table 7 or 7 A
Add the alternate standard to the extract to monitor the efficiency of the cleanup procedure
The LCS spikes shall undergo all of the same procedures as are performed on the solid
samples (Section 6.5.1.2) from the beginning of sample extraction through to the end of the
GC/MS analytical procedures.
Calculate:
(A) percent recoveries for die internal standards and alternate standard,
(B) the mass of each target analyte in jig/sample or ng/sample,
(C) the average of the results for the two analyses in ng/sample or ng/sample:
(D) the average recovery as a percentage of the amount added, aid
(E) the relative percent difference for the two analyses.
Report the results as required by Section 10.2.
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Add the results which satisfy the performance requirements of Section 8.2.6 to the results of
the initial LCS analyses (8.1.3.1) and previous ongoing data for each compound in the LCS
sample.
Update the (.harts as described in Section 8.4.1.
8.2 ACCEPTANCE CRITERIA
8.2.1 Blank Trains
The levels of any unlabelled analyte quantified in the blank train must not exceed 20 percent of
the level cf that analyte in the sampling train. If this criterion cannot be met, calculate a
reporting limit that is five times the blank value (Equations 429-32 and 429-33). Do not
subtract the blank value from the sample value.
8.2.2 Surrogate Standard Recovery
Acceptable surrogate (field spike) recoveries should range from 50 to 150 percent If field spike
recoveries are not within the acceptable range, this must be clearly indicated in the laboratory
report. The affected sampling run must be identified in the report of the calculated emissions
data.
8.2.3 Internal Standard Recovery
Recoveries for each of the internal standards must be greater than 50 percent and less than 150
percent of the known value.
If internal standard recoveries are outside of the acceptable limits, the signal to noise ratio of the
internal standard must be greater than 10. Otherwise the analytical procedure must be repeated
on the stored portion of the extract
NOTE: This criterion is used to assess method performance. As this is an isotope dilution
technique, it is, when properly applied, independent of internal standard recovery.
Lower recoveries do not necessarily invalidate the analytical results for PAH, but
they may result in higher detection limits than are desired.
If low internal standard recoveries result in detection limits that are unacceptable, the cleanup
and GC/MS analysis must be repeated with the stored portion of the extract If the analysis of
die archive sample gives low recoveries and high detection limits, the results of both analyses
must be reported.
8.2.4 Laboratory Method Blank
The laboratory method blank must not contain any of the target analytes listed in Table 1 at
levels exceeding the PQL or 5 percent of the analyte concentration in the field sample.
If the method blank is contaminated, check solvents, reagents, standard solutions apparatus and
glassware to locate and eliminate the source of contamination before any more samples are
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analyzed. Tabic 3 shows those compounds that commonly occur as contaminants in the method
blank, and the ranges of concentrations that have been reported.
If field samples were processed with a laboratory method blank that showed PAH levels greater
than 5 percent of the field sample, they must be re-analyzed using the archived portion of the
sample extract ' -*
Recoveries of the internal standards must satisfy the requirements of 8.2.3. If the internal
standard recoveries are less than 50%, the S/N ratio must be greater than 10 for the internal
standard.
8.2.5 Performance Evaluation Sample
The following will be a requirement when performance evaluation samples become available,
and performance criteria have been established:
Performance for die most recent quarter must be reported with the results of the sample analysis
If the performance criteria (to be established) are not achieved, corrective action must be taken
and acceptable performance demonstrated before sample analysis can be resumed.
8.2.6 Laboratory Control Samples
8.2.6.1 Initial and Ongoing Analysis
The signal of each analyte in the initial and ongoing laboratory control samples must be at
least 10 times that of the background.
Acceptable accuracy is a percent recovery between 50 and 150 percent Acceptable
precision for the initial LCS samples is a relative standard deviation (USD) of 30 percent or
less.
Acceptable precision for the ongoing analysis of duplicate samples is a relative percent
difference of 50 percent or less.
If the RSD for the initial demonstration exceeds the precision limit, or any calculated
recovery falls outside the range for accuracy, the laboratory performance for that analyte is
unacceptable.
If the RPD for any ongoing duplicate analyses exceeds the precision limit, or any calculated
recovery falls outside the range for accuracy, fee laboratory performance for that analyte is
unacceptable.
Beginning with Section 8.1.3.1, repeat the test for those analytes that failed to meet the
performance criteria. Repeated failure, however, will confirm a general problem with the
*"»»nirement system. If this occurs, locate and correct the source of the problem and repeat
the test for all compounds of interest beginning with Section 8.1.3.1 for the initial analysis
and Section 8.3.1.2 for the ongoing analysis.
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8.3 ESTIMATION OF THE METHOD DETECTION LIMIT (MDL) AND PRACTICAL
QUANTITATION LIMIT (PQL)
8.3.1 Initial Estimate of MDL and PQL
The analyst shall prepare a batch of XAD-2 resin as described in Sections 4.2.2.1 to 4.2.2.3,
then check for contamination as required by Section 4.2.2.4. Identify those PAH analytes
present at background levels that are too high for the MDL determination. Use the procedure of
Appendix A to calculate MDLs for the remaining target PAH compounds. The analyst may use
any of the five approaches described in Appendix A (A 1.1) to estimate an initial spike level for
the MDL determination. One of die suggested approaches is based on a theoretical method
quantitation limit (TMQL) estimated according to Equation 429-16.
TMQL = C x I x 100 x 2 429-16
Where:
C = die concentration of the PAH in the lowest concentration calibration standard
used in the initial calibration, (ng/jiL)
V = the final extract volume, (^L)
P = the assumed percent recovery (50%) of the internal standard
2 = a factor to account for the fact that the final extract volume (V> contains one
half of the analyte in the sample. The other half is archived.
8.3.2 Ongoing Estimation of MDL and PQL
Once every quarter in which this method is used, the analytical laboratory must analyze one
spiked resin sample as described in Appendix A. Include all initial and quarterly results in the
calculation of the standard deviation and MDL for each analyte that has not been identified as a
common contaminant of the XAD-2 resin.
If die MDL for any analyte exceeds the MDL established during the initial determination, take
corrective action as necessary, and repeat the monthly analysis. If any MDL still exceeds the
initial MDL, then the initial standard deviation estimation procedure (Appendix A) must be
repeated.
8.4 LABORATORY PERFORMANCE
The analyst must have documented standard operating procedures (SOPs) that contain specific
stepwise instructions for canying out this method. The SOPs must be readily available and followed
by all personnel conducting die work. The SOP must be made available for review upon request by
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the Executive Officer, the tester or reviewer of the analytical results. The analyst may impose
restrictions on the dissemination of the information in the SOP.
The analyst must have documented precision and accuracy statements (Section 8.4.1) readily
available.
The analyst must have results of the initial and ongoing estimates of the MDL (Sections 8.3.1 and
8.3.2) readily available.
8.4.1 Precision and Accuracy Statement
The precision and accuracy statements for the analytical procedure shall be based on the results
of die initial and ongoing LCS analyses. The frequency of analysis is stated in Section 8.1.3.
Prepare a table of the recoveries and the relative percent difference for each ongoing analysis of
Ihe LCS and LCS duplicate. Figure ISA is an example of such a table. This must be included in
the analytical data package submitted for each set of sample analyses.
Prepare a quality control chart for each target analyte that provides a graphic representation of
continued laboratory performance for that target analyte. Figure 15B is an example QC chart for
benzo(a)pyrene.
9 CALCULATIONS
Carry out calculations retaining at least one extra decimal figure beyond that of fee acquired data. Round
off figures after the final calculation.
9.1 ANALYSTS CALCULATIONS
The analyst shall cany out the calculations described in Sections 9.1.1 to 9.1.11.
9.1.1 Relative Response Factors (RRF) for Unlabelled PAH and Surrogate Standards
Calculate the RRF for each target unlabelled PAH analyte and surrogate standard in each
calibration solution . Use Equation 429-17 and die data obtained during initial calibration
(7.3.7) or continuing calibration (7.4.1).
RRFg =
A. x Qi,
K * Q,
429-17
Where;
As = Area of the response for characteristic ions of die unlabelled analyte or
surrogate standard (Tables 11 or 11A, 13, and )4).
AjS «= Area of die response for characteristic ions of the appropriate internal standard
(Tables 11 or 1IA, 13, and 14).
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Qs = Amount of the unlabelled PAH calibration analyte or surrogate standard
injected on to GC column, ng.
Qis = Amount of the appropriate internal standard injected on to GC column, ng.
9.1.2 RRF for Determination of Internal Standard Recovery
Calculate RRFis according to Equation 429-18, using data obtained from the analysis of the
calibration standards.
RRF:. =
Ai» * 429-18
A„ x Qi,
Where:
A^ = Area of the response for characteristic ions of the appropriate recovery standard
(Tables 11 or 11A, 13, and 14).
Qn = Amount of the appropriate recovery standard injected on to GC column, ng.
9.1.3 RRF for Determination of Alternate Standard Recovery
Calculate RRF^ according to Equation 429-19, using data obtained from the analysis of the
calibration standards.
x Qrs 429-19
" " Are x Qm
Where:
A^ = Area of the response for characteristic ions of the alternate standard
(Tables 13 and 14).
= Amount of alternate standard injected on to the GC column, ng.
9.1.4 Mean Relative Response Factors (RRF)
Calculate the mean RRF for each target unlabelled PAH, surrogate standard, internal standard
and alternate standard using Equation 429-20 and the RRFs calculated according to Sections
9.1.1,9.1.2, and 9.1.3.
RRF = - E (RRF); 429"2°
n j,i
Where:
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RRFj « RRF calculated for calibration solution "i" using one of Equations 429-17,
429-18 or 429-19.
n = The number of data points derived from the calibration. The minimum
requirement is a five-point calibration (Section 7,2.3, Tables 5 and 6 or 6A)
9.1.5 Percent Relative Standard Deviation (%RSD) of Relative Response Factors
Use Equation 429-21 to calculate the relative standard deviation of die Relative Response
Factors for each analyte.
%RSD = x 100% 429"21
RRF
Where:
RRF « Mean relative response factor of a given analyte as defined in
Sections 7.7.1.4 and 9.1.4.
SD - The sample standard deviation of the relative response factors used to
calculate the mean RRF.
\
9.1.6: Continuing Calibration ARRF
Use Equation 429-22 to calculate ARRF, the relative percent difference (RPD) between the daily
RRF and the mean RRF calculated during initial calibration.
RRF - RRF ajq -)")
A RRF = x 100% 429*22
RRF
Where:
RRFC « The RRF of a given analyte obtained from the continuing calibration
(Section 7.4).
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9.1.7 Percent Recovery of Internal Standard, Rjs
Calculate the percent recovery, R,s for each internal standard in the sample extract, mina
Equation 429-23.
R. = ^ X 100% 429"23
" K x RRF. x Q„
Where:
RRF:, = Mean relative response factor for internal standard (Equations 429-18 and
429-20).
9.1.8 Percent Recovery of Surrogate S tandard, R^
Calculate die percent recovery, for each surrogate standard in the sample extract, using
Equation 429-24.
Rss = A* " x 100% "29-24
Aj. x RRF. x Q
IS s ss
Where:
Au = Area of the response for characteristic ions of the surrogate standard
(Tables 13 and 14).
Qjj. = Amount of the surrogate standard added to resin cartridge before sampling,
ng.
RR_FS = Mean relative response factor for surrogate standard (Equations 429-17 and
429-20).
9,1.9 Percent Recovery of Alternate Standard, R^
Calculate the percent recovery, R^ for the alternate standard in the sample extract, using
Equation 429-25.
R = Aas X x 100% 429"25
Ab x RRFm x Qm
Where:
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RRF^ = Mean relative response factor for alternate standard (Equations 429-19 and
429-20).
9.1.10 Mass of the Target Analytes and Surrogate Standards in
Emissions Sample or Blank Train
Use Equation 429-26 to determine the total mass of each PAH compound or surrogate standard
in the sample:
Report the PQL (9.1.11) for those analytes that were not present at levels higher than the PQL
provided to the tester prior to testing (2.3.3).
M = Q's X A* 429-26
Ais x RRF
Where:
M ¦» Mass (ng) of surrogate standard (MJ or target analyte (M^ detected in the
sample.
Qis « Amount of internal standard or surrogate standard added to each sample
A$ = Area of the response for characteristic ions of the unlabelled analyte or
surrogate standard (Tables 13 and 14).
Ai$ « Area of the response for characteristic ions of the appropriate internal
standard (Tables 13, and 14).
kftF = Mean relative response factor of a given analyte calculated as required by
Sections 7.7.1.4 and 9.1.4.
9.1.11 Analytical Reporting Limit
The analyst shall report the PQL (Section 2.3.3) for those analytes that were not present in the
emissions sample or blank train at levels higher than the pre-test estimate of the PQL
9.2 TESTER'S CALCULATIONS
9.2.1 Sample/Blank Train PAH Mass Ratio
Use Equation 429-27 to calculate the sample/blank train mass ratio for each PAH detected at
levels above the MDL in both the field sample and the blank train.
RATIO = — 429"27
Mb?
Where:
July 28, 1997 M-429 Page 60
N-938
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Mj = Mass of target PAH analyte detected in the sampling train
(Equation 429-26).
Mbt = Mass of the same PAH analyte detected in the blank train.
If the sample to blank train PAH mass ratio is less than five, calculate the reporting limit for the
tested source as required by Section 9.2.4.2. Do not calculate Mc (Section 9.2.2) or Me (Section
9.2.3) for the emissions report
9.2.2 PAH Concentration in Emissions
Use Equation 429-28 to calculate the concentration in the emissions of 1) the PAH analytes
detected in the sampling train but not in the blank train, and 2) the PAH analytes that satisfy the
minimum sample to blank train mass ratio required by Section 9.2.1.
Mc =
Mt i
429-2c
0.028317
tn(std)
Where:
Mc = Concentration of PAH in the gas, ng/dscm, corrected to standard conditions
of 20°C, 760 mm Hg (68°F, 29.92 in. Hg) on dry basis.
Mt = Mass of PAH compound in gas sample, ng (Equation 429-26)
^m(std) = Volume of gas sample measured by the dry gas meter, corrected to standard
conditions, dscf (Equation 429-10)
0.028317 = Factor for converting dscf to dscm.
9.2.3 PAH Mass Emission Rate
Use Equation 429-29 to calculate the mass emission rate for each PAH compound that satisfies
the minimum sample/blank train PAH mass ratio (Section 9.2.1). ~
M = M* x — 429"30
B V„(1-) 60
Where:
Me = Mass emission rate for PAH analyte, ng/second
Mt = Mass of PAH compound in the gas sample, ng (Equation 429-26)
My 28, 1997 M-429 Page 61
N-239
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Qstd " Average stack gas dry volumetric flow rate corrected to standard
conditions, dscf/min.
60 « Factor for converting minutes to seconds
9.2:4 Source Reporting Limit
¦ t "
9.2.4.1 PAH Not Detected in Either Sampling or Blank Train
Use Equation 429-30 or 429-31 to calculate the reporting limit for those analytes that were
not detected at levels above the PQL in either the sampling or blank train.
RL = PQL x 1 429-30
CS VD(s{d) 0.028317
RL = -12=- x
PQL „ Q
std v 429-31
es
Vn(-) 60
Where:
Rlcs = Reporting limit for the tested source, (ng/dscm), corrected to standard
conditions of 20°C, 760 mm Hg (68°F, 29-92 in. Hg) on dry basis
Rl^ ¦ Reporting limit for the tested source, (ng/sec.).
0.028317 = Factor for converting dscf to dscm.
60 = Factor for converting minutes to seconds.
9.2.4.2 PAH Detected in Blank Train and Sample/Blank Train Ratio <5
If the sample to blank train PAH mass ratio is less than five, then Equation 429-32 or 425-
33 shall be used to calculate the reporting limit for that PAH.
RL^
RJL^
5 x ^BT ^ 1 429-32
V,(1-) 0.028317
5 X M^j. 429-33
V.(rt) 60
'Ahere:
July 28,1997
N-240
M-429 Page 62
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Rl^ = Reporting limit for the tested source, (ng/dscm), corrected to standard
conditions of 20°C, 760 mm Hg (68°F, 29-92 in Hg) dry bn-sis.
Rl^ = Reporting limit for the tested source, (ng/sec ).
Mbt - , The total mass of that PAH analyte in the field u.OiiA LlUiX*.
10 REPORTING REQUIREMENTS
The source test protocol must contain all the sampling and analytical data required by Sections 2.2 to 2.5,
4.2.1.1, and 4.2.2.4, as well as the information listed in Sections 10.1 and 10.2 that pertain to
identification and quantitation of the samples.
The emissions test report must contain all of the sampling and analytical data necessary to calculate
emissions values for the target analvtes or to demonstrate satisfactory performance of the method.
Hie end user or reviewer should be able to obtain from the source test report all information necessaiy to
recalculate all reported test method results or to verify that all required procedures were performed.
Any deviations from the procedures described in this method must be documented in the analytical and
sampling report
10.1 SOURCE TEST PROTOCOL
At a minimum, the source test protocol must include ail of the data required by Section 2.2 and the
information listed in Sections 10.1.1 through 10.1.4.
10.1.1 Preparation of Filters
A. Manufacturer's lot number for the batch of filters to be used in the test
B. Contamination check of filter (Section 4.2.1.1)
(i) Date of cleaning.
(ii) Date of PAH analysis.
(iii) Table of results of PAH analysis required by Section 4.2.1. The analytical report
must include all of the data listed in Section 10.2.
C. Storage conditions prior to the test (4.3.3)
10.1.2 Preparation of XAD-2 resin
A. ID for the batch to be used in the test The same batch must be used for the sampling train
and the laboratory QC samples.
B. Contamination check of resin (Sections 4.2.2.1 to 4.2.2.4)
(i) Date of cleaning.
(ii) Date of PAH analysis.
July 28, 1997 M-429Page63
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(iii) Table of results of PAH analysis required by Section 4,2.2.4, The analytical report
must include all of the data listed in Section 10.2.
C. Addition of surrogate standards to the resin cartridge.
(i) Amount of each compound.
(ii) Date of spiking.
D. Storage conditions prior to the test (Section 4.3.3)
f. 10.1.3 Method Detection Limits and Practical Quantitation Limits
!
' The MDL and PQL for each target analyte determined as required by Sections 2.3.2 and 2.3.3.
r
I 10.1.4 Target Sampling Parameters
A. Source target concentration of each emitted PAH of interest
B. Results of calculations required by Sections 2.5.2 to 2.5.5.
[ Figure 9 shows the minimum required calculations of target sampling parameters.
i -
10.2 LABORATORY REPORT
f :
v The analyst must generate a laboratory report for each pre-test analysis of the sampling media
(Sections 2.3,4.2.2.1, and 4.2.2.4) and each post-test analysis of the sampling trains and laboratory
QC samples.
A minimum of 7 post-test analyses are required to determine the emissions from the source and to
document the quality of the emissions data. These are the analyses of three sampling runs, one blank
^ train, one laboratory method blank and two laboratory control samples.
i
At a minimum, any report (data package) from the analyst to the tester shall contain the information
listed in Sections 10.2.1 to 10.2.6 pertaining to identification and PAH quantitation of all samples
10.2.1 Five-point Initial Calibration
The report of the results of die initial five-point calibration must include the data listed in A, B,
and C below:
A. Mass chromatograms for each initial calibration solution that show at a minimum
(i) Instrument ID,
(ii) laboratory sample ID on each chromatogram.
(iii) date and time of GC/MS analysis,
(iv) mass of monitored ions for each compound in the calibration solution - unlabeled
PAH, internal standard, surrogate standard, alternate standard and recovery standard,
(v) retention time for each compound in the calibration solution, and
July 28,1997 M-429 Page 64
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(vi) either peak height or area of the signals observed for the monitored ion masses.
B. A summary table of the data obtained for each initial calibration solution that shows at a
minimum
(i) Instrument ID,
(ii) laboratory sample ID,
(iii) date and time of GC/MS analysis,
(iv) retention time for each compound - unlabelled PAH, internal standard, surrogate
standard, alternate standard and recovery standard,
(v) relative retention time for each unlabelled PAH,
(vi) either peak height or area of the signals observed for the monitored ion masses,
(vii) the relative response factors for each unlabelled PAH, internal standard, surrogate
standard, and alternate standard, and
(viii) analyst's signature
Figure 14A is an example of a summary table that contains the minimum required information
for the analysis of a single calibration solution.
C. A summary table that shows at a minimum;
(i) Instrument ID,
s (ii) the date and time of the GC/MS analysis,
(iii) the relative response factor (RRF) calculated for each unlabelled PAH, internal
standard, surrogate standard, and alternate standard in each calibration solution,
(iv) the average relative response factor (RRF) calculated for the five point calibration,
(v) the relative standard deviation of the relative response factors, and
(vi) the recovery of each internal standard in percent
Figure 14B is an example of a report that contains the minimum required information for a five
point calibration summary.
10.2.2 Continuing Calibration
The report of tlr results of a continuing calibration must include the data listed in 10.2.2 A, B,
and C below:
A. Mass chromatogram that shows at a minimum the information listed in 10.2.1 A.
B. A summary table of the raw data obtained for the continuing calibration that shows at a
minimum, the information listed in 10.2.1B.
C. A summary table that shows at a minimum:
(i) the relative response factor (RRF) for each unlabelled PAH, internal st?ndard,
surrogate standard, and alternate standard in the continuing calibration solution,
(ii) the average relative response factor (RRF) for each compound calculated for the five
point calibration,
July 28, 1997 M-429 Page 65
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(iii) • ARRF for each unlabelled PAH, internal standard, surrogate standard, and alternate
standard in die continuing calibration solution,
(iv) the recovery of each internal standard in percent
Figure 14C is an example of a summary report that contains the minimum information required
by Section 10.2.2C for "the analysis of the continuing calibration solution.
10.2.3 Laboratory Method Blank
The laboratory report of the results of the analysis of the method blank must include at a
minimum the data listed in 10.2.3 A, B, and C below:
A. Mass chromatograms that show at a minimum the information listed in 10.2.1 A.
B. A summary table of the data obtained for each method blank that shows at a minimum, the
information listed in 10.2.S B.
C. A summary table that reports die same data as listed in 10.2.S C below.
10.2.4 Laboratory Control Samples
The report of die results of the analysis of the LCS samples must include at a minimum the data
listed in 10.2.4 A, B, and C below;
A. Mass chromatograms that show at a minimum the information listed in 10.2.1 A.
B. A summary table of the raw data for each sample that shows at a minimum, the informahm
listed in 10.2.1 B, and in addition:
(i) Ghent's sample ID
(ii) mass of each analyte,
(iii) the recovery of each internal standard, and alternate standard,
Figure 16A is an example of a summary table feat contains the minimum information required
by 10.2.4 B.
C. A summary table that reports for the two LCS analyses:
(i) ~ client's sample ID,
(ii) sample matrix description,
(iii) date of cleaning of the XAD-2 resin,
(iv) lot number for the resin (resin for all field samples and QA samples must come from
the same lot),
(v) date of extraction of LCS samples,
Figure 15A is an example of a summary table that contains the minimum information required
by 10.2.4 C.
My 28, 1997 M-429Page66
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10.2.5 Emissions Samples
The report of the results of the analyses of the three sampling trains and the blank train must
include the data listed in 10.2.5 A, B, and C below:
A. Mass chromatograms that show at a minimum the information listed in 10.2.1 A, and in
addition,
(i) clients sample ID
B. A summary table of die data for the analysis of each sample that shows at a minimum, the
information listed in 10.2.1 B, and in addition,
(i) client's sample ID
(ii) Date of five point initial calibration (ICAL)
(iii) ICAL ID,
(iv) mass of each analyte,
(v) . the recovery of each internal standard, alternate standard and surrogate standards in
percent
Figure 16A is an example of a summary table that contains the minimum information req"ired
by 10.2.5 B.
C. A summary table feat reports:
(i) client's sample ID (from a chain of custody record submitted by the tester),
(ii) sample matrix description,
(iii) date of cleaning of the XAD-2 resin,
(iv) lot number for the resin (resin for all field samples and QA samples must come from
the same lot),
(v) date of submittal of the tester's samples
(vi) date of extraction of samples,
(vii) Initial calibration Run ID,
(viii) Continuing calibration ID
Figure 16B is an example of a summary table that contains the minimum information required
by 10.2.5C.
10.2.6 Data Flags
The laboratory report must include an explanation of my qualifiers that are used to indicate
specific qualities of die data.
10.3 EMISSIONS TEST REPORT !
The emissions test report should include narrative that describes how the test was done. The tester's ,
report must also include all the appropriate sections used in a report from a Method 5 test such as a !
description of the plant process, sampling port locations, control equipment, fuel being used, general "i
July 28, 1997 M-429 Page 67 )
N-245
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plant load conditions during the test (description of plant production equipment problems, etc.), and
anything else necessary to characterize fee condition being tested.
Hie tester's report must also include all of the information listed in Sections 10.3.1 to 10.3.4.
10.3.1 Tester's Summary of Analytical Results
The tester must summarize the results of the minimum seven analyses required for each source
test At a minimum, the summary must contain fee information listed in Figure 17 A including
all data flags.
The tester must obtain the detailed analytical results (Section 10,2) from the laboratory and
include diem in the appendices as required below.
10.3.2 Field Data Summary
The report from the tester to the end user must contain a field data summary. This summary
must include at a minimum a table of the results of the calculations required by Section 4.5. as
well as the values which were used to calculate the reported results. Figure 17B is an example of
a field data summary that contains the minimum required information.
10.3.3 PAH Emissions Results
Figure 17C show the calculations of die concentrations and mass emission rates of the target
PAH. The reviewer should be able to use the data in Figures 17A and 17B to check fee
calculations in Figure 17C. The reviewer should also be able to check the appendix to the report
to determine the accuracy and the quality of the data summarized by fee tester in Figures 17 A
and 17B
10.3.4 Appendix to the Emissions Test Report
At a minimum, the following raw data or signed copies must be included in an appendix to the
emissions test report
A. Record of data for sample site selection and minimum number of traverse points.
B. Moisture determination for isokinetic settings.
C. Velocity traverse data.
D. Gas analysis for determination of molecular weight
E. Calibration records.
F. Method 429 sampling run sheets.
G. PAH laboratory reports listed in Section 10.2
July 28, 1997 M-429 Page 68
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The information listed above is to be considered as the minimum that should be included to
characterize a given operating condition. The end user or the executive officer m w require
additional information for any given project
11 BIBLIOGRAPHY
11.1 U.S. Environmental Protection Agency/Office of Water Engineering and Analysis Division (4303),
Washington D C., Method 1613. Tetra-through Octa-Chlorinated Dioxins and Furans by Isotope
Dilution HRGC/HRMS. EPA 821-B-94-005. (1994).
11.2 U.S. Environmental Protection Agency/Office of Solid Waste, Washington D.C., Method 3611A.
Alumina Column Cleanup and Separation of Petroleum Wastes. In "Test Methods for Evaluating
Solid Waste-Physical/Chemical Methods" SW-846 (1986).
11.3 U.S. Environmental Protection Agency/Office of S6hd Waste, Washington D C., Method 3630B.
Silica Gel Cleanup. In "Test Methods for Evaluating Solid Waste-Physical/Chemical Methods"
SW-846 (1986).
11.4 Thomason, J.R., ed., Cleaning of Laboratory Glassware. Section 3, A, pp 1-7 in "Analysis of
Pesticide Residues in Human and Environmental Samples", Environmental Protection Agency,
Research Triangle Park, N.C. (1974).
11.5 ARB Method 428. Determination of Polychlorinated Dibenzo-p-dioxin (PCDD) and Folychlorinated
Dibenzofiiran (PCDF) Emissions From Stationary Sources. September, 1990.
11.6 U. S. Environmental Protection Agency, Method 1625 Revision B - Semivolatik Organic
Compounds by Isotope Dilution. 40 CFR Ch. 1 (7-1-95 Edition) PL 136, App. A.
11.7 Rom, Jerome J., Maintenance, Calibration, and Operation of Isokinetic Source Sampling Equipment.
Environmental Protection Agency. Research Triangle Park, NC. APTD-0576. March, 1972.
11.8 Shigehara, R.T., Adjustments in the EPA Nomograph for Different Pitot Tube Coefficients and Dry
Molecular Weights. Stack Sampling News, 2: 4-11. October, 1974
11.9 "Prudent Practices in the Laboratory. Handling and Disposal of Chemicals;" National Academy
Press. Washington D.C. 1995.
July 28, 1997
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TABLE 1
METHOD 429 TARGET ANALYTES
Naphthalene
2-Methylnaphtfaalene
Acenaphthene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chiysene
Benzo(b)fluoraathene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyTene
Perylcne
Indeno(l ,2,3-cd)pyrene
Dibenz(aJj)anthracene
Benzo(ghi)perylene
July 28,1997
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M-429 Page 70
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TABLE 2
PRACTICAL QUANTITATION LIMITS FOR TARGET PAHs
Naphthalene
2-Methy lnaphth alene
Acenaphthene
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
B'"n2o(a)anthracene
Chiysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno(l,2,3-cci)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
LRMS
(yg/sample)
244
1.25
0.210
0.104
0.207
0.85
0.146
0.346
0.191
0.167
0.272
1.119
0.738
0.146
0.191
0.143
0.798
0.465
0.305
HRMS
(ng/sample)
480
66
5.0
5.0
16.5
22
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
370
19
5.0
5.0
5.5
14
5.0
5.0
5.0
5.0
5.C
5.0
5.0
5.0
5.0
5.0
5.0
5.0
5.0
July 28, 1997
M-429 Page 71
N-249
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TABLE 3
PAH ANALYSIS BY HRMS OF DIFFERENT LOTS OF CLEANED RESIN
M
CJ1
O
CONCENTRATION
(ng/sample)
PAH ANA! YTES
SAMPLE IDENTIFICATION
Ai
A2
| A3
A4
A5
| A6
A7
A8
A9
A10
All
A12
AI3
Naphthalene
480
220
19*
120
350
340
320
360
370
380
340
520
220
2-MethylnaphthaIene
65
32
38
15.6
32
15.6
32
26
19
45
15
32
48
Acenaphlhylene
<5.0
<5.0
<5.0
<50
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
Acenaphthenc
<5.0
<5.0
<5.0
<5,0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5,0
<5,0
<5,0
Fluorene
16.5
9.8
13
<5.0
5.7
5.4
7.4
5.8
S.5
10
5.5
6.8
50
Phenanthrene
22
16
32
<12.5*
14
14.8
16
12
14
24
13
<13.0*
14
Anthracene
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
Fluoranthene
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
Pyrcne
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
Benzo(a)anthraccnc
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
Chrysene
<5.0
<5.0
<5.0
<5 0
<5.0
<5.0
<5.0
<50
<5.0
<5.0
<5.0
<5.0
<5.0
Benzo(b)fluorBnthenc
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
Ekmzo(lc)fluoratithene
<5.0
<50
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5,0
<5.0
<5.0
<5.0
Benzo(e)pyrcne
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
<5.0
Benzo(a)pyfetK
<5.0
<5.0
<5.0
-------
TABLE 4
COMPOSITION OF THE SAMPLE SPIKING SOLUTIONS
' .• Concentration
Spiking ng/fil pg/pl
Solutions Analytes LRMS HRMS
1- Surrogate Standards
d10-Fluorene 1.0 250
d14-TeiphenyI 1.0 250
2. Intgrnffl fards
d8-Naphthalene 1.0 100
d10-2-Methylnaphthalene .. 1.0 100
dg-Acenaphthylene 1.0 100
d10-Pheoanthrene - 1.0 100
d10-Fluoranthene 1.0 100
d12-Benzo(a)anthraccoc 1.0 100
d12-Chrysene 1.0 100
d12-Benzo(b)fluoranthene 1.0 200
d12-Benzo(k)fluoranthene 1.0 200
d12-Benzo(a)pyrenc 1.0 200
d12-Pcrylene 1.0 200
d12-Indeno(lr2,3,c-d)pyrenc 1.0 200
dl4-Dibenz(a»h)aathracene 1.0 200
d12-Benzo(ghi)perylene 1.0 200
3. Alternate Standard
d j 0-Anthracene 1.0 100
4. Pwvg ry Standards
dI0-Acenaphtfaene 20.0 2000
d10-Pyrcae 20.0 2000
d12-benzo(e)pyrene 20.0 2000
28, 1997
N-251
M-429 Page 73
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TABLE4A
COMPOSITION OF ALTERNATIVE SAMPLE SPIKING SOLUTIONS
Concentration
Spiking pg/yl
Solutions Analytes HRMS
1A.
Surrogate Standards
d12-Benzo(e)pyrcne
d14-Tcrphcnyl
250
250
2A.
Internal Stiwdartfs
dg-Naphthalene
- dg-Acenaphtfaylcnc
dj0-Accnaphthene
dj0-Fluorene
d10-PhcDanthrcne
d10-Fluoranthcne
d12-Benzo(a)anthracene
d12-Chryscnc
d22-Benzo(b)fluoranthene
dl2-Benzo(k)fluoranthene
d 12-Betizo(a)pyrene
d 12-Indcno( 1 ^2,3,c-d)pyrene
d 14-Dibenz(a^3)anthracene
d12-Bcnzo(ghi)pcrylcnc
100
100
100
100
100
100
100
100
200
200
200
200
200
200
3A.
Alternate Standard
d10-Anthracene
100
4A.
Recovery Standards
dj 0-2-Mctfay [naphthalene
djo-Pyrene
d12-Perylene
2000
2000
2000
July 28,1997
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TABLE 5
CONCENTRATIONS OF PAHs IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR LOW RESOLUTION MASS SPECTROMETRY
CONCKNTRATf?^ r-N
Msom
-
1
2
3
4
5
Calibration Standards
Naphthalene
0.25
0.5
1.0
2.5
5.0
2-Methylnaphthalene
0.25
0.5
1.0
2.5
. 5.0
Acenaphthene
0.25 '
0.5
1.0
2.5
5.0
Acenaphthylene
0.25
0.5
1.0
2.5
5.0
Fluorcne
0.25
0.5
1.0
2.5
5.0
Phenanthrene
0.25
0,5
1.0
2.5
5.0
Anthracene
0.25
0.5
1.0
2.5
5.0
Fluoranthene
0.25
0.5
1.0
2.5
5.0
Pyretic
0.25
0.5
1.0
2.5
5.0
Bcnzo(a)anthracene
0.25
0.5
1.0
2.5
5.0
Chryscne
0.25
0.5
1.0
2.5
5.0
Benzo(b)fluoranthene
0.25
0.5
1.0
2.5
5.0
Bcnzo(k)fluoranthene
0.25
0.5
1.0
2.5
5.0
Benzo(e)pyrene
0.25
0.5
1.0
2.5
5,0 .
Bcnzo(a)pyrene
0.25
0.5
1.0
2.5
5.0
Perylene
0.25
0.5
1.0
2.5
5.0
Indcno( 1,2,3 -cd)pyrene
0.25
0.5
1.0
2.5
5.0
Dibcnz(arh)anthjacene
0.25
0.5
1.0
2.5
5.0
Beazo(ghi)perykne
0.25
0.5
1.0
2.5
5.0
Internal Standards
dg-Naphthalene -
1.0
1.0
1.0
1,0
1.0
d10-2-MethyInaphthalene
1.0
1.0
1.0
1.0
1.0
d^-Acenaphthylene
1.0
1.0
1.0
1.0
1.0
d10-Phenanthrene
1.0
1.0
1.0
1.0
1.0
d10-Fluoranthene
1.0
1.0
1.0
1.0
1.0
dj2-Benzo(a)antfaracene
1.0
1.0
1.0
1.0
1.0
d12-Chrysene
1.0
1.0
1.0
1.0
1.0
d l2-Benzo(b)fluorantfaene
1.0
1.0
1.0
1.0
1.0
d 12-Benzo(k)fluonmthene
1.0
1.0
1.0
1.0
1.0
d12-Beazo(a)pyrcne
1.0
1.0
1.0
1.0
1.0
d12-Perylcnc
1.0
1.0
1.0
1.0
1.0
d j 2-Indcno( 1 ^,3 ,c -d)pyrenc
1.0
1.0
1.0
1.0
1.0
d14-Dibenz(a4i)anthracene
1.0
1.0
1.0
1.0
1.0
dj 2-Benzo(ghi)perylene
1.0
1.0
1.0
1.0
1.0
July 28, 1997
N-253
M-429 Page 75
-------
TABLE 5 (CONT)
CONCENTRATIONS OF PAHs IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR LOW RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS fag/uLl
1
2
3
4
5
; Syrrgg^t? Standards
d10-Fluorene
1.0
1.0
1.0
1.0
1.0
d14-Terphenyl
1.0
1.0
1.0
1.0
1.0
Alternate Standard
d10-Anthracene
1.0
1.0
1.0
1.0
1.0
Uecoverv Standards
d |0-Acenaphthene
1.0
1.0
1.0
1.0
1.0
djg-Pyrene
1.0
1.0
1.0
1.0
1.0
d 12-benzo(e)pyrene
1.0
1.0
1.0
1.0
1,0
July 28,1997
N-254
M-429 Pege 76
-------
TABLE 6
CONCENTRATIONS OF PAHs IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
concentrate::;; ¦w™.
Solutions
1
2
3
4
5
Calibration Standard?
Naphthalene
10
50
100
200
500
2-Methylnaphthalene
10
50
100
200
500
Accnaphthylene
10
50
100
200
500
Acenaphthene
10
50
100
200
500
Fluorene
10
50
100
200
500
Phenacthrene
10
50
100
200
500
Anthracene
10
50
100
200
500
Fluoranthene
10
50
100
200
500
Pyrene
10
50
100
200
500
Beazo(a)anthracene
10
50
100 ¦"
200
500
Chiysene
10
50
100
200
500
Benzo(b)fluoranthene
10
50
100
200
500
Benzo(k)fluorantfaene
10
50
100
200
500
Benzo(e)pyrene
10
50
100
200
500
Benzo{a)pyrene
10
50
100
200
500
Perylene
10
50
100
200
500
Indeno( 1,2,3-cd)pyrene
10
50
100
200
500
Dibeaz(aji)anthracene
10
50
100
200
500
Benzo(ghi)perylene
10
50
100
200
500
Internal Standards
dg-Naphthalene
100
100
100
100
100
dgMethylnaphthalene
100
100
100
100
100
dg-Acenaphthy!ene
100
100
100
100
100
d10-Phenanthrene
100
100
100
100
100
dj0-Fluoranthenc
100
100
100
100
100
d [ 2-Benzo(a) anthracene
100
100
100
100
100
dj2-Chrysene
100
100
100
100
100
d 12-Bcnzo(b)fluorantfacne
200
200
200
200
200
d12-Benzo(k)fluoranthene
200
200
200
200
200
di2-Bcnzo(a)pyrene
200
200
200
200
200
d12-Perylene
200
200
200
200
200
d12-Indeno( 1.2,3 ,c-d)pyrene
200
200
200
200
200
d14-Dibcnz(aj3)anthracene
200
200
200
200
200
d12-Bcnzo(ghi)perylene
200
200
200
200
200
July 28, 1997
N-255
M-429 Page 77
-------
TABLE 6 (CONT)
CONCENTRATIONS OF PAHs IN WORKING GC/MS CALIBRATION STANDARD
SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS fpg/uL)
Surrogate Standards
dl0-Ruorene
d14-Terphenyl
Alternate Standard
d10-Anthracene
Recovery Standards
d j 0-Aceoaphtfaene
djQ-Pyrene
d 12-ben2o(e)pyrcne
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
200
200
200
200
200
200
200
200
200
200
200
200
200
200
200
July 28,1997
N-256
M-429 Page 78
-------
TABLE 6A
CONCENTRATIONS OF PAHs IN ALTERNATIVE WORKING GC/MS CALIBRATION
STANDARD SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
CONCENTRATOR V
Solutions
Calibration Standards
Naphthalene
10
50
100
200
500
2-Methylnaphthalene
10
50
100
200
500
Acenaphthylene
10
50
100
200
500
Acenaphthene
10
50
100
200
500
Fluorene
10
50
100
200
500
Phcnanthrene
10
50
100
200
500
Anthracene
10
50
100
200
500
Fluoranthene
10
50
100
200
500
Pyrene
10
50
100
200
500
Bemzo(a)anthracene
10
50
100
200
500
Chiysene
10
50
100
200
500
Benzo(b)fluoranthenc
10
50
100
200
500
Benzo(k)fluoranthene
10
50
100
200
500
Beazo(e)pyrene
10
50
100
200
500
Benzo(a)pyrene
10
50
100
200
500
Perylene
10
50
100
200
500
Indeno(l,2,3-cd)pyrene
10
50
100
200
500
Dibenz(aji)anthracene
10
50
100
200
500
Benzo(ghi)perylene
10
50
100
200
500
Internal Standards
dg-Naphthalene
100
100
100
100
100
d8-Acenaphthylene
100 .
100
100
100
100
d10-Acenaphthene
100
100
100
100
100
dj0-Fluorene
100
100
100
100
100
di(j-Phenanthrene
100
100
100
100
100
d10-Fluoranthene
100
100
100
100
100
d12-Bcnzo(a)anthracene
100
100
100
100
100
d12-Chrysene
100
100
100
100
100
di2-Benzo(b)fluorandiene
200
200
200
200
200
dj2-Benzo(k)£luoranthene
200
200
200
200
200
d12-Benzo(a)pyrene
200
200
200
200
200
d 12-Indeno( 1,2,3 ,c-d)pyrene
200
200
200
200
200
d14-Dibenz(a^i)anthraceQe
200
200
200
200
200
d] 2-Benzo(ghi)perylene
200
200
200
200
200
July 28,1997
N-257
M-429 Page 79
-------
TABLE 6A (CONT)
CONCENTRATIONS OF PAHs IN ALTERNATIVE WORKING GC/MS CALIBRATION
STANDARD SOLUTIONS FOR HIGH RESOLUTION MASS SPECTROMETRY
CONCENTRATIONS (rW,in
-
1
2
3 .
4
5
Surrogate Standards
d12-benzo(c)pyrcne
100
. 100
100
100
100
d14-Terphenyl
100
100
100
100
100
Alternate Standard
d j 0-Anthracene
100
100
100
100
100
Recovery Standards
d j 0-2-Metbylnaphthalene
200
200
200
200
200
d10-Pyrene
200
200
200
200
200
d12-Perylene
200
200
200
200
200
July 28,1997
N-258
M-429 Page 80
-------
TABLE 7
SPIKE LEVELS FOR LABELLED STANDARDS
Time of
Addition Analvte
LRMS
(pg/sample) (ng/sample)
Before
sampling
Before
extraction
Before
extraction
Before
GC/MS
Surropate Standards
d10-Fluorene
2.0
500
dl4-Terphenyl
2.0
500
Internal Standards
,
dg-Naphthalene
2.0
200
d10-2-Methylnaphthalene
2.0
200
dg-Acenaphthylene
2.0
200
dj0-Phenanthrene
2.0
200
d10-Fluoranthene
2.0
200
d12-Benzo(a)anthracene
2.0
200
d12-Chryseae
2.0
200
d |2-Benzo(b)fluoraiJtfaene
2.0
400
d]2-Bcrizo(d)fluoranthene
2.0
400
dI2-Benzo(a)pyrene
2.0
-400
d12-Perylene
2.0
400
d12-Isdeno( l,2,3,c-d)pyrene
2.0
400
d14-Dibenz(aJi)antbracene
2.0
400
d 12-Beazo(ghj)perylene
2.0
400
Alternate Standard
djQ-Aiithracene
2.0
200
Recovery Standards
d10-AceDaphthene
1.0
100
d10-Pyrene
1.0
100
d 12-benzo(e)pyrene
1.0
100
July 28, 1997
N-259
M-429 Page 81
-------
TABLE 7A
SPIKE LEVELS FOR LABELLED STANDARDS FOR ALTERNATIVE HRMS SPIKING SCHEME
Time of
HRMS
Addition
Anaiyte *
(ng/sample)
Before
Surrogate Standards
sampling
d12-benzo(e)pyrcne
500
d14-Terphcnyl
500
Before
Internal Standards
extraction
dg-Napbthalene
200
dg-Acenaphthylene
200
d10-Acenaphtbene
200
di0-Fluorrae
200
d10-Phenantbrene
200
d10-Fluoranthene
200
d12-Benzo(a)anthracene
200
d|2-Chrysene._
200
d12-Benzo(b)fluoranthene
400
;
d12-Benzo(d)£luorantfaene
400
d12-Benzo(a)pyrene
400
d 12-Indeno( I,2,3 ,c-d)pyrene
400
d14-Dibenz(aJj)anthracene
400
d12-Benzo(ghi)pcrylene
400
Before
Alternate Standard
extraction
d10-Anthracene
200
Before
Recovery Standards
GC/MS
d10-2-Methylnaphthalene
100
d|0-Pyrene
100
dyPeiylene
100
July 28,1997
M-429 Page 82
-------
TABLE 8
TARGET CONCENTRATIONS FOR LABELLED STANDARDS IN SAMPLE EXTRACT1
ng/jd iWnl
LRMS HRMS
Surrogate Standards
d10-Huorene
2.0
500
d14-Terphenyl
2.0
500
Internal Standards
dg-Naphthalene
2.0
200
d10-2-MetfaylnaphthaIenc
2.0
200
dg-Acenaphthykne
2.0
200
djQ-Phenanthrene
2.0
200
d10-Fluoranthene
2.0
200
d 12-Benzo(a)anthracene
2.0
200
d12-Chrysene
2.0
200
dj2-Beazo(b)fluoraathene
2.0
400
d 12-Ben2o(k)fiuoranthene
2.0
400
d 12-Benzo(a)pyrene
2.0
400
d12-Perylene
2.0
400
d 12-Indeno( 1^2,3 ,c-d)pyrene
2.0
400
d14-Dibenz(a,h)2cthracene
2.0
400
d 12-Benzo(ghi)pery lene
2.0
400
Alternate Standard
d10-Anthracene
1.0
200
Recovery Standards
d10-Acenaphthene
1.0
200
d20-Pyrene
1.0
200
d12-beazo(e)pyrene
1.0
200
1 Assuming 100 percent recovery.
July 28, 1997
N-261
M-429 Page 83
-------
TABLE 8A
TARGET CONCENTRATIONS FOR LABELLED STANDARDS IN SAMPLE EXTRACT
OBTAINED WITH ALTERNATIVE HRMS SPIKING SCHEME1
pg/pl
HRMS
Surrogate Standards
d12-benzo(e)pyrene 500
d|4-Terphcnyl 500
Stanfards
dg-Napbthalene 200
dg-Acenaphthylcne 200
d10-Acenaphthene 200
d10-Fluorene 200
d10-Phenanthrcne 200
dj0-Fluoranthene 200
d12-Benzo(a)anthracene 200
d12-Chrysene 200
dj2-Benzo(b)fluoranthene 400
d12-Bcnzo(k)fluorantfacne 400
d 12-Bcnzo(a)pyrene _ 400
d12-Indeno(l,2,3,c-d)pyrene 400
d14-Dibcaz(a4i)aiithracenc 400
d12-Renzo(ghi)perylene 400
Alternate Standard
d10-Anthracene 200
Recovery Standards
d j 0-2-Metby lnaphth alene 200
d10-Pyrene 200
dJ2-Pcrylcnc 200
1 Assuming 100 percent recovery.
July 28,1997 M-429 Page 84
N-262
-------
TABLE 9
CONCENTRATIONS OF COMPOUNDS IN LABORATORY CONTROL SPIKE SAMPLE
ng/sairple
LRMS HRMS
Unlabelled Compounds
Naphthalene
2.0
1000
2-MethyInaphthaJene
2.0
200
Acenaphthylene
2.0
200
Acenaphthene
2.0
200
Fluorcne
2.0
200
Phenanthrene
2.0
500
Anthracene
2.0
200
Fluoranthene
2.0
200
Pyrene
2.0
200
Benzo(a)anthracene
2.0
200
Chrysene
2.0
200
BetL2o(b)fluorantfaenc
2.0
200
Benzo(k)iuoranthene
2.0
200
Benzo(e)pyrene
2.0
200
Benzo(a)pyrene
2.0
200
Perylene
2.0
200
Indeno( 1,2,3 ,c-d)pyrene
2.0
200
Dibenz(arh)anthracene
2.0
200
Benzo(ghi)pcrylene
2.0
200
Alternate Standard
d10-Anthracene
2.0
200
July 28, 1997
N-263
M-429 Page 85
-------
TABLE 10
RECOMMENDED GAS CHROMATOGRAPHIC OPERATING
CONDITIONS FOR PAH ANALYSIS
Column Type
Length (m)
ID (mm)
Film Thickness (pm)
Helium Linear Velocity (cm/sec)
Injection mode
Splitless Time (sec)
Initial Temperature (°C)
Initial Time (min)
Program Rate (°C/min)
Final Temperature (°C)
Final Hold Time
DB-5
30
0,25
0,32
30
Splitless
30
.45
4
8
300
until benzo(ghi)
peiylene has eluted
Injector Temperature (°C)
320
July 28,1997
N-264
M-429 Page 86
-------
TABLE 11
ASSIGNMENTS OF INTERNAL STANDARDS FOR CALCULATION CF RRFs
AND QUANTITATION OF TARGET PAHs AND SURROGATE STANDARDS
Analyte
Internal Standards
Unlabeled PAH
Naphthalene
2-Metfaylnapbtfaalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoraathene
Pyrene
Benzo(a)anthracene
Cbrysene
Benzo(b)fluoraatheoe
Benzo(k)fluoranthene
Benzo(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1,2,3-cd)pyrene
Dibenz(a4i)anthracene
Benzo(ghi)perylene
dg-Naphthalene
di0"2 -Methylnaphthalene
dg-Acenaphtfaylene
dg-Acenaphthylene
d10-Phenanthrene
d10-Phenanthrene
dj0-Phcaanthrene
d10-Fluoranthene
di0-Fluoranthcne
d12-Benzo(a)anthracene
d12-Chrysene
d j2-Benzo(b)fluoranthene
d s2-Benzo(k)fluoranthene
d12-Benzo(a)pyrene
d 12-Benzo(a)pyrene
d12«Perylene
-d12-Indeno(l,2,3,c-d)pyrene
d j 4-Dibcnz( aji) anthracene
d 12-Benzo(ghi)peryIene
Surrogate Standards
di0-Fluorene
dj4-Terpheuyl
d10-Phenanthrene
dI0-Fluoranthcne
July 28,1997
N-265
M-429 Page 87
-------
TABLE ilA
ASSIGNMENTS OF INTERNAL STANDARDS FOR CALCULATION OF RRFs
AND QUANTITATION OF TARGET PAHs AND SURROGATE STANDARDS
USING ALTERNATIVE KRMS SPIKING SCHEME
Analyte
Internal Standards
Unlabeled f AH
Naphthalene
2-Methvlnaphthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)fluoranthene
Benzo(k)fluoranthene
Ben2o(e)pyrene
Benzo(a)pyrene
Perylene
Indeno( 1,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(ghi)perylene
dg-Naphthaiene
d10-Acenaphthene
d8-Acenaphthylene
d10-Acenaphthene
d10-Fluorene
djQ-Phenanthrene
djQ-Phenanthrene
dj0-Fluoranthene
d10-Fluoranthene
d 12-Benzo(a)anthracene
d12-Chrysene
d I2-Benzo(b)fluoranthene
d12-Benzo(k)fluoranthene
d 12-Benzo(a)pyrene
d 12-Benzo(a)pyrene
d 12-Benzo(a)pyrene
d i2-Indeno( 1,2,3 ,c-d)py rene
d 14-Dibenz(aJi)anthracene
d12-Benzo(ghi)peiylene
Surrogate Standards
d14-Terphenyl
A. --w»»n2o(e)pyrene
d10-Fluoranthene
d12-Benzo(a)pyrene
July 28,1997 M-429Page88
N-266
-------
TABLE 12
ASSIGNMENTS OF RECOVERY STANDARDS FOR DETERMINATION
OF PERCENT RECOVERIES OF INTERNAL STANDARDS AND
THE ALTERNATE STANDARD
Analyte - Recoveiy Standard
Interna! Standards
dg-Naphthalcne
dl0-Acenaphthene
d10 -2-Methytoaphthalene
d10-Acenaphthene
dg-Acenaphthylene
d10-Acenaphthene
d10-Phenanthrene
di0-Pyrcne
d10-Fluoranthene
dj0-Pyreee
d12-Beii2o(a)anthraceiie
d10-PyitDc
d12-Chrysene
d10-Pyrene
d j2 -Benzo(b)fluoranthene
d12-Bcnzo(e)pyrene
di2-Bcnzo(k)fluoranthene
dj2-Benzo(e)p>Tene
d12-Benzo(a)pyrene
d12-Bcnzo(e)pyrene
d12-PervIene
dI2-Benzo(e)pyrene
d12-Indeno(l,2,3,c-d)pyrene
d12-Benzo(e)pyrcnc
d14-Dibenz(aJi)anthracene .
d12-Benzo(e)pyreae
d12-Benzo(ghi)perylene
d l2-Benzo(e)pyrcQc
Alternate Standard
d10-Anthracene d10-Pyrene
i
i
July 28, 1997 M-429 Page 89
N-267
-------
TABLE 12A
ASSIGNMENTS OF RECOVERY STANDARDS FOR DETERMINATION OF
PERCENT RECOVERIES OF INTERNAL STANDARDS AND THE ALTERNATE
STANDARD USING ALTERNATIVE HRMS SPIKING SCHEME
Analyte
Recovery Standard
Interna' Standards
dg-Naphthalene
d10 -2-Methylnaphthalene
dg-Acenaphtbylene
diQ-Phcnantfarcne
d10-Fluorantfaene
d 12-Benzo(a)anthracene
d12-Chiysene
d12-Benzo(b)fluorantliene
d 12-Ben2o(k)fluoranthene
d12-Benzo(a)pyrene
d12-Perylene
d12-Indeao( 12,3 ,c-d)pyrcne
d14-Dibenz(a,h)anthracenc
d12-Benzo(ghi)perylene
d j Q-2-Mctfay Inaphtfaalene
d10-2-Methylnaphthalene
d 10-2-Methylnaphtfaalene
d10-Pyrene
di0-Pyrenc
djQ-Pyrcne
d10-Pyrene
d12-Paylene
di2-P«yJene
d|2-Pexylcne
dj2-Peiylcne
dirPerylene
d12-Perylene
djj-Pcrylene
Ajtgrpa^ Standard
d10-Anthraccne
dl0-Pyrenc
July 28, 1997 M-429 Page 90
N-768
-------
TABLE 13
QUANTITATION AND CONFIRMATION IONS FOR SELECTED
ION MONITORING OF PAHs BY HRGC/LRMS
. • Quant. Confirm. %Relative
Analyte .. Ion Ion Abundance of
Confirm. Ion
Naphthalene
128
127
10
{^-Naphthalene
136
68
80
2-Methylnaphthalene
142
141
80
d10-2-Methylnaphthalene
152
Acenaphthylene
152
153
15
d8-Acenaphthylene
160
Acenaphthene
154
153
86
d10-Acenaphthene
164
Fluorene
166
165
80
d10-Fluorene
176
Phenanthrene
178
176
15
d10-Phenanthrene
188
94
Anthracene
178
176
15
d10-Anthracene
188
94
Fluoranthene
202
101
15
d10-Fluoranthene
212
106
Pyrene
202
101
15
d10-Pyrene
212
106
Benzo(a)anthracene
228
114
15
d 12-Benzo( a)anthraccne
240
120
Chiysene
228
114
15
dl2-Chrysene
240
120
d^-Tcrphenyl
244
122
15
July 28, 1997 M-429Page91
N-269
-------
TABLE 13 (CONT)
QUANTITATION AND CONFIRMATION IONS FOR SELECTED
ION MONITORING OF PAHs BY HRGC/LRMS
Quant
Confirm.
%Relative
Analytc
Ion
Ion
Abundance of
-
Confirm. Ion
Bcnzo(b)fluoranthene
252
126
25
d 12 -Beii2o(b)fluoraEthene
264
132
Bcnzo(k)fluoraiithene
252
126
25
d12-Beazo(k)fluoranthene
264
132
Benzo(e)pyrene
252
126
25
di2-Benzo(e)pyrene
264
132
Benzo(a)pyrene
252
126
25
d12-Bcnzo(a)pyrene
264
132
Pcrylenc
252
126
26
d12-Perylene
264
132
Indeno(l,2,3-cd)pyrene
276
138
28
di:-Indeco(lf2,3-cd)pyrenc
288
Dibenz(ah)anthraeene
278
139
24
d14-Diberi2(2h)anthraccne
292
Benzo(ghi)pcrylcne
276
138
37
d j2-Bcn2o(ghi)perylenc
288
July 28,1997
N-270
M-429 Page 92
-------
TABLE 14
MASS DESCRIPTORS USED FOR SELECTED ION MONITORING FOR HRGC/PRMS
Descriptor Analyte Ion
No, Type" m/z
Naphthalene
M
128.0626
PFK
LOCK
130.9920
dg-Naphthalene
IS
136.1128
2-Methylnaphthalene
M
142.0782
d10-2-Methylnaphthalene
IS
152.1410
Acenaphthylene
M
152.0626
dg-Acenaphthylene
IS
160.1128
Acenaphthene
M
154.07S2
d10-Acenaphthene
RS
164.1410
PFK
QC
169.9888
Fluorene
M
166.0782
d10-Fluorene
SS
176.1410
Phenanthrene
M
178.0782
d10-Phenanthrene
IS
188.1410
Anthracene
M
178.0782
d10-Anthracene
AS
188.1410
Fluoranthene
M
202.0782
d10-Fluoranthene
IS
212.1410
Pyrene
M
202.0782
PFK
QC
204.9888
d10-Pyrcne
RS
212.1410
Ben2o(a)anthracene
M
228.0939
d12-Bcnzo-a-Anthracene
is
240.1692
Chrysene
M
228.0939
d12-Chxysene
IS
240.1692
PFK
LOCK
230.9856
d14-Terphenyl
SS
244.1974
IS - Internal Standard
SS » Surrogate Standard
AS = Alternate Standard
RS = Recovery Standard
LOCK = Lock-Mass Ion
QC = Quality Control Check Ion
July 28, 1997
N-271
M-429 Page 93
-------
TABLE 14 (CONT)
MASS DESCRIPTORS USED FOR SELECTED ION MONITORING FOR HRGC/HRMS
Descriptor Analyte Ion Accurate
No. Type _• mJz
Peiylene
M
252.0939
d12-Perylene
IS
264.1692
PFK
QC
268.9824
Benzo(b)fluoranthene
M
252.0939
d12-Benzo(b)fluoranth«ie
IS
264.1692
Benzo(k)fluoranthene
M
252.0939
d12-Benzo-k-£luoranthene
IS
264.1692
Benzo(e)pyrene
M
252.0939
dI2-Benzo(e)pyrene
RS
264.1692
Benzo(a)pyrene
M
252.0939
d12-Benzo(a)pyrene
IS
264.1692
Benzo(ghi)perylene
M
- 276.0939
d 12-8enzo(ghi)peryIene
IS
288.1692
Indeno( 1,2,3-cd)pyrene
M
276.0939
d12-Indeno(l,2,3-cd)pyrene
IS
288.1692
Dibenzo(ah)anthracene
M
278.1096
PFK
LOCK
280.9824
d 14-Dibenzo(ah)anthracene
IS
292.1974
The following nuciidic masses were used:
H = 1.007825 2H - 2.014102 C - 12,000000
IS = Internal Standard
SS , « Surrogate Standard
AS = Alternate Standard
RS = Recovery Standard
LOCK «* Lock-Mass Ion
QC » Quality Control Check Ion
July 28,1997
N-272
M-429 Page 94
-------
FIGURE 1
34
METHOD 42° FLOWCHART
'40
§1.3.9
§1.3.10
The end user Is identified
The tester Is designated
35
§2.1.1
The end user chooses:
1 source target concentration
36
§2.1.2
§8.4
§8.4.1
The tester selects analyst with documented
experience in satisfactory performance of analytical
procedures
37
§4.3.2
§4.2
§4.3.3
§4.3.4
Tester and laboratory coordinate:
1 pre-test cleaning of glassware
1 pre-test cleaning, contamination checks, and
storage of sampling materials and reagents
1 preparation of filter, sorbent cartridges, method blanks, and
LCS
38
§10.1.1
§10.1.2
§10.1.3
Tester requests pre-test analytical results from laboratory:
1 contamination check of filters
1 contamination check of XAD-2 resin
1 Method detection limits (MDLs) and
Practical quantitation limits (PQLs)
39
§25
Tester calculates and plans:
1 23 sampling runs and 21 blank sampling train
1 sample volume
1 sampling time
1 source reporting limit
1 chain of custody
Tester performs:
§4.3.1 I calibration of equipment
41
Tester writes:
§2.2 ! pre-test protocol
42
Tester performs:
§4.4.1 I preliminary field sampling determinations'
§4.4.2 ! sampling train preparation
§4.4.3 ! leak-checks
§4.4.4 I sampling procedure
! 2 3 sampling runs
1 21 blank sampling train
§S I recovery of all runs and blank sampling train
43
§53
§5.4
44
45
Tester delivers:
I recovered sampling runs and blank train(s)
I chain of custody record
Laboratory performs:
§6 I extraction of Held samples
§7 1 analyses
§8 I QA/QC procedures
§9 I chain of custody
§ 10.2 ! reporting requirements
Tester performs:
§4.3.1 I post-test calibrations
§9.2 I calculations
§10.3 I data recording and chain of custody
I reporting requirements
July 28, 1997
f 1-429 Page 95
-------
Heated Probe,
S-type Pitot
&Temp. Sensor
ns
Stack
Wal
Temp.
Readout
ce Water
Pitot
Manometer
Oven
Cyclone (Optional)
Filter Assembly
- Transfer Line
Condenser
(water cooled)
-Thermocouple
Sorbent Module
(water cooled)
Impingers in Ice Bath:
Buffer Solution in #1
#3 Empty
Silica Gel in #4
Check
j Valve
Orifice
Orifice
Manometer
Thermocouple
5—L
Dry Gas
Meter
Bypass
Valve
Pump
Main
Valve
¦e
Figure 2
PAH Sampling Train
July 28,1997
W.97A
M-429 Page 96
-------
e.
K»
oo
v£>
VO
-J
H37 cmf-
-I To Suit I-
M
01
8 mm Glass
Cooling. Coil
Glass Wool
k Plug
iii
mam
Water Jacket-
XAD-2
Glass Sintered
Disk
Condenser
Sorbent Trap
Figure 3
s Condenser and Sorbent Trap for Collection
s of Gaseous PAHs
T)
-------
Loose Weave Nylon
Fabric Cover
10.2 cm (4")
Pyrex Pipe
Liquid Take Off
0.95 cm (3/8')
/ Tubing
Liquid Nitrogen
Heat Source
«>
<*-w.
*****>«<•«» «6
***•«< **
*»««<*&£• •«-<* •*
$*<*$>«!*~:¦. :# «*«?~ «?* ^ >*¦ <* <* t* 5:J?
fcCMtttoOtx*- x» «* <~<* «*
fc^ar «*vy&
»»#"»**< #<•
***«>¦**¦«» V «c *»^ *<**»,
IMSMM****'*'«~*****"*''**>
nfctftttt** >*
*i q> 5£ *>
<*-<*>#" *>«v
4?
4s a» *¦ * ¦&. «* v «, «> .*•
&&<$<<::*: <» $x ^^v.-: »:
**' *<*%<£#
tf**•*:«.•«%-«»«. >T- «&*>**«*<*
..*% <•
#'*~»>*¦*'«'•***?*>'*>«•«' v? **'
^«jt^j»vc£.*> ^ ,«¦<*»> x>
3q ft
Fine Screen
Figure 4
XAD-2 Fluidized Bed Drying Apparatus
July 28,1997
N-276
M-429 Page 9S
-------
FIGURE 5
Run No. _
Location
Date
Operator.
METHOD 429 FIELD DATA RECORD
Meter Box No.
Local Time
Start/Stop
AH@
Stack Diameter
Meter Box Calibration
Factor (Y)
Pitot Tube Factor
Probe Tip Diri> in.
Probe Length
Sampling Train Leak Test
Before in. Hg
After in. Hg _
Leak-Check Volume
Pitot Tube Leak-Check
Before After
Leak Rate
cu.ft/min
cu.ft/min
cu. ft.
Project No.
Plant Name
Ambient Temp °F
Meter Temp °F
Bar. Press, "Hg
Stack Press, "H20
Assumed Moisture, % _
Heater Box Setting, °F _
Probe Heater Setting, °F.
Assumed M.W. (wet%)
Assumed M.W. (dry%)
M
•vl
-~4
Sampling
Point
Clock
Time
Dry Gas Meter,
cu, ft.
Pitot AP
in. HjO
Orifice AH
"H20
Temperature (°F)
Pump
Vacuum
in. Hg
Desired
Actual
Impinger
Filter box
Stack
Start
t
'
July 28, 1997
M-429 Page 99
-------
Figure 6
Recovery of PAH Sampling Train
Rfeise wttt known volume:
1.acatom
2. methylene chloride
3. hexane
jL
Nozzle and
Proba Lkwr
JL
Front half
fler holder
Container
No.1
Mailt BaukJ level
Stora at 4*C or lower
away from Ight
Ihmsfar
Fler
Contabwr
No. 2
Store it 4*0
or lower away
from IgM
Rinse will known volume:
1. acetone
2. mathyfcna chloride
/ 3. hexane
Flter support,
Back half
filer holder
I
JJe
\
jCondenser 1
Transfer
kia
Container
No. 3
Marie Iquid tovsl.
Store at 4\J or lower
away from light
Cap
Resin
cartridge
Resin
cartridge
Store it 4C or lower
away from Ight
A. Tare weigh Contatier 14
B. Decant contents of
ImplwarB Into tared
Contarar #4
Implnger knplwer Implfwer
No.l No. 2 No.3
c
Container
No. 4
T
C. Wetah Contalw #4
D.MarxIquUlnnl
Store at 4*C or tower
away from light
Rinse wth known volume:
1.anfone
2. methylene chloride
3.hexane
Implnger Implwar Imphger
No.l No. 2 No. a
^ 1 ^
Contaltar
No. 5
Maifclquld level
Stora at 4*C or lower
away (rom Ight ,
A. Tare weigh
cartrtrtdoe wth
sHfcagai
B, Weigh after
sampltig
I
Slfcapel
cartridge
Recycle
July 28, 1997
M-429 Page 100
-------
Figure 7
Flow Chart for Sampling, Extraction and Cleanup for
Determination of PAH in a Split Sample
1 Containers No. 1 and No. 3
Archive
Archive
XAD-2
Resin
Fitter
Solvent1
Rinses
Concentrate
Concentrate
G.C J Mass Spec.
G.C./ Mass Spec.
Impinger
Solution
Sampling
Internal
Standards
Concentrate
MeCI, Extraction
Alternate Standard
Alternate Standard
Internal
Standards
Column Cleanup
Solvent Exchange
Column Cleanup
Recovery Standards
Recovery Standards
Solvent Exchange
MeCI2
Soxhlet Extraction
Surrogate Standards
Added to XAD-2 Resin
July 28, 1997
N-279
M-429 Page 101
-------
Figure 8
Flow Chart for Sampling, Extraction and Cleanup for
Determination of PAH in a Composite Sample
Alternate'
Standard!
Combine
Extracts
J MeCI2 ,
i Extraction
Containers No. land No. 3
Archive
Teflon
Filter
XAD-2
Resin
Concentrate
Impinger
Rinses
Impinger
Solution
Sampling
Solvent
Rinses
Solvent Exchange
Column Cleanup
Internal
Standards
Concentrate
Recovery Standards
MeCI2
Soxhlet Extraction
Surrogate Standards
Added to XAD-2 Resin
July 28,1997
fci no a
M-429 Page 102
-------
FIGURE 9
EXAMPLE OF PRE-TEST CALCULATIONS FOR PAH EMISSIONS TEST
PST =
PSV
6 hours
ISO dscf
PQL
(ng/sample)
STC
(ng/dscm)
MSV
(dscf)
MST
(hours)
F
SRL
(ng/dscm)
Naphthalene
' 2400
<1500
>56.5
>1.89
NA
471
2-Msthylnaphthalene
*330
NA
NA
NA
NA
64.7
Acenaphthylese
5.0
180
0.98
0.03
183
0.98
Acenaphthene
5.0
6
29.4
0.98
6
0.98
Fluorene1
83
<6
>489
>16.3
NA
16.3
Phenanthrene
110
120
32.4
1.08
6
21.6
Anthracene
5.0 j
<6
>29.4
>0.98
NA
0.98
Fluoranthene
5.0
46
3.8
0.13
47
0.98
Pyrene
5.0
46
°q
***
i
1
l
0.13
47
0.98
Benzo(a)anthracene
5.0 I
<6
>29.4
>0.98
NA
0.98
Chrysene
5.0 |
42 |
4.2 !
0.14
43
0.98
Benzo(b)fluorantbene
5.0 !
50 |
3.5 j
0.12 i
51
0.98
Benzo(k)fluoranthene
5.0 j
50 i
3.5 [
0.12
51
0.98
Benzo(e)pyrene i
5.0 !
NA j
NA
NA I
NA
0.98
Benzo(a)pyrene 1
5.0 |
<6 i
>29.4 :
>0.98 |
NA
0.98
Perylene
5.0 1
NA
NA |
NA
NA
0.98
Indeno(l ,2,3-c,d)pyrene I
5.0 i
<6 1
>29.4 1
>0.98 j
NA
0.98
Dibenzo(aji)anthracene I
5.0 |
<6 ;
>29.4 i
>0.98
NA
0.98
Benzo(gii)perv'lene i
5.0 1
<6 i
>29.4 1
>0.98 |
NA
0.98
Average Volumetric Sampling Rate (VSR) = 0.5 dscfm = 30 dscf/br
PQL = Practical quantitation limit for analyte (based on pre-test analysis of XAD-2 resin)
STC = Source target concentration for analyte. (From previous emissions test Samples were analyzed by
HRGC/LRMS).
MSV = Minimum sample volume required to collect detectable levels of target analyte.
(MSV - PQL + STC) Equation 429-1
MST = Minimum sample time required to collect detectable levels of target analyte at VSR,
(MST = MSV + VSR) Equation 429-2
PST ~ Planned sampling time (6 hours chosen as the longest practical sampling time for die planned emissions
test)
PSV = Planned sample volume (PSV = PST * VSR) Equation 429-4
F = Safety factor (>1) that allows for deviation from ideal sampling and analytical conditions. (F = PSV + MSV)
Equation 429-5
SRL « Source reporting limit if the target analyte cannot be detected with the planned test parameters. (SRL = PQL
-i- PSV) Equation 429-7
NA This calculation is not applicable either because there is no STC value available or the STC is a detection
limit
1 PSV is lower than the MSV. Therefore, die analyte is not expected to be detected if it is present at the target
concentrations. It will only be detected if the actual concentration is higher than the indicated SRL.
July 28, 1997 M^29 Page 103
N-281
-------
FIGURE 10
CARB METHOD 429 (PAHs) SAMPLING TRAIN SET-UP RECORD
RUN NO.
PLANT NAME
SET-UP DATE
RECEIVED BY
COMPONENTS COMPONENT ID
1. NOZZLE -
2.
PROBE
3. FILTER HOLDER
TRANSFER LINE
AND CONDENSER
Fittings
XAD-2 RESIN
CARTRIDGE
IMPINGERS: No 1
U-Connectcr
No. 2
U-Conuector
No. 3
U-Connector
FILTER Lot#
PROJECT NO.
PLANT LOCATION
SET-UP BY
DATE/TIME
OTHER INFORMATION
Material
Diameter
Liner material
Length
Before set-up, all
.openings sealed with
Filter support type
Filter Type
Size
Contamination check?
Transfer line material
Both ends sealed in
lab prior to set-up
Fittings
Contamination check?
Spiked?
Charge with 100 ml.
impinger solution and weigh
Charge with 100 mL
impinger solution and weigh
Weigh empty
SILCA GEL
CARTRIDGE
Tare weight
Appearance
July 28,1997
N-282
M-429 Page 104
-------
FIGURE 11
CARB METHOD 429 (PAHs) SAMPLING TRAIN RECOVERY RECORD
RUN NO. ' PROJECT NO.
PLANT NAME PLANT LOCATION
RECOVERY DATE RECOVERED BY
1. CHECK whether openings were covered. RINSE 3x each with Acetone, MeClj,
MARK liquid level and STORE containers at temp. <4°C away from light
Openings Rinse volume fmT.1 Storage
Component covered? Acetone MsQia— Hexane CoafrSierf?) IPs
Nozzle
Probe liner .
Filter holder front ______ ______
2. STORE filter(s) at temp. <4*C away from light RECORD ALL sample storage information.
Storage Storage
Component Appearance after sampling ' fTemperature & lighfi Containers) ID
Filter
Filter
Filter
3. CHECK whether openings were covered. RINSE 3x each with Acetone, MeClj, Hexane.
MARK liquid level and STORE containers at temp. <4°C away from light
Openings Rinse volume (nUL) Storage Storage
covered1? Acetone MeCl, Hexane Temp. & light Container ID
Filter support and
filter holder back
Transfer line
Condenser _
4. STORE Resin cartridges at temp. <4°C away from light RECORD ALL storage information.
ID Apt*?armce after sampling Storage temperature & light conditions
5. WEIGH impinger contents and silica gel cartridge.
MARK liquid level and STORE impinger contents at temp. <4°C away from light
Additional impingers
Weight No. 1 No. 2 No. 3 No. 4 No. 5
Final (g) ' ~
Before sampling (g)
Gain (g) (A) (B) (C) (D) (E) (F).
. Total condensate (A) + (B) + (C) + (D) + (E) + (F) (a)
STORAGE CONTAINER ID(j) __
6. RINSE impingers 3i each with Acetone, MeClj, Hexane.
MARK liquid level and STORE impinger rinses at temp. <4*C away from light
Rinse volumes (mL) Acetone
MeCl2
Hexane ____ ______ __
STORAGE CONTAINER ID(s)
Silica gel
cartridge
July 28,1997
N-283
M-429Page 105
-------
FIGURE 12
CHAIN OF CUSTODY SAMPLE RECORD
Project # Date: Start:
Stop:
Source name: _• Sample/Run #:
Sampling location: . Sample type: _
Chain of Custody Log Record # (s) Operator:
SAMPLE STORAGE INFORMATION
SAMPLE PRESERVATION
Comments
Ice/Dry ice?
CHAIN OF CUSTODY
ACTION
DATE
TIME
GIVEN BY
TAKEN BY
RELATED
IDs
DESCRIPTION/COMMENTS
Log #s
FR
Front rinse (nozzle, probe,51ter holder front)
F
Filter in sealed storage container
CD
Back rinse (filter support, filter holder, samnle line & condenser
• - ------
C
Resin cartridge
I
Impinger contents
r nf"
Impinger rinses
July 28,1997
N-284
M-429 Page 106
-------
FIGURE 13
CHAIN OF CUSTODY LOG RECORD
PROJECT NO. Page of
Log #
Sample
ID
Date
Time
Comments
Given by
Taken by
V
Sample Identifier Sample Description
FR Rinses of probe and front half of filter holder
F Filter in sealed storage container
BR Rinses of filter support, back half of filter holder, sample transfer line and condenser
C Aluminum foil wrapped, capped resin cartridge
I Impinger contents
IR Impinger rinses
July 28, 1997
N-285
M429 Page 107
f
-------
FIGURE 14A
EXAMPLE GC/MS SUMMARY REPORT (HRMS) FOR INITIAL CALIBRATION SOLUTION #1
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POL YCYCLIC AROMATIC HYDROCARBONS
ICALID: ST1120A1 ACQUIRED: 12/3/94 16:23:24 INSTRUMENT: W
RUN#: PAHCS1 PROCESSED: 12/3/94 OPERATOR: MPA
RT,
RRT
Area
RRF
Naphthalene
8:20
1,006
6.66 E+07
0.75
2-Methylnaphthalene
9:42
1.007
1.44 E+07
1.30
Acenaphthylene
11:04
1.003
1.57 E+07
1.44
Acenaphthene
11:20
1.004
1.05 E+07
0.94
Fluorene
12:06
1.003
8.15 E+06
1.05
Phenanthrene
13:20
1.003
1.99 E+07
1.15
Anthracene
13:23
1.001
7.07 E+06
1.02
Fluoranthene
14:38
1.001
3.18 E+07
1.26
Pyrene
14:55
1.001
3.31 E+07
1.31
Benzo(a)anthracene
16:34
1.002
2.08 E+07
1.13
Cbrysene
16:39
1.003
2.26 E+07
1.13
Benzo(b)fluorantheDe
18:54
1.004
2.35 E+07
1.69
Benzo(k)fluoranthene
18:58
1.004
2.50 E+07
1.24
Benzo(e)pyTTOe
19:42
1.004
2.41 E+07
1.20
Benzo(a)pyrene
19:51
1.003
2.11 E+07
1.07
Poylene
20:06
1.004
1.38 E+07
0.70
Indeno( 1 ,2,3-c,d)pyrene
23:60
1.006
2.07 E+07
2.19
Dibenzo(aJi)anthracene
24:01
1.006
1.49 E+07
1.66
3enzo(g4i,i)peiylene
25:15
1.005
1.84 E+07
2.23
dg-NaphthaJene
8:17
1.000
3.54 E+08
4.22
dg-Acenaphthylene
11:02
1.000
1.09 E+08
1.29
d10-Acenaphthene
11:17
1.000
1.11 E+08
1.32
d10-Fluorene
12:04
1.000
7.78 E+07
0.93
dl0-Phenanthrene
13:18
1.000
6.92 E+07
0.82
dj0-Fluoranthene
14:37
1.000
2.53 E+08
1.03
d12-Benzo(a)anthr£cene
16:32
1.000
1.83 E+08
0.75
d12-Chrysene
16:36
1.000
2.00 E+08
0.82
dj2-Ben2o(b)fluoraathene
18:50
1.000
2.77 E+08
1.35
d j 2-Bei2C
-------
FIGURE 14B
EXAMPLE OF INITIAL CALIBRATION (ICAL) RRF SUMMARY
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POL YC YCLIC AROMATIC HYDROCARBONS
ICAL ID: ST 1120
RUN #: NA
ACQUIRED: 3-DEC-94 INSTRUMENT. V
PROCESSED: 3-DEC-94 OPERATOR: MPA
RR? frl
Rill" it 2
RRF #4
RRF #5
Mean
RRF
Naphthalene
0.75 ..
0.66
0.61
0.64
0.71
0.67
0.056
8.29%
2-Methylnaphthalene
1.30
1.15
1.10
1.12
1-26 _
1.19
0.089
TATA
Acenaphthylene
1.44
1.27
1.24
1.28
1.43
1.33
0.096
7.19%
Acenaphthene
0.94
0.84
0.80
0.83
0,94
0.87
0.067
7.72%
Fluorene
1.05
0.94
0.88
0.92
1.07
0.97
0.082
8.43%
Phenanthrene
1.15
1.06
1.01
1.05
1.23
1.10
0.088
8.00%
Anthracene
1 02
1.00
0.98
0.95
1.14
1.02
0.074
7.25%
Fluoranthene
1.2o
1.15
1.08
1.13
1.28
1.18
0,085
7.21%
Pyiene
1.31
1.27
1.13
1.15
1.41
1.25
0.115
9.22%
Beczo(a)anthracene
1.13
1.05
1.05
1.04
1.23
1.10
0.082
7.43%
Chiysene
1.13
1.02
0,97
C.98
1.11
J.04
0,073
7.00%
Benzo(b)fluoranthene
1.69
1.45
1.46
1.42
1.86
1.58
0.194
,12.33%
Benzo(k)£luoranth«ie
1.24
1.25
1.14
1.18
1.26
1.21
0.052
4.32%
Benzo(e)pyrene
1.20
1.12
1,06
1.06
1.19
1.12
0.066
5.89%
Benzo(a)pyrene
1.07
0.99
0.96
0.96
1.14
1.02
0.080
7.81%
Perylene
0.70
0.63
0.58
0.60
0.70
0.64
0.059
9.12%
Indeno( 1 ,2,3-c,d)pyrene
2.19
2.01
1.92
1.99
2.26
2.07
0.143
6.90%
Dibenzo(a>h)anthracene
1.66
1.60
1.56
1.61
1.87
1.66
0.122
7.35%
Benzo(gJtM)peryleiie
2.23
2.05
1.96
2.00
2.32
2.11
0.154
7.28%
dg-Naphtha]ene
4.22
4.15
4.16
4.18
4.10
4.16
0.044
1.05%
dg-Acenaphthylene
1.29
1.29
1.28
1.27
1:30
1.29
0.012
0,91%
d 10-Acenaphthene
1.32
1.34
1.32 .
1.30
1.32
1.32
0.013
1.00%
d10-Fluoteoe
0.93
0.95
0.94
0.95
0,95
0.94
0.011
1.21%
d I0-Phenanthrene
0.82
0,82
0.82
0.86
0.88
0.81
0.026
3.09%
djQ-Fluorarithene
1.03
1.00
1.07
1.07
0.99
1.03
0,038
3.71%
d l2-Benzo(a)anthracene
0.75
0.70
0.70
0.72
0.70
0.71
0.022'
3.09%
dl2-Chrysene
0.82
0.79
0.81
0.83
0.84
0.82
0.021
2,56%
dj2-Benzo(h)fluorainthene
1.35
1.39
1.46
1.27
1.32
1.36
0.072
5.32%
d 12-Benzo(k)fluoranthene
1.95
1.95
2.14
1.84
2.11
2.00
0.124
6.23%
d 12-Bei22o(a)pyrene
1.91-
1.96
2.11
1.82
1.99
1.96
0.107
5.46%
d l2-Indeno( 1 ,2,3-c,d)pyrene
0.92
0.88
0.98
• 0.85
0.98
0.92
0,059
6.40%
d 14-Dibenzo(aJi)anthracene
0.87
0.84
0.91
0.78
0.89
0.86
0.049
5,71%
dI2-Benzo(giy)perylene
0.80
0.76
0,83
0.73
0.80
0.78
0.042
5.36%
d14-Terphenyl
0.52
0.52
0,49
0.48
0.51
0.51
0.018
3.59%
dI2-Benzo(e)pyrei»
0.37
0.37
0.37
0.36
0.36
0.36
0.005
1.50%
d10-Aflthracene
0.69
0.73
0.74
0.80
0.90
0.77
0.080
10.40%
d 10-2-Methy inaphthalene
—
—
—
—
_
_
—
—
dj0-Pyrene
—
—
_
_
—
—
_
djj-Poyletse
_
—
—
—
—
—
_
—
July 28,1997
N-287
M-429 Page 109
-------
FIGURE 14C
EXAMPLE OF CONTINUING CALIBRATION (CONCAL) SUMMARY
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCUC AROMATIC HYDROCARBONS
CONCAL ID: CC1202
ICALID:
ST1120
CONCAL DATE; 12/3/94
ICALDATE:
3-DEC-94
• .RRF
ICALRRF
ARRF
RPD
Naphthalene
0.68
0.67
0.01
76
1.5
2-Methylnaphthalene
1.42
1.19
0.23
17.6
Acenaphthylene
1.42
1.33
0.09
6.6
Acenapbthene
0.91
0.87
0.04
4.5
Fluorcne
0.98
0.97
0.01
1.0
Phenanthrene
1.10
1.10
0.00
0.0
Anthracene
0,98
1.02
•0.04
4.0
Fluoranthene
1.12
1.18
-0.06
5.2
Pyrene
1.18
1.25
"-0.07
5.8
Benzo(a)anthxacene
1.08
1.10
-0.02
1.8
Chrysene
1.04
1.04
0.00
0.0
Benzo(b)nuoTimtfaene
1.46
1.58
-0.12
7.9
Benzo(k)fluoranthene
1.12
1.21
-0.09
7.7
Beazo(e)pyrene
1.04
1.12
-0.08
7.4
Benzo(a)pyreiie
0.95
1.02
-0.07
7.1
Peiylene
0.62
0.64
-0.02
3.2
Iadeno{ 1 ,2,3-c,d)p)Teiie
2.04
2.07
-0.03
1.5
Dibenzo(aJi)aD thracene
1.61
1.66
-0.05
3.1
Benzo(gJa,i)perylene
2.11
2.11
0.00
0.0
dg-Naphthaleoe
4.78
1.16
0.68
.15.3
d8-Acenaphthylene
1.20
1.29
-0.09
7.2
dI0-Acenaphth«oe
1.25
1.32
-0.07
5.5
d10-Fluorene
0.85
0.94
-0.09
10.1
d10-Phenanthrene
0.79
0.81
-0.02
2.5
d10-Fluoranthene
1.05
1.03
0.02
1.9
d12-Benzo(a)anthracene
0.69
0.71
-0.02
2.9
djj-Chrysene
0.82
0.82
0.00
0.0
d 12-Benzo(b)fluoraiithene
1.24
1.36
-0.12
9.2
dl2-Benzo(k)f]uoraiithene
1.91
2.00
-0.09
4.6
dj2-Bexjzo(a)pyrene
1.87
1.96
. -0.09
4.7
d j2-lndeno( 1 ,2,3-c,d)pyrene
0.84
0.92
-0.08
9.1
d l4-Dibenzo(aJb)anthiacene
0.80
0.86
-0.06
7.2
d12-BenzG(g,hi)peiylene
0.76
0.78
-0.02
2.6
d|4-Terphenyl
0.50
0.51
-0.01
2.0
d12-Benzo(e)pyrene
0.37
0.36
0.01
2.7
d20-Anthracene
0.71
0.77
-0.06
8.1
d10-2-MethylnaphthaJene
—
_
1.000
d12-Perylene
_
1.000
INSTRUMENT: W
OPERATOR: MPA
July 28,1997
N-288
M-429Page 110
-------
FIGURE ISA,
EXAMPLE OF SUMMARY REPORT OF LCS RESULTS
CALIFORNIA.AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
Client ID CARB
Lab ID: 1412 9/LCS1/LCS2
Instrument: W
MPA
Reviewer JCM
Sample Matrix: XAD-2
Date Received: NA
Date Extracted: 11/30/94
Dtte Analyzed: 12V3/94
Sample amount Sample
ICALID: ST1120
ICALDATE: 12/3/94
CONCAL ED: NA
Resin Lot #: LCJiOM
LCS IDs: NA
LCS DATE: NA
CONCAL DATE: NA
Units: NA
COMPOUND:
LCS1
%R
LCS2
%R
RPD
%
Naphthalene
100
103
3.0
2-Methytaflphthalene
96
95
1.0
Acenaphthylene
95
97
2.1
Acenapbthene
92
94
2.2
Fluorene
94
. 96
2.1
Phenanthrene
93
94
1.1
Anthracene
91
89
2.2
Fluoranthene
90
92
2.2
Pyrrae
87
89
2.3
Beozo(a)aathiaceoe
87
86
1.2
Chrysene
83
89
7.0
Benzo(b)fluoranthene
92
93
• 1.1
Benzo{k)fluoranthene
92
95
3.2
Benzo(e)pyrene
97
99
2.0
Benzo(a)pyrcne
89
92
3.3
Peryleoe
89
89
0.0
Indeno( 1 ,2,3-c,d)pyrene
87
90
3.4
Dibenzo(aJi)anthracene
88
90
2.2
Benzo(gii)perylene
89
91
1.2
Internal Standards (%R)
d8-Naphtfaalene
67
64
dj-Acenaphthylece
73
70
d l0-Acenaphthene
76
75
dj0-Fhiorene
79
81
djo-Phenanthrene
88
93
d10-Fluoranthcne
84
80
d 12-Benzo(a)anthraccr.e
96
98
d12-Chrysene
96
91
d12-Benzo(b)fluoranthene
88
85
d12-Benzo(k)fluoianthene
85
84
d12-Benzo(a)pyrene
92
90
d 12-Iadeno( 1 ,2,3-c,d)pyrene
104
105
d l4-Dibenzo(aJi)anthracene
96
96
dJ2-Benzo(gJu)pcry2ene
102
103
Alternate Standard (%R)
d10-Anthracene
83
85
July 28,1997 M429PagellJ
N-289
-------
FIGURE 15B
ICS RECOVERIES FOR BENZO(a)PYRENE
150
140
130
120
a) 110
9 100
90
80
70
60
50
8/18/92 - 5/21/93
July 28, 1997
M-429 Page 112
-------
FIGURE 16A
EXAMPLE GC/MS SUMMARY REPORT (HRMS) FOR SAMPLE RUN #32
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POLYCYCLIC AROMATIC HYDROCARBONS
Lab ID: 14129-02
ICALID:
12/3/94 16:23:40
Instiume v.:
w
Acquired: 12/3/94 16:23:40
ICALDATE: 12/3/94
Operator:
MFA
Client ID: M429-32
Reviewer.
JCM
.. _RT
RRT
Area
RRF
Amt (ng)
%REC
Naphthalene
8:21
1.053 E+10
0.67
10,478.37
2-Methytaaphthalene
9:41
1.790 E+08
1.19
140.98
Acenaphthylene
11:03
9.371 E+08
1.33
712.59
Acenaphthene
11:19
7.649 E+06
0.87
8.21
Fluorene
12:05
2.417 E-H37
0.97
30.02
Pbenantoene
13:1?
8.402 E+08
1.10
925.53
Anthracene
13:21
2.905 E+07
1.02
34.54
Fluoranthene
14:36
5.932 E+08
1.18
254.36
Pyrene
14:52
7.611 E+08
1.25
307.62
Benzo(a)anthracenc
16:32
3.120 E+06
1.10
1.9
-
Chrysene
16:32
9.620 E+06
1.04
6.2
Benzo(b)fluoraatheoe
18:49
1.030 E+06
1.58
7.6
Benzo(k)fhioranthene
Not found
0.0
1.21
Benzo{e)pyrene
19:36
1,646 E+07
1.12
13.61
Beczo(a)pyrene
19:46
4.936 E+06
1.02
3.95
Perylene
20:01
1.823 E+06
0.64
2.32
Indeno(l,2,3-c,d)pyrene
23:54
5.728 E+06
2.07
4.37
Dibpnzo(aJi)anthracene
23:56
5.875 E+Q5
1.66
0.59
Benzo(gJi,i)perylene
25:09
1.584 E+07
2,11
14.95
dg-Naphthalene
8:18
1.000
4.794 E+08
1.16
124.92
62.5
dg-Aceaaphthy lene
11:01
1.000
1.972 E+08
1.29
166.07
83.0
d10-Aeenaphtfaene
11:16
1.000
2.142 E+08
1.32
176.19
88.1
dj0-Fluorene
12:02
1.000
1.658 E+08
0.94
190.71
95.4
dl0-Phenanthrene
13:16
1.000
1.652 E+07
0.81
213.39
106.7
d10-Fluoranthene
14:34
1.000
3.955 E+08
1.03
116.22
58.1
d12-Benzo(a)anthracene
16:28
1.000
2.835 E+08
0.71
121.18
60.6
d12-Chiysene
16:31
1.000
2.987 E+08
0.82
111.08
55.5
d12-Benzo(b)fluoranthene
18:45
1.000
3.439 E+08
1.36
165.79
41.4
d j 2-Benzo(k)fluorantliene
18:50
1.000
4.304 E+08
2.00
141.02
35.3
d12-Benzo(a)pyrene
19:41
1.000
4.895 E+08
1.96
163.67
40.9
d 12-Indeno( 1 »2,3-c,d)pyrene
23:46
1.000
2.529 E+08
0.92
179.71
44,9
d 14-Dibenzo(aJs)aothmc«ie
23:45
1.000
2.400 E+08
0.86
182.65
45.7
d l2-Benzo(gJM)pery lene
24:60
1.000
2.006 E+08
0.78
167.24
41.8
d14-Terphenyl
14:55
7.988 E+08
0.51
523
105
d ]2-Benzo(e)p>Teiie
19:32
1.000
3.011 E+08
0.36
676.33
135.3
d j 0-Anthracene
13:20
1.000
6.795 E+07
0.77
95.29
47.6
d10-2-Methylnaphthalene
9:38
1.000
1.844 E+07
—
100
dI0-Pyreae
14:51
1.000
6.576 E+08
—
100
d12-Perylene
19:56
1.000
3.057 E+08
100
July 28,1997
N-291
M-429 Page 113
-------
FIGURE 16B
EXAMPLE LABORATORY REPORT OF PAH RESULTS FOR SAMPLE RUN #32
CALIFORNIA AIR RESOURCES BOARD METHOD 429 POL YCYCLIC AROMATIC HYDROCARBONS
Client ID M429-32
lab ID: \4\im
_2L
Instrument,
Operator.,
Reviewer,, J£M
MPA
COMPOUND:
Sample Matrix: M429
Date Received: 11/18/94
Date Extracted: 11/30/94
Date Analyzed: \W
-------
FIGURE !7A
EXAMPLE OF TESTER'S SUMMARY OF LABORATORY REPORTS
Rim#:
I 31
32
33
Field
Blank
Method
Blank
LCS #1
lcs n
I:..-. ' -
percent rerovery
Naphthalene
4300
10000
460000*
<1600
<1700
100
10 3
2-Methylnaphthalene
<94
140
6400 *
! <94
<78
96
95
Acenaphthylene
140
710
85000*
9.1
<50
95
97
Acenaphthene
Fluorene
1 ¦" -9.2
| 27
8.2
30 ~]
500
180
<5.0
<27
<5.0
<27
92
94
94
96
Phenanthrene
310
930
43000*
<80
<74
93
94
Anthracene
26
35
2400
5.3
<5.0
9i
89
Fluo ran then e
83
250
16000*
16
<5.0
90
92
Pyrene
110
310
20000*
19
<5.0
87
89
Benzo(a)anthracene
<5.0
< 5.0
170
<5.0
<5.0
87
86
Chrysene
<5.0
62
300
<5.0
<5.0
83
89
Benzo(b)£luoranthene
<5.0
7.6
340
<5.0
<5.0
92
93
Benzo(k)fluoranthene
<5.0
<5.0
89
<5.0
<5.0
92
95
Benzo(e)pvTene
35
<35
530
6.9
<5.0
97
99
Benzo(a)pyrene
<5.0
<5.0
240
<5.0
<5.0
89
92
Peryieae
<5.0
<5.0
110 i <5.0
<5.0
89
89
Indeno( 1 J,3-c,d)pyrene
<5.0
<5.0 j
100
<5.0
<5.0
87
90
Dibenzo - 1
• "" ' •• ••v\.
..
d,i-Terphenyl
125
105
90
123
130
d„-Beazo(e)pyreoe
72
135
112
103
112
S~ - 1
\ ^
dm-Anthacene
67
48 H 1
115
116
101
83
85
Test Date
11/15/94
11/16/94 ! 11/17/94 |
11/16/94
NA
NA
NA
Date received by lab.
11/18/94 j11/18/94 } 11/18/94 j 11/18/94
NA
NA
NA
Date extracted
11/30/94 ill/30/94 \ 11/30/94
11/30/94
11/30/94
11/30/94
U/30/94
Date analyzed
12/3/94 112/3/94 !
12/3/94
12/3/94
12/3/94 112/3/94
12/3/94
"<" denotes that the compound was not detected at levels above the indicated reporting limit
"H" indicates internal Standard Recovery Results below 50%, but signal-to-noise greater than 10:1.
**" indicates compounds reanalyzed at 1:50 dilution due to saturation.
July 28, 1997
N-293
M-429 Page! 15
-------
FIGURE 17B
FIELD DATA SUMMARY FOR PAH EMISSIONS TEST
RUN ID
31
32
33
DATE
11-15-95
11-16-95
11-17-95
• •
START/STOP TIME
1015/1435
1Q2W1645
0855/1525
LOCATION
STACK
STACK
STACK
STACK DIAMETER
35 JS in.
35 J in.
35.5 io.
NOZZLE DIAMETER
03105
0313 in.
03125 in.
METER BOX ID
5419
5419
5419
STANDARD DRY GAS VOLUME
YnM)
145.19
235.57
250.76
DSCF(68C F)
v
' m
132.65
213.67
228.10
cubic ft
Pb-
29.78
29.98
29.88
inches Hg
1.15
135
1.56
inches H-O
T,,,
60.0
60.0
60.0
°F
K,
17.64
17.64
17.64
Y
1.08
1.08
1.08
PERCENT MOISTURE
12.9
15.0
18.4
percent
Impinger + t»e
21S3J
20923
2063
gmms
FioaJ wt
2609.8
2934.9
3210.2
grams
Net imp. catch
426.5
842.6
1147,2
grams
Silica gel tare
1561.8
1788.8
1585.7
grams
Post sampling wt
1590.0
1826.9
1536.2
grams
Moisture gain
282
38.1 .
49.5
grams
Total moisture (V,e)
454.7
880.7
1196.7
gmms
V«<*0
21.43
41.50
5639
DSCF(68° F)
vmCo^
145.19
235.57
250.76
DSCF(68° F)
K2
. 0.0471
0.0471
0.0471
MOLECULAR WEIGHT
29.93
29.95
30.08
Ib/lbmole
M,
28.40
28.16
27.86
ib/lbmole
Oi
11.25
10.75
10.00
percent
CO
0.00
0.00
0.00
percent
CO,
9.25
9.50
10.50
percent
n2
79.50
79.75
79.50
pe rcer:'
12.86
14.98
1836
percent
GAS VELOCITY
38.4
40.88
43.2
feet'second
Ap
0.530
0.56
0.59
inches H-0
T,
420
428
427
°F
P,
-077
-0.27
-037
inches H-0
Pf
29.76
29.96
29.86
inches Hg
K
28.40
28.16
27.86
IMbmolt
*p
85.49
85.49
85.49
"0.83
0.83
0.83
VOLUMETRIC FLOW RATE
8241
8531
8641
DSCF(68° F;
12.86
14.98
18.36
percent
V,
3838
40.88
_ 43.23
feet'second
A
6.8736
6.8736
6.8736
sq. feet
sec/min
60
60
60
K,
17.64
17.64
17.64
ISOKINETIC RATIO
I
96
99
104
percent
T.
420
428
427
°F
VB(«
-------
FIGURE I7C
EXAMPLE OF EMISSIONS TEST REPORT
Run #31
Run #32
Run #33
T~-... „ ^:
*
Naphthalene '
1046
1499
"
64782
2-Methylnaphtha]ene
<23
21.0
'
901
Acenaphthylene
34
106
11971
Acenaphthene
2.2
1.2
70
Fluorene
6,6
4.5
25
Phenanthrene
75
139
6056
Anthracene
<6.3
5.3
338
Fluoranthene
20
38
2253
Pyrene
27 *
47
2817
Benzo(a)anthraeene
<1.2
<0.75 .
24
Chrysene
<1.2
0.92
1 42
Benzo(b)fluoranthene j <1.2
.11
48
Benzo(k)fluoranthene
<1.2
<0.75
13
Benzo(e)pyrene
<8.5
<5.3
75
Benzo(a)pyrene
<1.2
<0.75
'
34
Perylene
<1.2
<0.75
16
Indeno( 1,2,3-c,d)pyreue
Dibenzo(aJi)anthracene
<1.2 j
<1.2 |
<0.75
<0.75
14
0.90
Benzo(g»h,i)perylene \
<21 |
<13
62
i ': • ' • :
Naphthalene
4068 ;
6036
264180
2-Methylnaphthalene
<89 I
85
3676
Acenaphthylene j
132 I
429
48816
Acenaphthene I
8.7
5.0
287
Fluorene
26
18
103
Phenanthrene 1
293 f
561
I
24695
Anthracene 1
<25 {
_ 21
1378
Fluoranthene
79 =
151
9189
Pyreae
104 f
187
i
1
11486
Bajzo(a)anthracene j
<4.7 j
<3.0
i
99
Chiysene
<4.7 |
3.7
i
172
Benzo(b)fluoranthene j
<4.7 |
4.6
I
195
Benzo(k)fluoranthene j
<4.7 f
<3.0
1
51
Benzo(e)pyrcne j
<33 i
<21
j
304
Benzo(a)pyrene
<4.7 j
<3.0
!
138
Perylene
<4.7 |
<3.0
j
63
Indeno(l »2,3-c,d)pyrene ]
<4.7 |
<3.0
|
57
Dibenzo(aJi)anthracene
<4.7 j
<3.0
]
3.7
Benzo(g4i>i)perylene j
<80 {
<
<51
|
253
Standard Conditions: 68 deg.F (20 deg.C) & 29.92 in. Hg. (760 mm Hg)
"<" indicates that the compound was not detected above the reporting limit
July 28,1997 M-429 Page 117
N-29S
-------
METHOD 429 - APPENDIX A
DETERMINATION OF THE METHOD DETECTION LIMIT
This procedure is based on the approach adopted by the EPA and included as Appendix B to Title 40, Part
136 of the Code of Federal Regulations (40 CFR136). The samples shall be subjected to the same
extraction, concentration, cleanup, and analytical procedures as those required for the field samples.
A1 Procedure
A1.1 Make an estimate of fee detection limit (MDL) of each target compound using one of the
following:
(a) The concentration value that corresponds to an instrument signal/noise ratio in the range of
2.5 to 5.
(b) The concentration equivalent of three times the standard deviation of replicate instrumental
measurements of the analyte in reagent methylene chloride.
(c) That region of the standard curve where there is a significant change in sensitivity, i.e,, a
break in the slope of the standard curve.
! (d) Instrumental limitations.
*
(e) The concentration equivalent to five times the theoretical quantitation limit (Section 8.3.1 of
the test method)
The experience of the analyst is important to this process, but one of the above considerations
must be included in the initial estimate of the detection limit
A 1.2 Prepare according to the procedures described in Sections 4.2.2.1 to 4.2.2.4 enough XAD-2 resin
to provide, at a minimum, eight aliquots each with mass equal to that required to pack a Method
429 sorbent cartridge. A contamination check must be conducted to identify' those PAH for
which a MDL cannot be determined by this method.
A 1.3 To each of seven (7) aliquots of the clean resin, add an amount of each target analyte equal to the
estimated detection limit. The mass of each resin aliquot must be known, and should be
approximately 40 grams, the amount required to pack a Method 429 sorbent cartridge. Use
eighth aliquot shall be a blank.
A 1.4 Process each of the eight samples through the entire PAH analytical method. All quality criteria
requirements of die analytical method must be satisfied.
A 1.5 Report the analytical results. The laboratory report must satisfy all of the reporting requirements
uX Section 10 of the test method.
My 28, 1997 M-429 Page 118
N-296
-------
It may be economically and technically desirable to evaluate the estimated method detection limit
before proceeding with step A1.3. This will: (1) prevent repeating this entire pr?ccc,;:re and O.)
insure that the procedure is being conducted at the correct concentration. It is quite possible that
an inflated MDL will be calculated from data obtained at many times the real MDL even though
die level of analyte is less than five times the calculated method detection
estimate of the method-detection, it is necessary to determine that a lower concentration of
analyte will not result in a significantly lower method detection limit Take two aliquots of the
sample to be used to calculate die method detection limit and process each through the entire
method, including blank measurements as described above in step A 1.3. Evaluate these data:
(1) If the sample levels are in a desirable range for determination of the MDL, take live
additional aliquots and proceed. Use all seven measurements for calculation of the MDL
according to Section A2.
(2) If these measurements indicate die selected analyte level is not in correct range, re-estimate
the MDL with a new sample as in A 1.2 and repeat steps A 1.3 to A 1.5.
A2 CALCULATION
A2.1 Calculate the variance (S2) and standard deviation (S) of the replicate measurements, as follows:
A1.6
2 _ 1
S2 =
n-1
E *?-
„ ">
E *,2
i = l
i-1
429-(A)-(l)
s = Vs1
Where:
Xj, i = 1 to n, are the analytical results in the final method reporting units obtained
from the n sample aliquots and E refers to the sum of the X values from i = 1 to
n.
A2.2 (a) Compute the MDL as follows:
MDL = Wi. i-«-0.99) x (S) 429(A)-(2)
Where:
July 28, 1997 M-429 Page 119
N-297
-------
MDL «ifac method detection limit
t(n,j lHX. 0 99)» Students' t-value appropriate for a 99% confidence level and a
standard deviation estimate with 11-1 degrees of freedom. See Table 429(A)-1.
S « standard deviation of die replicate analyses.
(b) The 95% confidence interval estimates for the MDL derived in A2.2(a) are computed
according to the following equations derived from percentiles of fee chi square over degrees
of freedom distribution O^/df).
LCL-0.64 MDL
UCL = 2.20 MDL
where: LCL and UCL are the lower and upper 95% confidence limits respectively based on
seven aliquots.
A3 OPTIONAL ITERATIVE PROCEDURE
A3.1 This is to verify the reasonableness of the estimate of the MDL and subsequent MDL
determinations.
(a) If this is die initial attempt to compute MDL based on the estimate of MDL formulated in
Step A1.1, take the MDL as calculated in Step A2.2, spike the matrix at this calculated
MDL and repeat the procedure starting with Step A1.3.
(b) If this is the second or later iteration of the MDL calculation, use S2 from the current MDL
calculation and S2 from the previous MDL calculation to compute the F-ratio The F-ratio is
calculated by substituting the larger S2 into the numerator S2A and the other into the
denominator S2g. The computed F-ratio is then compared with
the F-ratio found in the table which is 3.05 as follows: if S2A/S2B<3.05, then compute the
pooled standard deviation by fee following equation:
Spooled
6Sa * 6S|
-
429(A)-(3)
if S2a/S2b>3.05, respike at the most recent calculated MDL and process fee samples through the
procedure starting with Step A1.3. If the most recent calculated MDL does not permit
qualitative identification when samples are spiked at that level, report fee MDL as a
concentration between the current and previous MDL which permits qualitative identification
July 28, 1997 M-429 Page 120
N-798
-------
(c) Use the as calculated in Equation 429(A)-3 to compute the final MDL according to
the following equation:
MDL = 2.68 429(A)-(4)
Where: 2.681 is equal to t(12i i.a - 99).
(d) The 95% confidence limits for MDL calculated using Equation 429(A)-4 are computed
according to the following equations derived from percentiles of the chi squared over degrees
of freedom distribution.
LCL - 0.72 MDL
UCL -1.65 MDL
where LCL and UCL are the lower and upper 95% confidence limits respectively based on
14 aliquots.
July 28,1997
N-299
M-429 Page 121
-------
TABLE 429(A)-1
SELECTED STUDENT'S t VALUES AT THE 99 PERCENT CONFIDENCE LEVEL
Number of Degrees
Replicates of Freedom
(D*1) '(n-l, ,99}
7
6
3.143
8
7
2.998
9
8
2.896
10
9
2.821
11
10
2.764
16
15
2.602
21
20
2.528
26
25
2.485
31
30
2.457
61
60
• 2.390
28,1997
N-300
M-429 Page 122
-------
N-4
Chlorine Protocol
N-301
-------
CHLORINE (RESIDUAL) (4500-CiyDPD Colorimetric Method
4-45
i. Thioaceiamide solution: Dissolve 250 mg CHjCSNH, in 100
bL distilled water. (Caution: Cancer suspect agent. Take care
to avoid skin contact or ingestion.)
j. Chlorine-demand-free water: See C.3m.
k. Glycine solution: Dissolve 20 g glycine (aminoacetic acid)
in sufficient chlorine-demand-free water to bring to 100 mL total
volume. Store under refrigerated conditions and discard if cloud-
iness develops.
L Barium chloride crystals, BaO2-2H20. -
3. Procedure
The quantities given below are suitable for concentrations of
total chlorine up to S mg/L. If total chlorine exceeds 5 mg/L,
use a smaller sample and dilute to a total volume of 100 mL.
Mix usual volumes of buffer reagent and DPD indicator solution,
or usual amount of DPD powder, with distilled water before
adding sufficient sample to bring total volume to 100 mL. (If
sample is added before buffer, test does not work.)
If chromate is present (>2 mg/L) add and mix 0.2 g BaG2-2H20/
100 mL sample before adding other reagents. If, io addition,
sulfate is >500 mg/L, use 0.4 g BaQ.-2H20/100 mL sample.
a. Free chlorine or chloramine: Place 5 mL eacfa of buffer
reagent and DPD indicator solution in titration Qask and mix
(or use about 500 mg DPD powder). Add 100 mL sample, or
diluted sample, and mix.
1) Free chlorine—Titrate rapidly with standard FAS tiBrant
until red color is discharged (Reading A).
2) Moaodiloramine—Add one very small crystal of KJ (about
0.5 mg) or'0.1 mL (2 drops) KI solution and mix. Continue
titrating until red color is discharged again (Reading B).
3) Dichloramine—Add several crystals KI (about 1 g) and mix
to dissolve. Let stand for 2 min and continue titrating until red
color is discharged (Reading C). For di chloramine concentra-
tions greater than 1 mg/L, let stand 2 min more if color driftback
indicates slightly incomplete reaction. When dichloramine con-
centrations are not expected to be high, use half the specified
amount of Id.
4) Simplified procedure for free and combined chlorine or total
chlorine—Omit 2) above to obtain monochloramine and dich-
loramine together as combined chlorine. To obtain total chlorine
in one reading, add full amount of KI at the start, with the
specified amounts of buffer reagent and DPD indicator, and
titrate after 2 min standing.
b. Nitrogen trichloride: Place one very small crystal of KI (about
0.5 mg) or 0.1 mL KI solution in a titration flask. Add 100 mL
sample and mix. Add contents to a second flask containing 5 mL
each of buffer reagent and DPD indicator solution (or add about
500 mg DPD powder direct to the first flask). Titrate rapidly
with standard FAS titrant until red color is discharged (Reading
iV).
c. Free chlorine in presence of bromine or iodine: Determine
free chlorine as in 1 3al). To a second 100-mL sample, add 1
mL glycine solution before adding DPD and buffer. Titrate ac-
cording to 1 3al). Subtract the second reading from the firs; to
obtain Reading A.
4. Calculation
For a 100-mL sample, 1.00 mL scan dare i-AS utrant = i.iW
mg Q as Gj/L.
Reading NQ, Absent NO, Present
A Free Q Free Q
B - A NHjQ NHjC
C - B NHdj NHCi, + 'ANQj
N — Free CI + WO,
2(N - A) — NClj
C - N — NHC3;
In the event that monochloramine is present with NG5, it will
be included in N, in which case obtain NCI, from 2(.V-5).
Chlorine dioxide, if present, is included in A to the extent of
one-fifth of its total chlorine conteac.
In the simplified procedure for free and combined chlorine,
only A (free G) and C (total G) are required. Obtain combined
chlorine from C-A.
The result obtained in the simplified total chlorine procedure
corresponds to C.
5. Precision and Bias
See B.5.
6. Bibliography
Palin, A.T. 1957. The determination of free and combined chlonne in
water by the use of diethyl-p-phenylene diamine J. Amtr. Water
Works Assoc. 49:873.
Palin, AT. 1960. Colorimetric determination of chlorine dioxide in
water. Water Sewage Works 107:45".
Palin, A.T. 1961. The determination of fres residual bromine in water
Water Sewage Works 108:461.
Nicolson, N.J. 1963, 1965, 1966. Determination of chlorine in water
Parts 1, 2, and 3. Water Res. Assoc. Tech. Pap. Nos. 29, 47, and
53.
Palin, A.T. 1967. Methods for determination, in water, of free acc
combined available chlorine, chlorine dioxide and chlorite, brorrke.
iodine, and azooe using diethyl-p-phenylenediamine ODPD). J InsL
Wtter Eng. 21:537.
Palin, A.T. 1968. Determination of nitrogen trichloride in water I
Amtr. Water Works Assoc. 60:847.
Palin, A.T. 1975. Current DPD methods for residual halogen com-
pounds and ozone in water. J. Amtr. Water Works Arioc. 67:32.
Methods for the Examination of Water* and Associated Matenala
Chemical Disinfecting Agents in Water and Effluents, and Chlorine
Demand. 1980. Her Majesty's Stationery OS., London. England.
4500-CI G. DPD Colorimetric Method
1. General Discussion
a. Principle: This is a colorimetric version of the DPD method
and is based on the tame principles. Instead of titration with
standard ferrous ammonium sulfate (FAS) solution as in the
titrimetric method, a colorimetric procedure is used.
b. Interference: See A.3 and F.ld. Compensate for color and
turbidity by using sample to zero photometer. Minimis chro-
N-302
-------
4-46
INORGANIC NONMETAL5 (4000)
mate interference by using the thioacetamide blank correction.
c. Minimum detectable concentration: Approximately 10 jig CI
as Gj/L. This detection limit is achievable under ideal conditions;
normal working detection limits typically are higher. •
2. Apparatus
a. Photometric equipment: One of the following is requited:
1) Spectrophotometer, for use at a wavelength'of 515 tun and
providing a light path of 1 cm or longer.
2) Filter photometer, equipped with a filter having maximum
transmission in the wavelength range of 490 to 530 urn and pro-
viding a light path of 1 cm or longer.
b. Glassware: Use separate glassware, including separate spec-
trophotometer cells, for free and combined (dichloramine) meas-
urements, to avoid iodide contamination in free chlorine meas-
urement.
3. Reagents
See F.2o, b, c, d, e, h, i, and
4. Procedure
a. Calibration of photometric equipment: Calibrate instrument
with chlorine or potassium permanganate solutions.
1) Chlorine solutions—Prepare chlorine standards in the range
of 0.05 to 4 mg/L from about 100 mg/L chlorine water stand-
ardized as follows: Place 2 mL acetic acid and 10 to 25 mL
chlorine-demand-free water in a flask. Add about 1 g Ki. Meas-
ure into the flask a suitable volume of chlorine solution. In choos-
ing a convenient volume, note that 1 mL 0.025.V Na^O, titraa!
(see B2d) is equivalent to about 0.9 mg chlorine. Titrate with
standardized 0.02JA' Na,S,0, titrant until the yellow iodine color
almost disappears. Add 1 to 2 mL starch indicator solution and
continue titrating to disappearance of blue color.
Determine the blank by adding identical quantities of acid,
Kl, and starch indicator to a volume of chlorine-demand-free
water corresponding to the sample used for titration. Perform
blank titration A or B, whichever applies, according to B.3d.
mg C! as Qj/mL <
{A + 3) x N x 35.45
mL sample
where:
A' - normality of Na^O,,
A " mL titrant for sample,
B ' mL litrut for blank (to be added or *»btr»eled according to
required blank titration. See B.Si).
Use chlorine-demand-free water and glassware to prepare these
standards. Dcelop color by first placing 5 mL phosphate buffer
solution and 5 mL DPD indicator reagent in flask and then adding
100 mL chlorine standard with thorough mixing as described in
b and c below. JFlIt photometer or colorimeter cell from flask
and read color at 515 nan. Return cell contents to Cask and titrate
with standard FAS titrant as 3 check on chlorine concentration.
2) Fot »n fcm.ar.g.matc solutions—Prepare a stock so-
lution containing 891 mg KM nO./1000 mL. Dilute 10.00 mL
stock solution to 100 mL with distilled water in a volumetric
flask. When 1 mL of this solution is diluted to 100 mL with
distilled water, a chlorine equivalent of 1.00 mg/L will be pro-
duced in the DPD reaction. Prepare a series of KMnO< standards
covering the chlorine equivalent range of 0.05 to 4 mg/L. Develop
color by first placing 5 mL phosphate buffer and 5 mL DPD
indicator reagent in flask and adding 100 mL standard with thor-
ough muting as described in fc and c below. Fill photometer or
colorimeter cell from flask and read color at 515 am. Return cell
contents to fiask and titrate with FAS titraat as a check on any
absorption of permanganate by distilled water.
Obtain aB readings by comparison to color standards or the
standard curve before use is calculation.
b. Volume of sample: Use a sample volume appropriate to the
photometer or colorimeter. The following procedure is based on
using 10-mL volumes;'adjust reagent quantities proportionately
for other sample volumes. Dilute sample with chlorine-demand-
free water when total chlorine exceeds 4 mg/L.
c. Free chlorine: Place 0.5 mL each of buffer reagent and DPD
indicator reagent in a test tube or photometer cell, Add 10 mL
sample and mix. Read color immediately (Reading A).
d. Monochloromme: Continue by adding one very small crystal
ofKI (about 0,1 mg) and mix. If dichloramine concentration is
expected to be high, instead of small crystal add 0.1 mL (2 drops)
freshly prepared KI solution (0.1 g/100 mL). Read color im-
mediately (Reading B).
e. Dichloramine: Continue by adding several crystals of Kl
(about 0.1 g) and mix to dissolve. Let stand about 2 min and
read color (Reading Q,
/. Nitrogen trichloride: Place a very small crystal of KI (about
0.1 mg) in a dean test tube or photometer cell. Add 10 mL
sample and mix. To a second tube or cell add 0.5 mL each of
buffer and indicator reagents; mix. Add contents to first rube or
cell and mix. Read color immediately (Reading N).
g. Chromate correction using thioacetamide: Add 0.5 mL
thioacetamide solution (F.21) to 100 mL sample. After mixing,
add buffer and DPD reagent. Read color immediately. Add
several crystals of Kl (about 0.1 g) and mix to dissolve. Let stand
about 2 min and read color. Subtract the first reading from Read-
ing A and the second reading from Reading C asd use in cal-
culations.
h. Simplified procedure for total chlorine: Omit Step d above
to obtain monochloramine and dichloramine together as com-
bined chlorine. To obtain total chlorine in one reading, add the
full amount of Kl at the start, with the specified amounts of
buffer reagent and DPD indicator. Read color after 2 min
5. Calculation
Reading
NQj Absent
NO, Present
A
B- A
c - a
N
UN-A)
C - N
Free Q
NHjCJ
NHd,
Free <3
NHjCl
NHOj + VSNCl,
Free Q + ViNQ,
NO,
nhq,
In the event that monochloramine is present with NCI,, it will
be included in Reading N, in which case obtain NO, from 2(A'~ S).
6. Bibliography
See F.6,
N-303
-------
Designation; 0 5233 - 92
Standard Test Method for
Single Batch Extraction Method for Wastes1
This standard ii issued under the fixed designation D 3233; the Dumber immediately followint the destination indicates the ytzr of
original adoption or, ill the case of revision, the year of last revision. A number is parentheses indicates the year of last peapproval A
superscript epsiloti {«) indicates aa editorial chatije ante the last revision or (approval.
1. Scope
1.1 This test method is applicable to the extraction of
samples of treated or untreated solid wastes or sludges, or
solidified waste samples, to provide an indication of the
leaching potential.
1.2 This test method is intended to provide an extract for
measurement of the concentration of the analytes of con-
cern. The measured values may be compared against set or
chosen acceptance levels in some applications.
1.3 If the sole application of the test method is such a
pass/fail comparison and a total analysis of the waste
demonstrates that individual analytes are not present in the
waste, or that the chosen acceptance concentration levels
could not possibly be exceeded, the test method need not be
tun.
1.4 If the sole application of the test method is such a
pass/fail comparison and an analysis of any one of the liquid
fractions of the extract indicates that the concentration of the
target analyte is so high that, even after accounting for
dilution from the other fractions of the extract, it would be
equal to or above an acceptance concentration level, then the
waste fails the test In such a case it may not be necessary to
analyze the remaining fractions of the extract.
1.5 This test method is intended to provide an extract
suitable for the measurement of the concentration of
analytes that will not volatilize under the conditions of the
test method.
1.6 Presence of volatile analytes may be established if an
analysis of the extract obtained using this test method detects
the target volatile analyte. If its concentration is equal to or
exceeds an acceptance level for that analyte, the waste Ms
the test However, extract from this test method shall not be
used to determine the concentration of volatile organic
analytes.
1.7 This test method is intended to describe only the
procedure for performing a batch extraction. It does not
describe all of the sampling and analytical requirements that
may be associated with the application of this test method.
1.8 The values sated in either SI or inch-pound units are
to be regarded as the standard. The values given in paren-
theses are for information only.
1.9 This standard does not purport to address all of the
setfety problems, if my, associated with its use. It is the
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use. For a specific
1 This test method is under the jurisdiction of ASTM Committee D-34 on
**oe Disposal and is the direct responsibility of Subcommittee D34.02 on
Kysical tad Chemical Chaiactosmon.
Current edition approved March 15. 1992. Published Mar 1991
precautionary statement, see Note 8.
2. Referenced Documents
2.1 ASTM Standards:
D75 Practices for Sampling Aggregates2
D420 Practice for Investigating and Sampling Soil and
Rock for Engineering Purposes3
D653 Terminology Relating to Soil, Rock, and Contained
Fluids3
D1129 Terminology Relating to Water4
D1193 Specification for Reagent Water4
D2234 Test Method for Collection of a Gross Sample of
Coal3
D 3370 Practices for Sampling Water4
E 122 Practice for Choice of Sample Size to Estimate A
Measure of Quality for a Lot or Process4
ES 16 Practice for the Generation of Environmental Data
Related to Waste Management Activities7
3. Terminology
3.1 Definitions—For definitions of terms used but not
defined in this test method, see Terminology D 1129.
4. Summary or Test Method (See Figure 1)
4.1 For wastes containing less than 0.5 % dry solid
material, the filtrate of the waste, after filtration through a
0.6 to 0.8-^m glass fiber filter, is defined as the method
extract Extraction of the solid is not required for such
wastes.1-9
4.2 For wastes containing greater than or equal to 0.5 %
dry solid material, the liquid, if any, is separated from the
solid phase and stored for later analysis. The solid phase is
extracted with an amount of extraction fluid equal to 20
times the weight of the solid phase. The extraction fluid used
is a function of the alkalinity of the solid phase of the waste
Following extraction, the liquid extract is separated from the
solid phase by filtration through a 0.6 to 0.8-^m glass fiber
filter.
4.3 If compatible (that is, multiple phases will not form
upon combination), the initial liquid phase of the waste is
added to the liquid extract, and these are analyzed together.
If incompatible, the liquids are analyzed separately and the
» Amaai Book of ASTM Standards. Vol 04.03.
'Aiamat Book of ASTM Standards, Voi 04.08.
« Animal Book of ASTM Standards, Vol 1 LCI.
1 Annual Book of ASTM Standards, Voi 0S.03.
* Annual Book of ASTM Standards, Vol 14.01
' Annuel Book of ASTM Standards, Vol 11.04 (ice 1991 edition).
* Federal JUtfuer, Voi 53, No. 61, March 29. 1990. Toitidtv Characteristics
Revisions, final Rule.
'Federal Register, Voi 55, No. 126, June 29, 1990, Tonicity Characteristic
Revisions. Final Ride, Corrections.
N-304
-------
[
fit asy-e
DH
Analyze
# 0 5233
Samairior.
*c#!lmmary
£*atuatisn
IS.6EM3
ah Phases
ScHc Only
L»Qj!(3 Of.lv
same;*
rrsfirmatioft
Or,-¥
SeHd
Stoinu
UQUlfl/SOUd
cnitari
LWg »»m
Oiscare
SoltOS
Disease
ones
Content
* X»0-5*
sens
Sample
Disease
L iQUI
FffSft
5«me?e -•
$nsed 10
10 Kimnir!, T. A., and Friedman. D. A., "Model Assumptions and RwionaJe
5thind the Development of EP III." ASTM STF m. i. K. Petros, el *!. Eds.,
iSTM. Philadelphia, PA, 1SK, pp. 36-53.
5.4 One intent of this test method is to not allow the pH
of the extraction fluid to be lower than that of the leachate of
a specific landfill where municipal and industrial wastes were
co-disposed. Therefore, the pH of the extraction fluid was
chosen with the following considerations:
(1) Not to be less than 4.93 ± 0.05 for the extraction of
wastes with an acid neutralization capacity of less than the
acid available in the total volume of extraction fluid used in
the method (Extraction Fluid No. 1).
(2) At 2.88 ± 0.05, as defined by the pH of the acid, for
the extraction of wastes with an acid neutralization capacity
of more than the add available in the extraction fluid used in
the method (Extraction Flvii No. 2).
5.5 The interpretation and use of the results of this test
method are limited by the assumptions of a single co-
disposal scenario and by the factors affecting the composi-
tion of a landfill leachate and chemical or other differences
between a selected extraction fluid and the real landfill
leachate.
5.6 This test method may be affected by biological
144 N-305
-------
#5 0 5233
Meter
Estrtettea VttMl MoW»f
(30 11 rpm)
^UUUU
FIG. 2 dotary Agitation Apparatus
changes in the waste, and it is not designed to isolate or
measure the effect of such processes.
5.7 This test method produces extracts that are amenable
to the determination of both minor and major constituents.
When minor constituents are being determined, it is espe-
cially important that precautions be taken in sample storage
tod handling to avoid possible contamination of the sam-
ples.
5.8 The agitation technique, rate, liquid-to-solid ratio,
mi filtration conditions specified in the method may not be
suitable for extracting all types of wastes,
5.9 This test method is intended to extract the samples in
their original physical state as is, without any size reduction.
However, the sample/extractor interaction is expected to
correlate with the environmental conditions to which a waste
may be exposed.11
5.10 The extraction conditions defined by this test
method are expected to yield steady-state concentrations,
determined by the extraction liquid-to-solid ratio and the
duration of the extraction, which may or may not agree with
the concentration of an equilibrium.
6. Apparatus and Materials
6.1 Agitation Apparatus, capable of rotating the extraction
vessel in an end-over-end fashion (see Fig. 2), at 30 ± 2
r/min, such that the axis of rotation is horizontal and passes
through the center of the bottle.
Note i—Similar devices may be used having a different axle
arrangement if equivalency can be demonstrated.
6.2 Extraction Vessel—Suitable vessels include cylindri-
cafly shaped, minimum 2-L size, with capacity sufficient to
hold the sample and the extraction fluid. Head-space is
•Bowed in this vessel. The extraction bottles may be con-
structed from various plastic materials, depending on the
Mialytes of interest and the nature of the waste. Plastic
bottles, other than polytetrafluoroethylene, shall not be used
if organics are to be investigated. The bottles should be
*urdy, in order to withstand the impact of the Ming sample
fragments, and shall have a leak-free seal The use of
Polytetrafluoroethylene tape is recommended to ensure a
*>Sht seal. Due to their potential for breakage, the use of glass
bottles is not recommended.
. " Ffdtral Rigour, Vol 53. No. 100, May 24, IMS. Projxaed Cm Modifio-
•"¦ofTCLP.
Note 2—Suitable bottles range from 4 0 to 4 5 in (102 to 114 mm)
in diameter and from 8.5 io 13.0 in. (216 to 330 ir.m) in height.
6.3 Filtration Device—It is axOiVt eicr; *r:: sS" illa-
tions be performed in a hood. Wastes should be filtered using
positive-pressure filtration using a pre-purifled grade inert
gas such as nitrogen.
6J. I Filter Holder, capable of supporting a glass fiber
filter and able to withstand the pressure needed to accom-
plish separation {maximum 50 psi or 345 kPa). These
devices shall have a minimum internal volume of 300 raL
and shall be equipped to accommodate a minimum filter size
of 47 mm. (Filter holders having an internal capacity of 2.2 L
and equipped to accommodate a 142-mm diameter filter are
recommended.)
6.3.1.1 Materials of Construction—Filtration devices shall
be made of inert materials that will not leach or adsorb the
.analytes of concern. Glass, polytetrafluoroethylene, or type
316 stainless steel equipment may be used when both
organic and inorganic analytes are of concern. Devices made
of high-density polyethylene (HDPE), polypropylene (PP). or
polyvinyichloride (PVC) may be used when only inorganics
are of concern.
6.4 Fillers, made of borosilicate glass fiber, containing no
binder materials, and having an effective pore size of 0.6 to
0.8 pm. Pre-filters must not be tised. When inorganic
analytes are of concern, the filter shall be acid washed prior
to use by rinsing with I N nitric acid followed by three
consecutive rinses with Type II reagent water as defined in
Specification D 1193. (A minimum of 1 L per rinse is
recommended.) Glass fiber filters are fragile and should be
handled with care.
6.5 plf Meter, with a readability of 0.01 unit and an
accuracy of ±0.05 unit at 25*C.
6.6 Laboratory Balance, accurate to within ±0.01 g. (All
weight measurements are to be within xO. 1 gj
6.7 Beakers or Erlenmeyer Flasks, glass 500-mL, and 2-L.
6.8 Watch-Glass, with an appropriate diameter to cover
the beaker or Erlenmeyer flask.
6.9 Magnetic Stirrer.
6.10 Mold, cylindrical, mad; of inert, non-adsorbing and
non-contaminating material for casting of laboratory sam-
ples.
6.11 Straightedge, made of stainless steel.
6.12 Impermeable Sheet or Glazed Paper.
6.13 Volumetric Flask, I-L me.
6.14 Drying ~Oven—Any thermostatically controlled
drying oven capable of maintaining a temperature between
85 and U5*C within ±5'C.
6.15 Graduated Pipet, readable to 0.1 mL.
6.16 Hot Plate, equipped for agitation and temperature
control capable of maintaining a 50 ± 3*C temperature.
6.17 Graduated Measuring Cylinder, with a precision of
±3%.
7. Reagents
7.1 Purity of Reagents—grade chemicals shall be
used is all tests. Unless otherwise indicated, it is intended
that all reagents shall conform to the specifications of the
Committee on Analytical Reagents of the American Chem-
145
N-306
-------
© D 5233
TABLE 1 Sample Maximum Holding Timet, Dey»
Period Oompounc
From FmkJ Cotectxjn
to Method Extractor!
From We End of
Extraction to the Star! of
FltraW. h
From Method EKTOWxi
to Ana(y9Cil
Extraction
From the Analyt>cal
Extraction to She
Cmm«aii Anaivsis
Total Time,
Days
Orgsnics
Mercury
koyancs except Mercury
u
28
180
7
NA
NA
40
28
180
61
56
360
ical Society, where such specifications are available.1' Other
grades may be used, provided it is first ascertained that the
reagent is of sufficiently high purity to permit its use without
lessening the accuracy of the determination.
7.2 Purity of Water—Reagent water is defined as water in
which an interfering analyte is not observed at or above the
method detection limit of the aaalyte(s) of interest. Type D
of Specification D 1193 or equivalent meets the definition of
reagent water.
7.3 Hydrochloric Acid (HQ), 1 N, made from ACS
reagent grade.
7.4 Nitric Acid (HNOj), I N, made from ACS reagent
grade.
7.5 Sodium Hydroxide (NaOH), 1 N, made from ACS
reagent grade.
7.6 Glacial Acetic Acid (CH3COOH), ACS reagent grade.
7.7 Extraction Fluids—Several batches or multiple vol-
umes of extraction fluids should be prepared in accordance
with the number of extractions. The volume needed for an
individual extraction is approximately 2 L. The extraction
fluids should be monitored frequently for impurities. The pH
should be examined prior to extraction to ensure that these
fluids were made up accurately. If impurities are found or the
pH is not within the specifications, the fluid shall be
discarded and fresh extraction fluid prepared.
7.7.1 Extraction Fluid No. 1—Add 5.7 mL glacial acetic
acid to 500 mL of reagent water, add 64.3 mL of I N NaOH,
and dilute to a volume of 1 L. When correctly prepared, the
pH of this fluid will be 4.93 ± 0.05.
7.?,2 Extraction Fluid No, 2—Dilute 5.7 mL glacial
acetic acid with reagent water to a volume of 1 L. When
correctly prepared, the pH of this fluid will be 2.88 ± 0.05.
8. Sampling
8.1 If representative samples of the waste must be tested,
use ASTM Sampling methods developed for the specific
industry where available (see Practices D 75, D 420, D 3370,
Terminology D 653, and Method D 2234).
8.2 All samples shall be collected using an appropriate
sampling plan to ensure sample integrity and representative-
ness (see Practice E 122).
8.3 Where no specific methods are available, sampling
methodology for materials of similar physical form shall be
used.
8.4 Ii is important that the sample of the waste be
*.w surface area, as variation? ir
surface area would directly affect the extraction characteris-
""Rtagern Ciiemicals, American Chemical Society Specifications," Am.
Chemical Soc., Washington, DC. For suggestions on the letting of reagents not
Used by the American Chemical Societ>, let "Reagent Chemi«*is and Standards,"
by Joseph Rosin. D. Van Noctrand Co.. Inc., New York, NY, lad the "United
Slues Pharmacopeia "
tics of the sample. Waste samples should contain a represen-
tative distribution of particle sizes.
Note 3—Information on obtaining representative samples can also
he found in Pierre Cy's Sampling Theory and Practice."
8.5 Approximately 100 g of solid phase samples are
required for each extraction. Preliminary evaluation also
requires 100 g of solid phase sample. A larger sample size
may be required, depending on the solids content of the
waste sample (percent solids; see 10.2.9).
8.6 Enough extract should be generated such that the
volume will be sufficient to support all of the analyses
required. If the volume of extract generated by the perfor-
mance of a single extraction will not be sufficient to perform
all of the analyses to be conducted, it is recommended that
more than one extraction be performed and that the extracts
from each extraction be combined and then aliquoted for
analysis.
8.7 For the evaluation of solidified or stabilized wastes, or
both, samples may be cast in the form of a cylinder that will
fit into the extraction apparatus. Such cylinders may be used
for the evaluation. The casting may be allowed to cure for 30
days before the extraction procedure is performed. For other
monolithic materials, a coring may be produced that will fit
into the extraction apparatus. Waste materials to which these
casting and coring procedures apply include concrete mate-
rials, rock, wood, slag, and so forth.
8.8 Quality control measures may require additional sam-
ples.
9. Sample Handling and Preparation
9.1 For free-flowing particulate solid wastes, obtain a
sample in accordance with the requirements of Section 8 by
quartering the sample received for testing on an imperme-
able sheet of glazed paper, or other flexible non-contami-
nating materia], as follows:
9.1.1 Empty the sample container into the center of the
sheet »
9.1.2 Flatten out the sample gently with a suitable
straightedge until it is spread uniformly to a depth at least
twice the maximum particle diameter.
9.1.3 Remix the sample by lifting a comer of the sheet
and drawing low across to the opposite corner in the manner
that the material is made to roll over and over and does not
merely slide along. Return that corner to its original position.
Continue the operation with each corner, proceeding in *
ut v* i* I..is v^cle ten t.ni*»»*.
9.1.4 Lift all four corners of the sheet toward the center,
and holding all four corners together, raise the entire sheet
into the air tc form a pocket for the sample.
11 Pitard, F„ Pime Gy's Sampling Theory ami Practice, Volumes 1 and 11, C*C
Press, 1989.
146
N-307
-------
# D 5233
9.1.5 Repeat 9.1.2.
9.1.6 Gently divide the sample into quarters with a
straightedge, one at least as long as the flattened mound of
sample. Make an effort to avoid using pressure on the
jtraightedge sufficient to cause damage to the particles.
9.1.7 Discard alternate quarters.
9.1.8 If further reduction of the sample volume is neces-
sary, repeat 9.1.3 through 9.1.7. Use a sample volume to give
100 g of solid for each extraction. Provide additional samples
for the preliminary evaluation.
9.2 For field-cored solid wastes or castings produced in
the laboratory, cut a representative section weighing approx-
imately 100 g for each extraction plus the preliminary
evaluation. Take samples for the preliminary evaluation at
the same time as the test samples.
9.2.1 If necessary, shape the sample so that its largest
dimension would not exceed the radius of the extraction
bottle. (The material shall move freely while fully covered
with the extraction fluid.)
9.3 Preservatives shall not be added to the samples prior
to extraction.
9.4 For multi-phasic wastes, mix thoroughly to ensure
that a representative sample will be withdrawn.
9.3 Samples shall be stored at 4*C to minimize changes
due to biological processes. If precipitation occurs, the entire
sample (including precipitate) of the precipitate existing at
room temperature (see 4.1 and 4.2) should be used.
9.6 IJte method filtrates and extracts should be prepared
for analysis and analyzed as soon as possible. Filtrates and
extracts or their portions for metallic analyte determinations
should be acidified with nitric acid to pH <2 unless
precipitation occurs. To minimize losses, filtrates or extracts
or their portions for organic contaminant determinations
shall not be allowed to make contact with the atmosphere
(that is, head-space).
9.7 Sample maximum holding times (days) are given in
Table 1.
10. Preliminary Evaluations and Pre-E*traction Procedures
10.1 Perform preliminary method evaluations on a min-
imum 100-g aliquot of waste. This aliquot may not undergo
the actual extraction. These preliminary evaluations include
the determination of the following: (I) percent solids, (2)
whether the waste contains dry solids in excess of 0.5 %, and
(3) which of the two extraction fluids are to be used for
extraction of the waste.
10.2 Preliminary Determination of Percent Solids—Per-
cent solids is defined as that fraction of the waste sample (as
* percent of the total sample w/w) from which no liquid may
be forced out by an applied pressure as described below.
'0-2.1 If the waste will obviously yield no free liquid when
subjected to pressure filtration of this method (that is, 100 %
»Ms)» proceed to 10.4.
Noti 4—Some materials may look like dry solids but amy release
""l % of the original sample
weight) has obviously adhered to the container used to transfer the
sample to the filtration apparatus, determine the weigh: of this residue
and subtract it from the sample weight determined io 10.2.5 to
determine the weight of the waste sample that will be filtered.
10.2.7.1 Gradually apply gentle pressure of 1 to 10 psi (7
to 70 kPa), until the pressurizing 'gas moves through the
filter. If this point is not reached below 10 psi (69 kPa), and
if no additional liquid has passed through the filter in any
2-min interval, slowly increase the pressure in 10-psi (69-
kPa) increments to a maximum of 50 psi (345 kPa). After
each incremental increase of 10 psi (69 kPa), if the pressur-
izing gas has not moved through the filter, and if no
additional liquid has passed the filter in any 2-min interval,
proceed to the next 10-psi (69-kPa) increment. When the
pressurizing gas begins to move through the filter, or when
the liquid flow has ceased at 50 psi (345 kPa) (that is,
filtration does not result in any additional filtrate within any
2-min period), stop the filtration.
Note 6—Instantaneous application of high pressure can degrade the
glass fiber filter and may cause premature plugging.
10.2.8 The material in the filter holder is defined as the
solid phase of the waste, and the filtrate is defined as the
liquid phase.
Note 7—Same wastes, such as oily and some paint wastes, w.'j
obviously contain some material that appears to be liquid Even after
applying the pressure filtration as outlined in 10.2.7, this material may
not filter. If this is the case, the material within the filtration device is
defined as solid. Do not replace the original filter under any circum -
stances. Use only one filter.
10.2.9 Determine the weight of the liquid phase by
subtracting the weight of the filtrate container (see 10.2.3)
from the total weight of the container plus filtrate. Deter
mine the weight of the solid phase of the waste sample by
subtracting the weight of the liquid phase from the weight of
die total waste sample, as determined in 10.2.5 or 10.2.7,
Record the weight of the liquid and solid phases. Calculate
the percent solids as follows:
weight of solid (10.2.9)
VI *J11U ^ 1U.&. 7/
percent solids — x 100
-------
I
5.0, add 3.5 mL 1 N HQ,
slurry briefly, cover with a watch-glass, heat to 50*C, and
hold at 50*C for 10 min.
10.4.4 Let »he solution cool to room temperature and
record the pH. If the pH is <5.0. use Extraction Fluid No. 1.
If the pH is >5.0, use Extraction Fluid No. 2. Proceed to
Section II.
10.5 If the aliquot of the waste used for the preliminary
evaluation (10.2 through 10.4) was determined to be 100 %
.vlIsL IC.II, /. !. _;;d for Section 11 extraction
(assuming that at .'east 100 g remains). The aliquot subjected
to the procedurt ir» 10.2.7 might be appropriate for use in
Sectior 1! :frn adequate amount of solids (as determined by
10.2.9) was obtained. The amount of solids necessary is also
dependent on whether a sufficient amount of extract will be
produced to support the analyses for the target analytes. If an
adequate amount of solids remains, proceed to 11.11.
PH
Use
Extractor
Fluid
•2
FIG. 3 Determination of tha Extraction Fluid
11. Extraction
11.1 A sample size of minimally 100 g (solid and liquid
phases) is required. A larger sample size may be appropriate
in some cases, depending on the solid contents of the waste
sample (percent solids; see 10.2); whether the initial liquid
phase (filtrate) will be miscible with the aqueous extract of
the solid; and whether inorganics, semivolatile organics,
pesticides and herbicides are all analytes of concern. If the
amount of extract generated by a single extraction will not be
sufficient to perform all of the analyses, more than one
extraction may be performed and the extracts from each
combined and aliquoted for analysis.
11.2 If the waste will, obviously yield no liquid when
subjected to pressure filtration (that is, is 100 % solid; 10.2),
weigh out a sub-sample of the waste (100 g minimum) and
proceed to 11.10.
11.3 If the sample is liquid-like or multi-phasic, liquid-
solid separation is required. This involves the filtration
device described in 6.3 and is outlined in 11.4 through 11.9-
11.4 Pre-weigh the container that will receive the filtrate
11.5 Assemble the filter holder and filter following the
manufacturer's instructions. Place the filter on the support
screen and secure. Acid wash the filter if inorganics are of
concern (see 6.4).
Norc 9—Acid washed filters may be used for all extractions, eve#
when inorganics are not of concern.
148
N-309
-------
# D 5233
11.6 Weigh out a sub-sample of waste (100-g minimum)
jjd record the weight. If the waste contains <0.5 % dry
solids (10.3), the liquid portion of the waste, after filtration,
is defined as the method extract. Therefore, enough of the
sample should be filtered so that the amount of filtered liquid
will support all of the analyses required. For wastes con-
taining >0.5 % dry solids <10.2 or 10.3), use the percent
solids information obtained in 10.2 to determine the op-
timum sample size (100-g minimum) for filtration. Sufficient
solid should be generated by filiation to support the analyses
to be performed on the method extract
11.7 Allow slurries to stand to permit the solid phase to
settle. Wastes that settle slowly may be centrifuged prior to
filtration. Use centrifugation only as an aid to filtration. If
the waste is centrifuged, the liquid should be decanted and
filtered followed by filtration of the solid portion of the waste
through the same filtration system.
11.8 Quantitatively transfer the waste sample (liquid and
solid phases) to the filter holder. Spread the waste sample
evenly over the surface of the filter. Allow the sample to
warm to room temperature in the device before filtering.
Note 10—If some waste material (>l * of original sample weight)
has obviously adhered to the container used to transfer the sample to the
fitration apparatus, determine the weight of this residue and subtract it
ton the sample weight determined in 10.2.5 to determine the weight of
die waste sample that will be filtered.
11.8.1 Gradually apply gentle pressure of 1 to 10 psi (7 to
70 kPa), until the pressurizing gas moves through the filter. If
this point is not reached below 10 psi (69 kPa), and if no
additional liquid has passed through the filter in any 2-min
interval, slowly increase the pressure in 10-psi (69-kPa)
increments to a maximum of 50 psi (345 kPa). After each
incremental increase of 10 psi (69 kPa), if the pressurizing
gas has not moved through the filter, and if no additional
liquid has passed the filter in any 2-mio interval, proceed to
the next 10-psi (69-kPa) increment When the pressurizing
gas begins to move through the filter, or when the liquid flow
has ceased at 50 psi (345 kPa) (that is, filtration does not
result in any additional filtrate within any 2-min period),
stop the filtration.
Nora 11—Instantaneous application of high pressure can degrade
the glass fiber filter and may cause premature plugging.
11.9 The material in the filter holder is defined as the
solid phase of the waste, and the filtrate is defined as the
liquid phase. Measure the pH of the filtrate. Measure the
volume of the filtrate (F,) if the data are to be combined
i mathematically. Use a graduated measuring cylinder for the
volume measurement The liquid phase may now be ana-
lyzed (see 11.13) or stored at 4*C until the time of analysis.
Note 12—Some wastes, such as oily and some paint wastes, will
obviously contain some material that appears to be liquid. Even after
•PPfying the pressure filtration as outlined in !0.2.7, this material may
¦wt filter. If this is the case, the material within the filtration device is
defined as solid. Do not replace the original filter under any circum-
**aces. Use only one filter.
11.10 If the waste contains <0.5 % dry solids (see 10.3),
Proceed to 11.14. If the waste contains >0.5 % solids (see
1Q-2 or 10.3), proceed to 11.11.
11.11 Quantitatively transfer the solid residue retained by
Jhe filter, or the solid sunple if it did not require filtration,
an extractor bottle. Include the filter if it was used to
separate the initial liquid from the solid phase.
11.12 Determine the amount of extraction fluid to add to
the extractor as follows:
weight of extraction fluid
20 x percent solids (10.2.°)
x weigh:¦—'.2.1.7,
100
Slowly add this amount of appropriate extraction fluid (see
10.4) to the extractor vessel. Close the extractor borJe tightly
(it is recommended that polytetrafluoroethy'cne tape be used
to ensure a tight seal), secure in a rotary agitation device, and
rotate at 30 ± 2 r/min for 18 ± 2 h. Ambient temperature
(that is, temperature of the room in which the extraction
takes place) shall be maintained at 23 ± 2'C during the
extraction period.
Note 13—As agitation continues, pressure may build up within the
extractor bottle for some types of wastes (for example, limed or calcium
carbonate-containing waste may evolve gases such as cartxm dioxide).
To relieve excess pressure, the extractor bottle may be taken under a
hood and opened carefully from time to time (for example, after 15 miit
30 min, and 1 h).
11.13 Within 2 h, following the 18 ± 2 h extraction,
initiate the separation of the material in the extraction vessel
into its component liquid and solid phases by filtering
-through a new glass fiber filter, as outlined in 11.8. For final
filtration of the method extract the glass fiber filter may be
changed, if necessary, to facilitate filtration. Filters) shall be
acid-washed (see 6.4) if inorganics are of concern.
11.14 Prepare the method extract as follows:
11.14.1 If the waste contained no initial liquid phase, the
filtered liquid material obtained from 11.13 is defined as the
method extract Proceed to 11.15.
11.14 2 If compatible (for example, multi-phase waste will
not result upon combination), combine the filtered liquid
resulting from 11.13 with the initial liquid phase of the waste
obtained in 11.8. This combined liquid is defined as the
method extract Proceed to 11.15.
11.14.3 If the initial liquid phase of the waste, as obtained
from 11.8, is. not or may not be compatible with the filtered
"liquid resulting from 11.13, do not combine these liquids
Analyze these liquids, collectively defined as the raethoc
extract and combine the results mathematical!). as de-
scribed in 11.15.
11.15 Following collection of the method extracr. the pH
of the extract should be recorded. The volume of the extract
(V2) shall be measured if the data are to be combined
mathematically. Use a graduated measuring cylinder for
volume measurement Immediately aliquot and preserve the
extract for analysis. Metals aliquots must be acidified with 1
N nitric acid to pH <2. If precipitation is observed upon the
addition of nitric acid to a small aliquot of the extract the
remaining portion of the extract for metals analyses shall not
be acidified and the extract shall be analyzed as soon as
possible. All other aliquots must be stored under refrigera-
tion (4*Q until analyzed. The method extract shall be
prepared and analyzed according to appropriate analytical
methods. Hie method extracts to be analyzed for metals shall
be acid-digested except in those instances in which digestion
causes a loss of metallic contaminants. If an analysis of the
undigested extract reveals that the concentration of any
149
N-310
-------
# D 5233
regulated metailic contaminant exceeds the acceptance level,
the waste fails the test and digestion of the extract is not
necessary. However, data on undigested extracts alone
cannot be used to demonstrate that the waste met the set
acceptance level. If the individual phases are to be analyzed
separately, determine the volumes of the individual phases
(to ±3 %), using a separator}- funnel and graduated cylinder.
Conduct the appropriate analyses, and combine the results
mathematically by using a simple volume-weighted average:
... .
final analyte concentration «= (4)
K, + V2
where:
V, « volume of the initial phase (filtrate, L),
C, ¦ concentration of the contaminant of concern in the
initial phase (mg/L),
V2 m volume of the extract (L), and
C2 ¦= concentration of the analyte of concern in the extract
(mg/L).
Nan !0.5 %.
13. Quality Assurance Requirements
13.1 Maintain all data, including quality assurance data,
and keep them available for reference or inspection.
13.2 All quality control measures described in the appro-
priate analytical methods shall be followed. If the analytical
quality control requirements are not specified in the appro-
priate method, follow the requirements in 13.3 and 13.4 and
refer to Practice ES 16.
13.3 A minimum of one blank (using the same extraction
fluid and equipment as used for the samples) for-every ten
extractions that have been conducted shall be used as a check
to determine whether any memory effects from the extrac-
tion equipment are occurring.
13.4 A matrix spike shall be performed for each waste
type where the compositions of the waste matrices are
significantly different.
TABLE 2 Precision Data
Ugh Strtngth
Low Strang* ~
Mean. S
21.0
1.9
Standard deviation. *
3.0
0.63
Note IJ—It is recommended that it be assumed that each sample
has a significantly different composition unless previous data would
indicate otherwise (for example, regular sampling of steady-state ptoses
streams). If more than 20 samples of the same waste are being tested, i
matrix spike must be performed for every 20 samples.
13.4.1 The matrix spikes are to be added after filtration
and combination, if necessary, of the method extract and
before preservation.
13.4.2 Matrix spike levels should be established at the
appropriate acceptance levels. If the analyte concentration in
the method extract is less than one half of the acceptance
level, the spike level may be as low as one-half the analyte
concentration. However, it shall not be less than the
quantitation limit or one-fifth of the acceptance level. la
order to avoid differences in the matrix effects, the matrix
spikes must be added to the same nominal volume of the
method extract as that which was analyzed for the unspiked
sample.
13.4.3 The purpose of the matrix spike is to monitor the
performance of the analytical method used and to determine
whether matrix interference exists. The use of other internal
calibration methods, modifications of the analytical
methods, or the use of alternate analytical methods may be
needed to measure accurately the analyte concentration of
the method extract when recovery of matrix spike is below
the expected analytical method performance.
13.4.4 Acceptable sample holding times are outlined in
9.7. Exceeding the holding time is not acceptable to establish
any compliance with the acceptance levels, but it may be
used if the samples are not in compliance.
14. Precision and Bias
14.1 Precision—The precision of the procedure in Test
Method D 5233 for measuring the sample disintegration,
surface area increase, has been evaluated. The fractions
retained on 9.5 mm sieve were measured in three laborato-
ries. In each laboratory, duplicate, monolithic samples not
passing a 9.5 mm sieve of four high strength and four low
strength materials were extracted (see Table 2). The weight of
the residual 9.5-mm size fractions was measured and ex-
pressed as a percent of the initial sample weight.
14.2 Bias—The procedure in Test Method D 5233 for
measuring extract generation has no bias because the value
of extract is defined only in terms of this method.
15. Keywords
15.1 batch; extraction; laboratory; leaching; single; sludge;
solid; solidified; testing; waste
The American Society lor Tasting and Materials takes no position respecting the validity of any patent rights assarted in connection
with any item mentioned in this standard. Users at the standard are asprassly advised that determination ot 11m validity 0I arty mcfi
patent righ.s, anC tnc ris« o: intringement at such rights, are entirety therr own responsibility.
This standard is subject to revision a! any time by the responsible technical committee and must Be reviewed every five years and
Knot revised, either reapproved or withdrawn. Your comrmnts are Invited either tor revision of mis standard or tor additional standards
and should be addressed to ASTU Headquarters. Your comments will receive careful consideration at a meeting cf the responsible
technica! committee, which you may attend. It you laei that your comments nave not received a /air hearing you should make your
views known to the ASTM Committee on Standards, 1916 flae» Sr.. Philadelphia. PA 19103.
-------
N-5
Percent Solids
N.-515
-------
2-S4
the sample. Refrigerate sample at 4*C up to the time of analysis
to minimize microbiological decomposition of solids. Preferably
do not hold samples more than 24 h. In no case hold sample
more than 7 d. Bring samples to room temperature before anal-
ysis.
4 Selection of Method '
Methods B through F are suitable for the determination of
solids in potable, surface, and saline wateis, as well as domestic
and industrial wastewaters in the range up to 20 000 mg/L.
PHYSICAL 4 AGGREGATE PROPERTIES (2000)
Method G is suitable for the determination of solids in sedi-
ments, as well as solid and semisolid materials produced during
water and wastewater treatment.
S. Bibliography
Thejuauit, E.J. A H.H. Wagenhals. IVU. stuoies oi jepiesewauve
sewage plants. Pub. Health Bull. No. 132.
U.S. Environmental Protection Agency, 1979. Methods for Chem-
ical Analysu of Water and Wastes. Publ. 600/4-79-020, rev. Mar.
1983, Environmental Monitoring ind Support Lab., U.S. Environ-
mental Protection Agency, Cincinnati, Ohio.
2540 B. Total Solids Dried, at 103-105°C
1. General Discussion
a. Principle: A well-mixed sample is evaporated in a weighed
dish and dined to constant weight in an oven at 103 to 105°C.
The increase in weight over that of the empty dish represents
the total solids. The results may not represent the weight of actual
dissolved and suspended solids in wastewater samples (see above).
b. Interferences: Highly mineralized water with a significant
concentration of calcium, magnesium, chloride, and/or sulfate
may be hygroscopic and require prolonged drying, proper des-
iccation, and rapid weighing. Exclude large, floating particles or
submerged agglomerates of nonhomogeneous materials from the
sample if it is determined that their inclusion is not desired in
the final result. Disperse visible floating oil and grease with a
blender before withdrawing a sample portion for analysis. Be-
cause excessive residue in the dish may form a water-trapping
crust, limit sample to no more than 200 mg residue (see 2540A. 2).
2. Apparatus
a. Evaporating dishes: Dishes of 100-mL capacity made of one
of the following materials:
1) Porcelain, 90-mm diaro.
2) Platinum—Generally satisfactory for ail purposes.
3) High-silica glass,*
b. Muffle furnace for operation at 550°C.
c. Steam bath.
d Desiccator, provided with a desiccant containing a color
indicator of moisture concentration or an instrumental indicator.
e. Drying oven, for operation at 103 to 105*C.
/. Analytical balance, capable of weighing to 0.1 mg.
g. Magnetic stirrer with TFE stirring bar.
k Wide-bore pipeaA
3. Procedure
a. Preparation of evaporating dish: If volatile solids are to be
measured ignite clean evaporating dish at J50*C for 1 h in a
muffle furnace. If only total solids are to be measured, heat clean
dish to 103 to 105°C for 1 h. Store and cool dish in desiccator
until needed. Weigh immediately before use.
b. Sample analysis: Choose a Simple volume that will yield a
residue between 10 and 200 mg. When very low total solids are
encountered (less than 10 mg/L), less residue may be collected;
compensate by using a high-sensitivity balance (0.002 mg). Pipet
a measured volume of well-mixed sample to a preweighed dish
and evaporate to dryness on a steam bath or in a drying oven.
Stir sample with a magnetic stirrer daring transfer. If necessary,
add successive sample portions to the same dish after evapora-
tion. When evaporating in a drying oven, lower temperature to
approximately 2°C below boiling to prevent splattering. Dry
evaporated sample for at least 1 h in an oven at 103 to lOS'C,
cool dish in dericcator to balance temperature, and weigh. Re-
peat cycle of drying, cooling, desiccating, and weighing until a
constant weight is obtained, or until weight change is less than
4% of previous weight or 0.5 mg, whichever is less. When weigh-
ing dried sample, be alert to change in weight due to air exposure
and/or sample degradation. Duplicate determinations should agree
within 5% of their average.
4. Calculation
mg total Jolidi/L
(A - B) x 1000
sample volume, mL
* Vycm, product 0i Coming GUu Works, Coniiag, N.Y., or »quivikci.
f Kimble No». JTOOS or 370MB, or equivalent.
where:
A - weight of dried residue 4- dish, mg, and
B • weight of dish, mg.
£ ftl« ,111 il¦ ?,ii .hi
o. precision
Single-laboratory duplicate analyses of 41 samples of water
and wastewater were made with a standard deviation of differ-
ences of 6.0 mg/L.
6. Bibliography
Symons, G.E. 4 B. Morey. 1941. The effect of drying time 00 the
determination of solids in sewage and sewage sludges. Sewage Works
J. 13:936.
N-313
-------
SOUDS (2540)/lntrodudion
2-53
2540
2540 A.
The terms "solids," "suspended," and "dissolved," as used
herein, replace the terms "residue," "nonstable," and "fil-
trable" of editions previous to the 16th. Solids refer to matter
suspended or dissolved in water or wastewater. Solids may affect
water or effluent quality adversely in a number of ways. Waters
with high dissolved soiids generally are of inferior palatabUity
and may induce an unfavorable physiological reaction in the
transient consumer. For these reasons, a limit of500 mg dissolved
solids/L is desirable for drinking waters. Highly mineralized waters
also are unsuitable for many industrial applications. Waters high
in suspended solids may be esthetically unsatisfactory for such
purposes as bathing. Solids analyses are important in the control
of biological and physical wastewater treatment processes and
for assessing compliance with regulatory agency wastewater ef-
fluent limitations.
1. Definitions
'Total solids" is the term applied to the material residue left
in the vessel after evaporation of a sample and its subsequent
drying in to oven at a defined temperature. Total solids includes
"total suspended solids," the portion of total solids retained by
a filter, and "total dissolved solids," the portion that passes
through the filter.
The type of filter bolder, the pore size, porosity, area, and
thickness of the filter and the physical nature, particle size, and
amount of material deposited on the filter are the principal fac-
tors affecting separation of suspended from dissolved solids.
"Dissolved solids" is the portion of solids that pases through a
filter of 2.0 nm (or smaller) nominal pore size under specified
condition. "Suspended solids" is the portion retained on the
filter.
"Fixed solids" is the term applied to the residue of total,
suspended, or dissolved solids after beating to dryness for a
specified time at a specified temperature. "lie weight loss on
ignition is called "volatile solids." Determinations of fixed and
volatile solids do not distinguish precisely between inorganic and
organic matter because the loss on ignition is not confined to
organic matter. It includes losses due to decomposition or vol-
atilization of some mineral salts. Better characterization of or-
ganic matter can be made by such tests as total organic carbon
(Section 5310), SOD (Section 5210), and COD (Section 5220).
"Settleable solids" is the term applied to the material settling
out of suspension within a defined period. I> may include floating
material, depending on the technique (2540F.3i).
2. Sources of Error and Variability
Sampling, subsampling, and pipe ting two-phase or three-phase
ssr.p:.*. iruv .ntrod-ice serious errors. Make and keep such sam-
* Appiwtj by Stsadard Methods Conotocc, !»I.
SOLIDS*
Introduction
pies homogeneous during transfer. Use special handling to insure
sample integrity when subsampling. Mix small samples .with a
magnetic stirrer. If suspended solids are present, pipet with wide-
bore pipets. If part of a sample adheres to the sample container,
consider this in evaluating and reporting results. Some samples
dry with the formation of a crust that prevents water evaporation;
special handling is required to deal with this. Avoid using a
magnetic stirrer with samples containing magnetic particles.
The temperature at which the residue is dried has an important
bearing on results, because weight losses due to volatilization of
organic matter, mechanically occluded water, water of crystal-
lization, and gases from heat-induced chemical decomposition,
ts well as weight gains due to oxidation, depend on temperature
and time of heating. Each sample requires close attention to
desiccation after drying. Minimize opening desiccator because
moist air enters-. Some samples may be stronger desiccaats than
those used in the desiccator and may take on water.
Residues dried at 103 to 1Q5°C may retain not only water of
crystallization but also some mechanically occluded water. Loss
of C02 will result in conversion of bicarbonate to carbonate.
Loss of organic matter by volatilization usually will be very slight.
Because removal of occluded water is marginal at this temper-
ature, attainment of constant weight may be very slow.
Residues dried at 180 ± 2°C will lose almost all mechanically
occluded water. Some water of crystallization may remain, es-
pecially if sulfates are present. Organic matter may be lost by
volatilization, but not completely destroyed. Loss of CO; results
from conversion of bicarbonates to carbonates and carbonates
may be decomposed partially to oxides or basic salts. Seme chlo-
ride and nitrate salts may be lost. In general, evaporating and
drying water samples at 180°C yields values for dissolved solids
closer to those obtained through summation of individually de-
termined mineral species than the dissolved soiids values secured
through drying at the lower temperature,
To rime filters and filtered solids and to dean labware us:
Type HI water. Special samples may require a higher qualm-
water, see Section 1080.
Results for residues high in oil or grease may be questionable
because of tbe difficulty of drying to constant weight in a rea-
sonable lime.
To aid in quality assurance, analyze samples in duplicate. Dry
samples to constant weight if possible. This means multiple drying-
oooling-weighing cycles for each determination
Analyses performed for some special purposes may demand
deviation from the stated procedures to include an unusual con-
stituent with the measured solids. Whenever such variations of
technique are introd'iced, record and present th»m with the rr-
suits.
3. Sample Handling and Preservation
Use resistant-glass or plastic bottles, provided that the material
is suspension does not adhere to container walls. Begin analysis
as soon as possible because of the impracticality of preserving
N-314
-------
N-6
Proximate and Ultimate Protocols
N-3T5
-------
Designation: D 3172 - 89 (Reapproved 1997J7)
AMCRCAN 90OETY FOR TESHNO AND MATERIALS
100 9m Hvtttr Or. Wm Ccmbchsxkm, P* 1««38
»tm tw *mM bom of AST** Saneares. Copyn^t ASTM
Standard Practice for
Proximate Analysis of Coal andd Coke1
Ito atadud n mart undo' lie bad tefeuiioa D 3JT2j Ac bunumber unmtiiiattijf (bOmmf tbc dniiailica bsdiorai the yar of
idoptiDO or, in lb* eat oficvifioo. H* yew ofl«* iwaioiioa. A luaktbpuothaa Mksta the jor ofM f-appcwL A
¦umiuU* tpelon (0 initiaim in •d&eriai rtiiny «ioc» Ac tut it rrvmoo or mppronL
1. Scope
1,1 This practice covers the determination of moisture,
volatile matter, and ash and the calculation of fixed carbon
oa coals and cokes sampled and prepared by prescribed
methods and analyzed according to ASTM established pro-
cedures.
1J This standard does not purport to address all of the
safety concerns. If any, associated with its use. It is the
responsibility of the user of this standard to establish appro-
priate safety and health practices and determine the applica-
bility of regulatory limitations prior to use.
2. Referenced Documents
2.1 ASTM Standards:
D346 Practice for Collection and Preparation of Coke
Samples for Laboratory Analysis5
D388 Classification of Coals by Rank2
D 2013 Method of Preparing Coal Samples for Analysis1
D2234 Test Methods for Collection of a Gross Sample of
CoaF
D 3173 Test Method for Moisture in the Analysis Sample
of Coal and Coke3
D3174 Test Method for Ash in the Analysis Sample of
Coal and Coke from Coal2
D3175 Test Method for Volatile Matter in the Analysis
Sample of Coal and Coke2
' IMi wc«ic» a uadtr tti« jurisdiction of ASTM Cnmmittw D4 aa Coil «ad
Cak* ud ia Ibe dk«ct rapoaabiiny of Sabcoaustee D0J.2I 00 Mnbodi of
AMtfym.
Current sdiiioa «pprowxi Sept 29, 1989. PabBhed Fdxmry 1990. Ontitifi;
fatttted «» D Jl« - 73. U* ptrrfam aditioa D 3m-73(19S4)«'.
3 Ammai Mali of ASTM SlMdardt, VolQS.03.
3. Terminology
3.1 Definition:
3.1.1 proximate analysis of coal and coke—an assay of the
moisture, ash, volatile matter, and fixed carbon as deter-
mined by prescribed methods. Other constituents such as
sulfur and phosphorus ire not included.
4. Significant* and Uk
4.1 Test methods, as herein described, can be used to
establish the rank of coals, show the ratio of combustible to
incombustMe constituents, provide the basis for buying and
¦effing, tad evaluate for beneficiation or for other purposes.
5. Sampling
S.I Coal sample collection shall be in accordance with
Sections 5 and 6 of Classification D 388, if the proximate
analysis is to be used for classification of coal by rank, la all
other cases, sample collection shall be is accordance with
Test Methods D 2234. Preparation shall be in accordance
with Method D 2013. Coke sampling shall be in accordance
with Method D 346.
«. Test Methods
6.1 Moisture—Tact Method D 3173.
6.2 Ash—Test Method D 3174.
6.3 Volatile Matter—Test Method D 3175. If the modi-
fied procedure is required, the report should show that the
modified procedure was used.
6.4 Fixed Carbon—The fixed carbon is a calculated value.
It is the resultant of the summation of percentage moisture,
ash, and volatile matter subtracted from 100. All percentages
shall be on the same moisture reference base.
Fixed carbon. * - 100 -
' (moisture, %
+ ash, % + volatile matter, %)
T?» Am** SedNr tor rwig emf «¦¦*» Hi* flBpemnebi leipeellie »• nld^f of aoyflWfliiew* ewrW Jo eom*a*n
¦« eny «wi me«te*< »i t6* ewdeifli Uw* fl# Ws itmaw ef sri «»nwiy ediiW tt* dWeinWen o< #» wWiry e# wy euefi
fimt /fern, and m rkt of tMngmm* at ausft ngm. m ««htwy Weir own r«pamfe*tr.
«»«r fMnpnMtf or Mtridram. r«ur eomnMiammiPMM eitarlariwMMt of KM aewnted or
mdtnoJd t>t mXtmte »A57M H—fcmrwn your octnmrttntt trff iveaAw OMftjf NfNttmMon « • (nidng ct w rmpomib*
IkAM eommee* wwi iw alwid.» y* W W |«r w eemeimei Jew w mertW « M #w*» jee efieuy ifw«» your
rtm mam b tr» AS7V Commem on Standana; 100 tmr IHrimba Mm. mm CnnrttfMMn, PA nm.
1
N-316
-------
(Jjjjm Designation: D 4238 - 97
MBKAN soeam KR TCSTMB Me kWTSIMLS
f00 tor Haitxx Or. W« Cmncftocw. f>A
Standard Test Methods for
Sulfur in the Analysis Sample i of Coal and Coke Using High-
Temperature Tube Furnace (Combustion Methods1
Tim Basted a toued under the bed todtmHoo D 423* *e lie Baate Jaac&Mr Marias A* dotewcies hdetts te jar of
animal tdcptioa ar, in toe cm of miriaa, 1M ym of M mMta. A tamtac io psranfeaa iadkau tfee ym at iMt nm&nrtL a
mpeneript cp>0oo (<) iadkaai
1. Scope
1.1 These test methods cover three alternative procedures a
using high-temperature tube furnace combustion methods Is
tor the rapid determination of sulfur in samples of coal and d
coke.
1J These test methods appear in the following order
Uttkoi A—Kith-TempCTturt Corafcueioo Method vitfc Add
'SueTluvioftOeuciixm Procedural • *>*
Method *—Hfch.TetnpcraUue CombiotiOB Method will)
loifimflric Tilistkat Detection Procedure 10 to IJ
Method C—Higb-Tcrapwimre Corabtotioe Method wkk I»
Bared Atampuat) Deudion Procedural 14 la U
1JLI When automated equipment is used to perform my y
of the three methods of this test method, the procedures can n
be classified as instrumental methods. There are several il
manufacturers that offer to the coal industry equipment with h
instrumental analysis capabilities for the determination of jf
the sulfur content of coal and coke samples.
13 This standard does not purport to address MI of these
safety concerns, if any, associated with its use. It is thew
responsibility of the user of this standard to establish appro- >
priaie safety and health practices and determine the apptica- j-
bility of regulatory limitations prior to use. See 7.8 and 152. L
2. Referenced Documents
XI ASTM Standards:
D346 Pnactix for Collection and Preparation of Cokex
Samples for Laboratory Analysis'
D1193 Specification for Reagent Water1
D 2013 Method of Preparing Coal Samples for Analysis2 ;
D 2361 Test Method for Chlorine in CoaP
D3173 Test Method for Moisture in the Analysis Samplele
of Coal and Coke3
D3176 Practice for Ultimate Analysis of Coal and Coke3 1
D3180 Practice for Calculating Coal and Coke Analyses*
from As-Determined to Different Bases*
D4208 Test Method for Total Chlorine in Coal by the*
Oxygen Bomb Combustion/Ion Selective Electrode le
Method1
D462I Guide for Accountability and Quality Control inn
the Coal Analysis Laboratory2
> Tha tat mrJiod ii under the juriidictiaa of ASTM Gans&ue D-J os Coal ai
tw* Coke tad b the diras nwooibiliiy of Satcernmilwr DC121 oo Metfcodi of of
A>z!ym.
C-t.tni einicn arpraved June 10, 1997. Pabtisfcad May 1991. OrifauilyBy
pubtaiud •> D42J9-13. Ljb! prevxnu edition D 420 >94.
* Annuel Book of ASTM Standards, Vol 03.03.
» Ahum! Book ofASTU Slmdarts, Vol 1UH.
DS142 Test Methods for the Proximate Analysis of the
Analysis Sample of Coal and Coke by Instrumental
¦ Procedural*
3. Summary of Ted Methods
3.1 Method A—High-Temperature Combustion Method
with Acid-Base Titration Detection Procedures—A weighed
sample is homed is a tube ftirnace at a minimum operating
temperature of I35CC in a stream of oxygen. During
combustion, all sulfur contained in the sample is oxidized to
gaseous oxides of sulfur (sulfur dioxide, SO* and sulfur
trioxide, SOJ and the chlorine in the sample is released as
02. These products ate thai absorbed into a solution of
hydrops peroxide (HjOa) where they dissolve forming
dilute solutions of sulfuric (HjS04) and hydrochloric (HQ)
acids. The tjnantities of both acids produced are directly
dependent upon the amounts of sulfur and chlorine present
in the original coal sample. Once the amounts of eacii acid
ptesent have been determined, the pcrcentagt of sulfur
contained in the coal may be calculated
3.1.1 This method is written to inchide commercially
available sulfur analyzers that must be calibrated with
appropriate standanl reference materials (SSMs) to establish
recovery fectors or a caHbraticn curve based on the range of
sulfur in the coal or coke samples bdng.analyzed
Hon 1—Beams ort&urfly present b eori do bm intnfat in
Method A (3. IX irifli the aeeptao ofehloene; mato mm he coawsed
for chlorine content af the auupla 3.1).
3 2 Method B—High-Temperature Combustion Method
with Iodimetric Detection Procedures—A weighed sample is
burned in a tube furnace at a minimum operating tempera-
ture of 1350*C in a stream of oxygen to ensure the oxidation
of sulfur. The combustion products axe absented in an
aqueous solution that contains iodine. When sulfur dioxide
is scrubbed by the diluent, the trace iodine originally present
in the solution is reduced to iodide, thus causing an increase
in resistance. The detection system of the instrument consists
of t polarized dual platinum electrode. Any change in
resistance of the solution in the vessel is detected. Iodine
titraut is then added proportionally to the reaction vessel
until the trace excess of iodine is replenished and the solution
resistance is reduced to its initial level The volume of titrant
b wrt»« nriclate the n'B»r nf
sample. The method is empirical; therefore, the apparatus
must be calibrated by the use of standard reference mated?.]
(SUM).
3X1 Tim method is designed to be used with «»imer-
daBy available sulfur analyzers, equipped to perform the
preceding operation automatically, and must be calibrated
N-317
-------
D 4:4239
wlili an appropriate sample {5.4} based on the range of sulfiar
is each coal or coke sample analyzed.
Han 2—Notuutomatic systems may be used with tbe titration
procedures and calculations performed manually by quaUScd laboratory
teehainm. the resulting loa in accuracy or speed, or both, wotdd then
negate die advaautet of toing tbe fully automatwi instrumental
approach. /
3.3 Method C—High-Temperature Combustion Method
with Iitframd Absorption Detection Procedures—The sample
Is bunted ia a tube furnace at a minimum operating
temperature of 1350*C in a stream of oxygen to oxidize tbe
aulKir. Moisture and particulates are removed from the gas
by traps filled with anhydrous magnesium perchlorate, The
gas stream is passed through a cell in which sulfur dioxide is
measured by an infrared (LR) absorption detector. Sulfur
dioxide absorbs IR energy at a precise wavelength within the
IR spectrum. Energy is absorbed as the gas passes through
tbe ceO body in which the 1R energy is being transmitted:
thus, at the detector, less energy is received. All other IR
energy is eliminated from reaching tbe detector by a precise
wavelength filter. Thus, the absorption of IR energy can be
attributed only to sulfur dioxide whose concentration is
proportional to the change is energy at the detector. One cell
is used as both a reference and a measurement chamber.
Total sulfur as sulfur dioxide is detected on a continuous
baas. This method is empirical; therefore, the apparatus
must be calibrated by the use of SRMs.
33.1 This method is for use with commercially available
sulfur analyzers equipped to carry out the preceding opera-
tions automatically and must be calibrated using standard
reference material (coal) of known sulfur content based on
the range of sulfur in each coal or coke sample analyzed.
4. Significance and Use
4.1 Determination of sulfur is, by definition, part of the
ultimate analysis of coal
42 Results of the sulfur analysis are used to serve a
number of interests: evaluation of coal preparation, evalua-
tion of potential sulfur emissions from coal combustion or
conversion processes, and evaluation of the coa] quality in
relation to contract specifications, as well as other scientific
purposes.
4,3 The instrumental analysis provides a reliable, rapid
method for determining the concentration of solftir in a lot
of coal or coke and are especially applicable when results
must be obtained rapidly for the successful completion of
industrial, beneficiatioc, trade, or other evaluations.
5. Sample
3,1 The sample shall be the material pulverized to pass
No. 60 (250-tun) sieve and mixed thoroughly ia accordance
with Method D 2013 or Practice D 346.
Han 3—it atty be dHfictik to mm (be pfCCisOO S&tt6EB€8t9> of
Section 19 wtohijh mineral contest ctah are pound to jama 60 meih.
Wbe» the precision at analysis required caoaot b« obtained, b ia
recommended that the coals be ground to p*ai through a No. 100
(tSOiua) neve. The icdncod particle fee dwold mail in a more
i as-detennined basis can be made.
5 J Procedures for converting tt^ieisrsjiauu jvi'V c'ccs
t obtained from the analysis sample to other bases are de-
t scribed is Practices D 3176 and D 31&5.
5.4 Standard Reference Material (SRM) such as SRM
1 Not 2682 through 2685Sktyvr in coa' wniui consist ot
1 four different coals that have been individually crushed and
I ground to pass a 60-mesh sieve, and bottled it SO-g units, or
« other commercially available reference coals with a certified
t sulfur content.
METHOD A—eiCH-TEMPERATUEI COMBUSTION
method wrra jusd-base tmutiON detection
ROCEDUKES*
i 6. Apparatus
6.1 Tube Furnace—Capable of hearing 150- to 175-mm
> area thot zone) of the combustion tube (6.2) to at least
. 1350*G It is usually heated electrically using resistance rods,
i a resistance wire, or molybdenum dialicide elements. Spe-
< cific dimensions may vary with manu&ctum'j design.
Hon 4—Induction tenaee MfNiqaet may be used jro-ided is oa
I be riwwritbattfcey meet tf* precis^ rtquirraenti of Sectioc 19.
62 Combustion Tube—Approximately 28-om internal
< diameter with a 3-mm wall thickness and 750 mm in length
l made of porcelain, zircon, or mnllite. Ft must be gastight at
i working temperature. The combustion may be carried out in
i a tapered-end tube that is dosdy connected to the ps
t abaorber by high temperature tubing with gastight joints.
< Acceptable configurations include connecting the tapered-
< end tube directly to Ihedbow of the Bitted gas bubbler or to
< a 10/30 standard taper-ground joist that is attached to a hest
i resistant glass right a^e bend. The tempetatuie at the
1 tapered end of the tube should be maintained high enough to
I prevent condensation in the tube hsd£
6.2.1 Alternativriy, a high-temperature straight refractory
t tube may be used, if available. It requires a silica adaptor
( (641) with a flared end that fits inside the combustion tube
i and serves as aa exit for the gases.
6 J Flowmeter, for measuring as oxygen flow rate op to
: loymin.
6.4 Sample Combustion Boats, most be made of iron-free
i material and of a convenient size suitable for the dimensions
< flf thf mcH
6.5 Boat PuBtF—Rod of a heat-resistant material with a
\ bent iff disk end to insert and remove boats from the
< combustion tube.
6J.I Ifthe boat pulkr is to remain within the combustion
I tube while the boat is moved into the hot zone, it is necessary
t to pass tlie poller through a T-piece that ia fitted into a
i robber stopper at the inlet ofthe combustion, tube. The open
« end of tbe T-piace is sealed with a rubber stopper to permit
t movement of tbe pusher and prevent escape of tbe oxygen
52 A separate portion of the analysis sample should be
analyzed for moisture content in accordance with Test
Method D3I73, so that calculation to other than the
i 4f Ssinjuil ItaSsc&cc MifiBEBfeb y.ttTffT
¦ afStaadar*, W«hia ftacesu tlui
1 taw bmm mtoiiaot la vmmm iftb rMoriamd bylnxtrtxi fre—a rf to
N-318
-------
CD) I'D4239
To Vet ww
« SOIMll
f\f H
to It mm
3»ikcc
Moptor
• mm 0 0
X300*«
Vacuum
R«fyl«t«r
129ml 1 60s Afcwpito*
BofflM viift
friMvtf DiiM
•ttmoi 1.0
CmiMIIm Into*
7-TuM
Py^> SCM& Kgffc»r
¦ ¦ ¦' ¦' ¦ *
C«mbu«tk*n I Furaact
Staff*
••at »um
Mo.I St****'
« Ritttar TuM
l«v Mittr .Prttturt Rtfulaiar
¦M Nn«i Voir*
FIG. 1 Apparatus to tha DalanntwiaUun of feifur IMng AcM-Baaa Titration
-thai enters at the side limb of the T. The rubber stopper or r
tube should be checked often to avoid Itakagr
6.6 Gas Absorber or Analyzer Titration Vessel—A narrow
vessel or such diameter that the end of the tube from which
the gasses exit is inside the vessel and submerged to a depth
or at least 90 mm, when 200 mL of the peroxide solution
(7.4) is added to the vessel.
6.6.1 Alternatively, I25-mL capacity bottles with fritted
disk can be used for gas absorption. The bottles should be of
such a diameter that the fritted end is covered by the
peroxide solution to a depth of at least SO mm. The fritted
glass end porosity should be 15 to 40 nm. The bottles are
fitted in a series of two to the outlet end of the combustion
tube.
6.7 Gas-Purifying Train—Designed to be used with spe-
cific instruments, or a U-tube packed with soda asbestos may
be used. See configuration in Fig. I.
6.8 Vacuum Source—Needed if a negative pressure is
used to transport the gasses and combustion products
through the system.
6.9 Vacuum Regulating Bottle, containing mercury with
an open-ended tube dipping into the mercury, used with a
vacuum source.
6. JO Silica Adaptor, 300 mm long by 8 mm in outside
diameter and flared at one end to 26 mm. To be used with a
straight refractory combustion tube.
6.11 Other Cortfiguratiois of Apparatus—Complete sulfur
analyzer assembly units designed to perform functions sim-
ilar to this method, with automated features that perform the
sulfur analysis in a more rapid manner are commercially
available. These instruments may have combustion tube
dimensions and oxygen purifying apparatus that differ
slightly from those described in this method, but are accept- >
aide, provided equivalent values within the precision state- >-
stent of Section 19 are obtained
7. Reagents
7.1 Purity of Reagents—Reagent grade chemicals shall be e
lisei 10 zJl u-sti. Unless otherwise indicated, it is intended d
that all reagents shall conform to the specifications of the e
Committee on Available Reagents of the American Chem-1-
ical Society, where such specifications are available.' Other
grades may be used, provided it b first ascertained that the
reagent is of sufficiently high purity to permit its use without
lessening the accuracy of the detennination.
12 Purity of Water—Unless otherwise indicated, refer-
ences to water shall be understood to mean reagent water,
Type IV, conforming to Specification D 1193.
7.3 Aluminum Oxide (AJjOi)—findy divided and dried at
135CTC.
7.4 Hydrogen Peroxide (H3O3) Solution—One volume
percent (50 mL of 30 % HjOj with 1450 mL or water). The
pH is adjusted (using KaOH or H^SO* as appropriate) to that
which is used for the end point in the titration. Solutions
should be discarded after two or three Jays.
7.5 Indicator—Indicators that change color (titration end
point) between pH 4 and 3 are recommended, bat in no case
should the pH exceed 7. Adequate lighting and stirring to
ensure proper detection of the end point is essential A
choice of indicators or use of a pH meter is permitted (Note
5). Directions for preparing two acceptable mixed indicators
are as follows:
7.5.1 Mix 1 part methyl red solution (dissolve 0.125 g in
60 mL of ethanol and dilute to 100 mL with water) with 3
parts bromcresol green solution (dissolve 0.0S3 g in 20 mL of
ethanol and dilute to 100 mL with water). Discard the mixed
solution after 1 week.
7.5 J Mix equal volumes of methyl red solution (dissolve
0.125 g in 60 mL of elhand and dilute to 100 mL with
water) and methylene blue solution (dissolve 0.083 g in 100
mL of ethanol and store in a dark glass bottle). Discard the
mixed solution after 1 week.
Nora 3—Althoufh two cad-point indfctteis or a pH meter method
are rtnrrfhrrt, the me of the pH meter b accepted t* more definitive of
the end pohu of die titration proces and considered <0 five store
icpradaeible mwtti,
7.6 Soda-Asbestos, 8 to 20 mesh, if a U-tube is used.
7.7 Sodium Hydroxide. Standard Solution, 0JX5N—Dis-
• Ktaftnt Ckonfaob. Aiimiam Chemical Society Spte&katieas, Aacricts
Chmicil Society, WmMihwi. DC Fur muwiIom ea ibt *-**if ot ut
lined by the Ananas Chunks Society, tet Axalar Sumdanb Jor Laboratory
Chmkah, BDH Ud_ Fooie, Danet, UJL, and fix Untied Stales Pharmacopeia ¦
axJ National formulary, l)£ Phamuiceutical Cocraaio*, lac (USPQ.
Xfiekv&e, MD.
N-319
-------
# D 43239
TO
imiAMr jiwiw
tmyt
CiKCTROOf
KKUMMT UMC
AWT H«D>
COMUITIU*
tuu
RS&tr
woo
now
MCTtA
flt/Mif
—BH «TM
AMD NEtfitJ MWE
HQ. 2 Apparatus tor iiaOttMminaaon of
solve 2.05 g of sodium hydroxide (NaOH) la water and
to I L. Standardize against a primary standard.
- 72 Oxygen, 99,5 % Pure—Compressed gas contained in a
cylinder equipped with a suitable pressure regulator and a
needle valve to control gas flow. Wanting—Pure oxygen
vigorously accelerates combustion. All regulators, lines, and
valves should be ftte of grease and oiL
8. Procedure
8.1 Assemble tbe apparatus, as directed, by the instruc-
tions of tbe instrument manufketurer. Alternatively, tbe
apparatus shown to Rg. 1 can be assembled except do not
initially connect the rubber tube from the oxygen supply to
tbe soda asbestos U-tube.
82 Calibration—Sulfur analyzers must be calibrated at
least once on each day they are used, following the analysis
procedure outlined in Section 8, using coal or coke standards
(5.4) with sulfur values in the range of tbe samples being
analyzed. A recovery factor (F) or calibration curve must be
established and appropriately used is each calculation.
j. Actual Suite in Standard, Dry Baas
Analyzed SulAir Is Saadaid, Dry Basis
8 J Furnace A4/ustme>tt—^j3x the temperature of the
flinace to at least 1350*C. Bring the temperature op slowly,
allowing approximately 3 to 4 b in advance, to aOow
sufficient tiff to to a stable temperature. Be sue to
check tbe manufacturer's instructions for raising the temper-
ature of the furnace and heed any precautions for protecting
betting dfiisciits deterioration or thermal shock.
8.4 Titration Vessel Preparation—EH the titration vessel
is accordance with die manufacturer's instructions with
approximately 200 tnL of the gas absorption fluid (hydrogen
peroxide) (7.4). Adjust the pH of the solution to make it
definitely acidic by adding dilute sulfuric acid. If chemical
indicators (Instead of a pH meter) arc used, add five or six
drops of the indicator aad then add a very small quantity (as
required) of dilute sodium hydroxide (NaOH) to teach the
by th» ImBiwMc Dctaetfen Malted
e end point color that will be developed in tbe sulfur analysis.
8.4.1 If the apparatus with two gas absorption bottles is
n used, add 100 mL of 1 * H2Oj (7.4) to tbe bottles su that at
k least 30 ma of the Bitted disk is covered in the first bottle.
8.5 Oxygen Flow—Connect the oxygen supply and adjust
ti the oxygen flow to approximately 2 LA*iin with die oxygen
b baffle inserted in the entrance end of the ccmbustion tube.
£ Be sure to check manufacturer's instructions. The flow rate
a at tbe temperature of 1350*C should be sufficient to prevent
ti the formation ofoxida of nitrogen. Allow the oxygen to Sow
ti through the combustion tube for at feast 1 min before
u inserting any sample. Check the system for any possible
1) leaks.
8.5.1 If a vacuum source is used, daw air through tbe
a apparatus at about 350 mLfam, then connect tbe oxyges
s supply to tbe ttenbe and adjust the rate of flow of the oxygen
t> to 300 mL/min. The flow rate is adjusted by changing tbe
£ depth of the penetration into the mercury of the open-ended
I glass tube is the vacuum regulating bottle. The preliminary
a adjustment to 330 mL/min of air ensures that the cotmeo
t tioss at the outlet rfwt of the combustion tube are under
s slightly reduced internal pressure and no leak of combustion
I products should occur.
tfai* 6—A ftticlu MMbutioB tma nam be ecub&fand wife ta
t •dKpjWrf^prtxriamdy 300 B^min of pure oaysni
$ prior to t>»<« u yw^ptt«>w<
d toSa« »t* period the WaMempetmat tube ftmace » brousht to is
e epntiaa UMpwitiint at 1350X1 Tbe required pa flow nay be
• Mtibtttad by the we «t Mtead iunal mrnme, or ahoold the
¦ auaiALniiM-ipceay or t>* opetste-pnfcr, it aa be otolaai by ifae
a «se of a positive i»e*n«»*»iiep*»Mi«ili»faiJy above ttmoipherie
f «—tui to obtain iM nquired oxnpat Sow iws. is aB aura, tbe
I rmtwtimw aftiM ¦wimftrntrer of the emapaect ibeoU be Mowed.
1 TO»»l»*ppto»tbB«ddiikaof»ffideM|M«b»tptj»fi^»wdB
I M ID tfefittKBlfafy OfttelppBJWS.
t.6 Aiuftiis Sample Sat-Wo# out 0.5 g of the analysis
s sample to the nearest 0.1 log for coils containing up to 4.0 %
s sulfur, and 0.25 g to the nearest 0.1 mgofaaatyassmplefor
N-320
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# CD4239
RESISTANCE HEJkTMase IMS C
——
OOEN K»T COU»U«t»M TUfUBE
FLOW
coNmoitina
UUltirt*
OXYSEN
0U3HT
TftAlAP
aouo-
STATl
>—HCUaAaU!
•°*T 1
W
OfTaCTOM
SXHAU8T f
MEASUREMENT
UNIT
¦y *
MTESfBRAl
•LSCTNOMCS
AM)
MCROraocuaon
¦MJUKNCf
.
c
srstfwi
MKTS ,
no. 3 App*r*tu» rwtJMD^nmkMaloremoJ Sulfur by OwWiwwdDrt^fcnlfcrthod
coals containing over 4.0 % sulfur. Spread the ample evenly
in a combustion boat.
8.6.1 A this layer of AJ203 can be wed to line the sample
boat and^oover the sample to ensure complete combustion
and reduce splattering or loss of sample.
8.7 Sample Combustion—Remove the oxygen baffle or
robber stopper or both from the combustion tube aad put
tite charged sample boat into the islet end of the combustion
tube, approximately 270 mm from the center of the combus-
tion tube hot «ne. dose the combustion tube by replacing
the oxygen baffle or rubber stopper or both and, if necessary,
readjust the rate of Dow of the oxygen. Leave the boat in this
position for I to 3 min until the volatile® have been driven
off. This wiU also eliminate the "popping" and soot accumu-
lation in the right angle bend. Remove the oxygen baffle or
rubber stopper and move the sample boat slowly forward
until the boat is in the center of the hot zone, approximately
30 mm at the beginning of esch minute for 6 min is the
suggested schedule to ensure a slow heating rate. Be sure to
Remove the boat puller bow the hot zone and replace the
baffle or stopper after each movement AHow the sample to
bum in the hot zone for approximately 3 to 4 min until all
sulfur in the sample Is oxidized to sulfur dioxide (SOj) or
sulfur trioxide (S03). The complete sample burning time it
not more than 14 to IS min. This heating program has been
established for all types of coaL Where it is shortened for a
particular coal or by instruction of the manufacturer of a
particular sulfur analyzer, results should be checked against
those obtained by using fte longer heating schedule.
8.7.1 If the rubber stopper with the T-piece is used (6J.1),
the robber stopper remains in the end of the combustion
j permitted movement Into the
furnace through the T-piece. See Fig. I.
2.E Titration—Tai. g*sxs of combustion leave the com-
b'lcint] a-fy i*wj;sh the exit end and are dissolved in the
hyuufcin peroxide in the gas absorption bottles or analyzer
titration vessel forming a dilute sulfuric acid. Titrate the
contents of this vessel with 0.0SN sodium hydroxide (7.7),
i
backwashia* the titration vessel and inlet tubes acconfing to
manufacturer's instructions. The total acidity, because of
oxides of auHur and chlorine, is given according to the
following reactions:
SQj + H jOj -* HjSO*
dj+HjOj-ffla+o,
8.8.1 If die contents of the gas absorption bottles must be
transferred to a suitable titration flask, be sure to wash the
bottles and islet tube or silica adaptor with water (7 J) and
add these washings and five or six drops of indicator to the
titration flask before titrating with the 0.05N NaOH solution
(7.7).
8.8 J High-temperature combustion acid/base titration
suite analyzers may be designed to give a bam reading
directly in percent sulfur content of the coal sample, bat a
correction 931 must be made for acidity caused by chlorine
present in the sample using Test Methods D23€l or D 4208.
Nots ?—Ofteaaocotreclkm a m»de for the presence of chlorine in
tbe sunpie, or a percentage value (foond x a iclathciy invariant value
upon pdarkoowied|e of tlx hwny aaiiyxcd) s aitoicttd
from tbe pereesa salfiir toarmiaed. Tha method eao fee acceptable lor
cods of knows eUorise content however, far work of tbe highest
accuracy, the ynmu*g» of mast be
detemusiod analogically, asd oooectioa its prese&oe by
tubtoctmj aa eqabafcat value from a nine equivata to tfse total
aodxiy determined by tfw wiftw
9. Calculation*
9.1 Some anlfiir analyzers are designed to give buret
rea£ngs in percent julfiir, if the tstrast is adjusted and
BiadardiTfd to exactly QXfiN and the sample weight is
. exactly 0.500 g. After the observed percent sulfur has been
adjusted using the recovery factor or calibration curve, then
It must be collected for chlorine using the following calcula-
tion:
St- 1.503 (S*/l.«3 X F - £3, */3J4Q
where:
N-321
-------
41 D 4:4233
Se m sulfur corrected for chlorine {as determined), %\
St ¦ sulfur from buret reading, %;
F ¦» the recovery factor or fector taken from a calibra-
tion curve for the analyzer, and
a,* ¦ chlorine in sample (as determined), %.
9-2 0.. £X_Iyzi:s ;hit are dtsiiaet ~ y.i "Jim.: li&Zzz
in percent sulfur, but where the normafity of the titrantor
sample weight may vary from that prescribed,the following
calculation must be used:
St - 1.603 RJ» x N, * F x 10) - a %/3M6]/W
where:
Se - sulfur corrected for chlorine {as determined), %;
S* - sulfur taken from buret reading, %;
- normality of the sodium hydroxide:
F «¦ recovery factor or factor taken &om a calibration
curve for the analyzer;
a, *-chlorine in sample (as determined), %¦, aad
W - weight of sample, g.
93 When sulfur analyzers are used that have buret
reading} in nulHlitres of titrant, the following calculation will
apply.
St - 1.603 UV, x Nt x Fi - a */3J46]/H'
where:
Sg » sulfur corrected for chlorine (as determined), 9b;
St — sulfur taken from buret reading, %;
V, - sodium hydroxide, mL;
Nx * normality of sodium hydroxide;
CX%" chlorine in sample (as determined), R;
F "the recovery factor or factor taken from a calibra-
tion curve for the analyzer, and
W - weight of sample, g.
METHOD B—HIGH-TEMFERATUH COMBUSTION
METHOD Wrm IODIMETRIC TITRATION DETECTION
WtOCEDUHES
10. Apparatus
10.1 Analytical Apparatus—Designed to perform the
analysis procedure described in 3.2 automatically.
Not* S—It it Ksommended thai As analytical equipment be an
automated sulfur analyzer. Otherwise, the restrictions and limitations
given in Note 3 for nonautomaud systems apply.
102 Tube Furnace—Set 6.1.
103 Combustion Tube—Made of muflite, porcelain, or
zircon, approximately a 27-mm inner diameter, a 33-mm
outer fiameter, and 750 mm in length, with the last 23 mm
of the exit ***< reduced to 10-mm outer diameter and 5-mm
inner diameter to facilitate exit and collection of the gsses in
the titration vessel
10.4 Sample Combustion Boats—See 6.4.
10J5 Boat Puller—See 6.5.
11. Reagents
11.1 Pwily of Reagents—See 7.1.
I12 Purity of Water—See 7.2.
t iJ Iodine Tltram—Dissolve 2.5 f of iodine is 280 mL
of pyridine. Mix well and be certain all iodine is dissolved.
Add 7QC mL of methanol and 20 mL of water. (See Note 9.)
11.4 Diluent—Mix 280 mL of pyridine with 700 mL of
methanol and 20 mL of water. Mix well.
Now 9—Ahereat&e fbrmultoooi tsay be sutatiuiw! to the extent
t that t&ey as be demonstrated to yield equmlert tsdu ;s regirr to
i accuracy sud pedsion.
11J Oxygm-Sec7.i.
I 12. Procedure
12.1 Instrument Preparation:
12.1.1 Assemble the analytical apparatus according to the
i manufacturer's instructions. Check ill connections carefully
t to avoid leaks.
12.1.2 Set furnace temperature to 1350*G
I2.1J Set oxygen flow rate according to manufacturer's
i instructions.
1X1.4 Place approximately ISO mg of a coal sample in a
1 boat and insert into the 1350*C region of the furnace.
2 Sample boot should remain within the hot zone of the
i ftirnace for at least 2 min or until sample is completely
I burned. This action win serve to condition the apparatus in
t all functions.
122 Calibration:
122.1 Select a cod standard reference material (SRMX as
« described hi 3.4, which has a sulfur value in the range of the
: sample to be analyzed. Weigh out about 150 mg of this
1 previously dried coal standard and record the weight to the
i nearest 0.1 mg.
12.22 Inter the wei^it and sulfur content of the standard
t reference material sample into the memory of the analyzer.
12J3 Insert SRM sample into the 13S0*C region of the
1 furnace.
122.4 After outpoint is reached, not tag 2 min.
i record the titrant factor as milligrams sulfur per mQlilitre of
t titrant (mgS/mL). If analy2er does not have an integral
c computer, record the volume of titrant used and calculate
t titrant factor as instructed in 13.1.
12JLS Remove sample boat and repeat steps 122.1
t through 122.4 two more times.
12J2.6 If analyzer does not automatically average the
t titrant factors obtained in the calibration step and ester the
t average into the microprocessor, then do so manually.
{ Successive calibrations should yield titrant &ctors within
( 0.0! mgS/mL of each other.
113 Analysis Procedure:
12.3.1 Use an instrument that has bees conditioned and
( calibrated according to 12.1 and 12^.
1232 Weigh to the nearest 0.1 mg, approximately 150
i mg of the coal analysis sample into a boat
1233 Enter the ample weight into the sulfur analyzer
t memory.
123.4 Inset fee coat sample into the 1350*C region of the
i ftimace.
123.5 After the endpoint is readied (not less than 2 una)
t record the sulftir eosoentration of the sample. ST analyzer
c does not have m integral computer, record the volume of
t titrant used and qlrrilatt the sulfur concentration as in-
l jot 132.
J
-------
# > D 4239
where:
T — titraat factor, mg of sulfur/mL;
Sa - sulfur concentration of standard, dry boss:
W - weight of standard, mg; and
Vt m volume of titraat, mL
13.2 On analyzers that do not calculate the percent folftirir
in the analysis sample automatically, the following calcula-i-
tioo must be used:
¦s«ioo
-------
Q D 414239
reCercnc* coals, or calibrating agents toed for calibration and At
sample lo be analyzed should be approximately die bum so thit both
materials produce about the same amount of infrared cefl saturation ($0
to 70*).
16.2.3 Periodic Calibration Verification—Qn a periodic .
>««¦«, verity the stability of the instrument and its calibration
by' analyzing a portion of the SRM, itfeieace coal, or
calibrating agent used to calibrate the instrument. The value
determined for this material, when used as an unknown
sample, must be within the certified value plus or minus the
TtrW precision limits of the material. If the criteria for a
successful verification of calibration in accordance with Tea
Method D 4621 is not met, the calibration procedure of
162.1 must be repeated and samples analyzed since the last
successful verification must be repeated.
16.3 Analysis Procedure—Stabilize and calibrate the ana-
lyzer (see 16 J).
16.3.1 Raise the furnace temperature as recommended by
the manufacturer to at least 1350*C. Weigh the sample (Note
12). Spread the sample evenly in a combustion boat and use
a boat puller to position the sample in the hot zone of the
furnace for at least 2 min (Note 13) or until completely
combusted.
Nurx 13—The analytical cycle should betio autoomicaly as soon at
sulfur a detected
) 6-3-2 When the analysis is complete, the Instrument
should indicate the sulfur value. Refer to the manufacturer's
recommended procedure.
17. Report
17.1 The percent sulfur value obtained using any of the
described methods is on an as-determiaed basis.
ill The results of the sulfur analysis may be reported on
any of a number of bases, differing from each other in the
manner by which moisture is treated.
17 J Use the percentage of moisture in the sample passing
a No. 60 (250-iim) sieve to calculate the as-determined
results of the analysis sample to a dry basis.
17.4 Procedures for converting the value obtained on the
analysis sample to other bases are described is Practices
D 3176 and D 3180.
II. Precision and Bias
18.1 These are empirical methods that are highly depen-
dent upon the calibration of the equipment, the closeness of
the standards to the samples in sulfur content, chlorine
content, iron content, and so forth.
18-2 Precision Statement for High-Temperature Combus-
tion Method Using Add Base Titration Detection Proce-
dures—The relative precision of this method for the detenni-
nation of total sulftir coven the concentration range torn QJ
to 6.0 %.
18.2.1 Repeatability—The difference in absolute value
between two consecutive test results carried out on the same
sample of 60-mesh pulp, in the same laboratory, by the same
operKor, using the same apparatus, should not exceed the
repeatability interval /(r) more than 5 * of such paired
values (95 % confidence level). When such a difference is
found to exceed the repeatability interval, there is reason to
question one or both of the test results. The repeatability
interval may be calculated by use of the Mowing equation;
JW-0.06 +0.01 X
i where * is the average of the two test rec am.
Note 14—'This equation applies to tic relative spxad cf t ixisn*.
I neat that a etpreaal «aa popentafe Mat it derived from the statistical
• evaluation of (be round-robin analytic' rwn—.
< asatjnb fir total ioKir gave tallies or :.S2 and 1.57 ft, Tbe average
1 aiHur oftbe rftipfictte asalyaa value is 1.53 91 aad the cairn,tatwi
I repeatability /(r) is 0.11, The difference between the two suite values is
( 0i>S and docs not exceed the Hi) of 0.11; therefore, thoe two value* ait
1 acceptable at the 9S% confidence leveL
18.2.2 Reproducibility—The difference in absolute value
1 between the averages of replicate determinations, carried out
i in different laboratories on representative 60-mesh samples,
I prepared from the same bulk sample after the last stage of
t reduction, should not exceed the reproducibility interval /(/?)
i more.thaa 5 % of such paired values (95 % confidence level).
' Whejj such a difference is found to exceed the reproduo
i ibOity interval, there is reason to question one, or both, of the
1 test results. The reproducibility interval ma> be calculated by
1 the use of the following equation:
m -0.03 + 0.1 IX
» where lis the averse of between-laboratory results.
Not* 15—Tics equation applies to the relative spread of a measure.
I «cat that la cipnisatid as a peranum and is derived from the statin,ical
« evaluation of the muad-robin analytical results. Example Duplicate
i analysis for total salftir is eae laboratory save as awerap value of
; 3J1 %, aad a value of 4.00 % was obtained is a different laboratory.
* The betwees»4ahotattcy average suite vahie is 3-91 %, the cairntatrri
i 4X) interval Is 0l46*, tad the di&itaee between the different
1 kbocato? vabet is 0.19 *. Sbss this dtfioxace ia kas than the
t tea two values are acoepcable at the 9S JS confidence level
18 J Precision Statement for High-Temperature Combus-
i Hon Method Using lodimetric Detection Procedures—Tbe
t relative precision of this method for the determination of
t total sulfiir coven the concentration range from 0 J to 6.0 %.
18.3.1 Repeatability—Tht difference in. absolute value
1 between two cansccutrw test results carried out on the same
t sample of 60-taesh pulp, is the same laboratory, by the same
< operator, using the tame apparatus should not exceed the
i repeatability intern! Xfi more than 5 % of such paired
' values (93 % confidence level). When such a difference is
I found to exceed the repeatability interval, then; is reason to
< question one, or both, of the test results. The repeatability
i interval may be determined by use of the following equation:
i(r) - 0.0a i
« where * is the average of the two test results.
Nora 16—'Tbis aquation applies to tt* relative spread of a measire-
1 gMM thai is estxened as a percentage aad is deoved from the statistical
i evaluation of tb* rooad^obin analytical iwahs. Example Dopticue
I aoalyais far total anlte |m vatoes of 1-52 aad IS? X. Tbe avenge
i adtar of tiw daplcn analysis value St US *, *ad the cajralsmi
t upwttbfflry haarval^fjk 411 TtadllleraKe between the two sulfur
i viln« la 0t05 and does not exceed tbe J/) of 0-12: tterefare, these two
» v»hw are aec«p«bte st tbe 95 * coniSdeacr itveL
ISJJ Reproducibility—The difference in absolute value
I between dse averages of replicate determinations, carried out
i is different laboratories on representative 60-mesh samples
1 prepared from tbe sums bulk sample after the last stage of
t reduction, should not exceed the reproducibility interval l(i?)
I more than 5 % of such paired values (95 % confidence level}.
1 When such a difference is found to exceed the reproduc-
N-324
-------
# ( D4239 ,
ibility Interval, there is reason to question one, or both, of the e
Test results. The reproducibility interval may be determined 1
by a* of the following equation:
W - 0.CS + 0.09 *
where X is the average of the between-laboratory results.
Not* 17—Tliii equation applies to the relative jpread of a «ea»we- ~
ment thaii»«»prenedaj a percentage and is derived from the mteieal i
evahutioe of the round-robin analytical note. Example Duplicate e
anaiys« for total tulfur in one laboratory as average nkt ^ f
3.81 *, and a value of 4.00 S was obtained ¦ a diffeicnt laboratory. '.
The befweea-tabonioTy averse toUur value a 3.91 S. the calculated 1
HJ?) interval k 0,43 91, aa£ the difference between
hbomory values it 0.19 V Since this difference b lev than tiae JUO, i>
these two values are acceptable at the 95 * confidence level
18.4 Precision Statement for High-Temperature Combus- •
^ Hon Method Using Infrared Absorption Detection Procedures s
18.4.1 Precisian—The relative precision of this test t
method for the determination ofsul&r covets the concentra- •
tios range from 0.28 to 5.61 %.
18.42 Repeatability—The difference in absolute value !
between two consecutive test results, earned out on the same :
sample In the same laboratory by the same operator using j
the same apparatus, should not exceed the repeatability t
interval (limit) I(r) more than 5 % of sod) paired values i
(95 * confidence level). When such a difference is found to >
exceed tie repeatability interval (limit), there is reason to >
question one or both of the test results. The repeatability f
interval on a dry bass nay be determined by use of the
following equation:
JW - Q.Q2 + 0.03 X
where Sis the average of the two test results (see Note 18).
18,4.3 Reproducibility—"Tim difference in absolute value
of rcplisste determinations, carried out is different laborato-
ries on representative samples prepared from the same bulk
ample after the last stage of redaction, should not exceed the
reproducibility interval (limit) HR) more than 5 % of such
paired values (95 % confidence level). Wtwn nsdt a diSer-
eace is found to exceed the reproducibilily interval (limit),
there is reason to question one or both ofthe test results. The
reproducibility interval on a dry basis nay be determined by
use of the Mowing equation:
JU?) - 0.02 + 0.09 i
where* is the average of the two test results (see Note 18).
Mont IS—Theae equation appty to the relative *ntad of a meaaurs-
inent that b atptmta m • penxsaae as derive* from a Uttffcil
aahuBka of the mad-nfein rente.
18J Bias—Bias is eliminated when the instrument is
property calibrated against certified reference standards.
Proper calibration includes comparison of instrumental
results to certified sulfur values. Results for certified stan-
dards above and below anticipated analysis sample results
should be within certified precision levels for all standards
over the calibration range for the instrument
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' 9
N-325
-------
(jjjfm Designation: D 5373 - 93 (Reapproved 199B7)
tmacH* soc*ty k* tes-m urn wims
nemnHMccir vmiCuwmMr.pt t»ua
n^»M ton tmJmj* Bockirf Asm Sanavot. CwyrigM astu
Standard Test Methods for
Instrumental Determination of f Carbon, Hydrogen, and
Nitrogen In Laboratory Samplees of Coal and Coke1
nil tnaM a iMMd trader tte ted d^iBdioa D $773; te <• BBBtar taBBiAaiy UowlBt At teitaMoa iai&na A* }«V sf
artful adopti«a or, la tht en sf *««<*, tt* jwr ofiatt moan. A nusbs n pmntoa ovfiaux tba jw of !m i«wro*aL A
•peaotipi «pOm («} iadleao as afiiorul dmm mmm *¦ tew mat* o»
1. Scop*
1.1 These test methods cover the instrumental determina-
tknj of caiboa, hydrogen, and nitrogen in laboratoiy samples
of coal and coke prepared la accordance with Test Methods
D 2013 sad D 346.
U Within the limitations outlined below, these test
.methods are applicable to either the air-dry or moisture-free
laboratory sample, or both.
1X1 Fbr instrumental systems in which the moisture and
watsn of hydration in the sample are liberated with (and
only with) the oxidation products spoil combustion, the
analyses can be performed on a test specimen of the air-dry
ample (Note I). Concentrations determined on this air-
dried basis represent the total carbon (including that present
as carbonate), total hydrogen (inririding that present as
water), and total nitrogen.
Nor* I—Tboe lyttemi trc tlso ttmftrtoty toe dctawkng the »
ftitgcct ibtteriaJt ia the mobture-&te tuapie.
1.22 For systems ia which the moisture and hydrates are s
otherwise liberated, the analysis shall be performed on the :
moisture-free sample. Values obtained on this basis represent t
the total carbon, organic hydrogen, and total nitrogen.
1J These test methods can be used to provide for the !
requirements specified in Practice D3176 for the ultimate :
analysis.
1.4 The values stated is SI units shall be regarded as the :
standard.
1J This standard does not purport to address all of the t
safety concents, if any, associated with Us use. It is the •.
responsibility of the user of this standard to establish appro- •
prime safety and health practices and determine the applica- •
bility of regulatory limitations prior to use. Specific precau- •
tionary statements are gives in 8.3.1.
iftafaranra 1 TWimin mntm
msicreflCM uoenmefits
2.1 ASTM Standards:
D346 Test Method for Collection and Preparation of I
Cola Samples for Laboratory Analysis2
D2013 Test Method for Preparing Coal Samples for :
Analysis1
D3171 Test Method for Moisture in the Analysis Sample s
of Coalmn/* Coke2
imCTdgHaJminflniMtfASnirnninrtttMtMaa
Cod tad Gob tod an the direct ir^wntihTjiy of Satrwn millce DOSJl at
Mdbabaf Aaafru.
Ctratafctm approved Mtreb IS. IHlMIMMvim
*AMmlaeak
-------
#1
322.1 Removal or* the halides sad sulfur oxides and
liberation of tfae associated hydrogen (as water), by con-
ducting the combustion gases through a series of absorption
traps containing appropriate absorbing materials.
3222 Reduction of the nitrogen oxides to elemental
nitrogen (see Note 2) by passing the resultant gases w
copper at an elevated temperature. The carbon dioxide,
water vapor, and nitrogen may then be determined via one
of several satisfactory detection schemes. '
Hon 2—In (Mi prooen. iririml oxypai a also itmotd.
32J In one configuration, die gases are conducted
through a series of thermal conductivity detectors and gas
absorbers aligned so that, at the water vapor detector level,
the gases pass through the ample side of the detector, a
water vapor absorber, and the reference side of the detector.
At the carbon dioxide detector level, the gases are then
conducted through the sample side of the detector, a carbon
dioxide absorber, and the referenc* side of the detector,
"finally, the resultant gases, which contain only nitrogen and
the carrier gas, pass through the sample side of die nitrogen
detector and art vented. At this detector level, high-purity
carrier gas is used as the reference gas. In these ways, the
detectors determine the thermal conductivities solely of the
specified components.
3.2.4 In a second configuration, the carbon dioxide and
water vapor are determined by infrared detection, using an
aliquot of the combustion gases from which only the halides
and sulfur. oxides have been removed. These detectors
determine the infrared absorption of the pertinent gases at
precise wavelength windows so that the absortances result
from only the specified components. In these systems,
nitrogen ii determined by thermal conductivity, using a
second aliquot of the gases, additionally treated to also
reduce the nitrogen oxides to nitrogen and to remove the
residual oxygen, carbon dioxide, and water vapor.
3.2.5 In £ third configuration, which is essentially a
modified gas chromatographic system, the nitrogen, carbon
dioxide, and water vapor in the tinted combustion gases are
eluted from a chromatographic column and determined (at
appropriate retention times) by thermal conductivity detec-
tion.
3.3 In all cases, the concentrations of carbon, hydrogen,
and nitrogen are calculated as function of the Mowing:
3.3.1 Measured instrumental responses,
3.3 J Values for response per unit mass for the dements
(established via instrument calibration), and
3.3.3 Mass of the sample.
3.4 Or to the following: the instrument response is pro-
portional to the gas density, which has been calibrated
against a gas density of known concentration.
3.5 A capability for perfctxning these computations auto-
matically can be included in the instrumentation used fir
these test methods.
4.1 Carbon sad hydrogen values are used to determine
the amount of oxygen (air) required in combustion processes
ornl for vI.l otfelai^us of efficiency of combustion pro-
cesses.
42 Carbon and hydrogen determinations are used is
material balance calculations on coal conversion processes;
also, one or the other is used frequently is correlations of
chemical and physical properties, such as yields of products
in liquefaction reactivity in gasification and the density and
porosity of coaL
4.3 Mttrogen data are required to fulfill Use requirements
of the ultimate analysis, Practice D3176. Abo, tfae data
obtained cap be used to evaluate the potential formation of
nitrogen oxides as a source of atmoq&eric poUntion.
4.4 Nitrogen data are used for comparing cods and is
research. If the oxygen content of coal is estimated by
difference, it is oecesary to make a nitrogen determination.
5. Appmtss
5.1 Because a variety of instrumental components and
configurations can be used satisfactorily for these test
methods, no specifications are presented here with respect to
overall system deign.
3.2 Functionally, however, the following requirements are
specified for all approved instruments (Note 3):
Nora 3—the approval of an Inurnment with rapect to the*
ftaetknu is jnaaooiat to that test method* linee such spjsoial taridy
provides ipprtml offcotb the mAanb and the pracedam used with the
•yiten to pmadt for these ftmaiom.
52.1 The conditions for combustion of the sample shall
be such that (for the foil nop of applicable samples) the
subject components shall be converted completely to csutcm
dioxide, water vapor (except for hydrogen associated with
volatile halides), and nitrogen or nitrogen oxides. Generally,
instrumental conditions that effect complete combustion
include (J) aviiability of the oxidant, (2) temperature, and
(J) time.
522 Representative aHquots of the combustion gases
shall then be treated for the following reasons:
5.2.2.1 To liberate (as water vapor) hydrogen present as
hydrogen halides and sulfiir oxyadds; and
5222 To reduce (to the dement) nitrogen yicauit as
nitrogen oxides.
(1) The water vapor and nitrogen so obtained shall be
included with the m«t stream in which the water A»pi*i
carbon dioxide are determined. For combusted gases is
which the nitrogen is determined, the water, carbon dioxide,
and residua] oxygen shall also be removed.
5.13.3 For the configuration described m 3.2.5, the ha-
lides and sulfur oxides shall be removed from the combusted
N-327
-------
#> D
gases obtained from the single test specimen.
5.2.4 The detection system (in its fiilJ scope) shall deter-r-
mine the analytical gases individually and without interfer-r-
ence. Additionally, for each aoalyte, other of the following ig
applies:
53.4.1 The detectors themselves shall provide linear re-i-
sponses that correlate directly to concentration over the Mill
range of possible concentrations from the applicable sam-*>
yjff or
5.2.4.2 The system shall include provisions for evaluating lg
nonlinear responses appropriately so that the nonlinear jt
responses can be correlated accurately with these concentra-i-
tion&
(/) Such provisions can be integral to the instrumenta-i-
tion, or they can be provided by (auxiliary) computation o
schemes.
5.2.5 Finally, except for those systems in which the«
concentration data are output directly, the instrument shall ill
indude an appropriate readout device Tor the detectonr
responses.
f. Reagents
6.1 Purity of Reagents—Reagent grade chemicals shall be w
used in all tests. Unless otherwise indicated, H is intended d
that all reagents shall conform to the specifications of theie
Committee on Analytical Reagents of the American Chem-i-
ical Society, where such specifications are available.1 Other ^
grades may be used, provided it is first ascertained that theie
reagent is of sufficiently high purity to permit its use without it
warning the accuracy of the determination.
62 Helium, Carrier Gas, as specified by the instrument it
manufacturer.
6J Oxygen, as specified by the instrument manufactures, r.
6.4 Additional Reagents, as specified by the instrument it
manufacturer. This specification refers to the reagents usedd
to provide for the functional requirements cited is 5222
through 5.23.3. These reagents can vary substantially fbrir
different instruments; in all cases, however, for systems that it
are functionally satisfactory (and therefore approved), theie
reagents recommended by the manufacturer are also tacitly ly
approved. Consequently, these reagents shall be those recom-1-
mended by the manufacturer.
7, Preparation of Analysis Sample
7.1 The samples shall initially be prepared in
with Test Methods D 2013 or D 346.
12 If required by of the instrumental il
system, reduce die air-dry samples (7.1) typically to pass 75'5
)im (No. 200 U.S.A. Standard Sieve Series) to obtain lest it
units of the analysis sample in the size range recommended d
by the instrument manufacturer. If required by cbaractaia-*-
tics of the instrumental system, as specified in 1.2^, treat the te
test specimens is accordance with Test Method D 3173 lo»
provide moisture-free materials solely approptiate for these*
*Mmtm Ottmkeh iwtn Ckntterf Stdmy SfdflcmlaB, AMrisun
CWmkal Saamt, Wwhiajsoo. DC fa naabam qb &§ tnBtsg ot mjBtti wok d
iOd by Ibe Awwfinn Qgmal Sodtty, wt.imhr Stmnitnii Jar labarmtrny
Qnoeaii, BDH UA. Foote, Done, UJL. ud the UMMiSma fiuu iim tyiitlt
md Hmimt! fenmlarj, US. Hwiwwnial Coeieatiee, tot (USPQ.3,
a«*vak.MD.
systems. Is this and all subsequent sample handling steps,
exercise care to minimize chsngss is r3ristu_~ contrat
resulting from exposure to the atmosphere.
8. Instrument Preparation
1.1 Assemble the instrumental system in accordance with
the manufacturer's Instructions.
&2 Adjustment of Response of Measurement System~
Weigh an approptiate test portion of standard reference
material (SRM), calibrating agent, or referer.se coal Analyze
the test portion (see 9,1). Repeat this procedure. Adjust
insteument response, as recommended by the manufacturer,
until the absence of drift is indicated.
8.3 Calibration—Select coal SRMs or other calibrating
agents and materials specified by the manufacturer th?t have
certified carton, hydrogen, ud nitrogen values in
of samples to be analyzed. At least three such SRMs or
calibrating agents are recommended for each range of
carbon, hydrogen, and nitrogen values to be tested. When
possible, two of the SRMs or caUbiating agents shall bracket
the range of caibon, hydrogen, and nitrogen to be tested,
wife the third falling within the range.
8J.1 All coal SRMs should be in accordance with 7.1 and
shall be supplied by or have traceabiiity to as internationally
recognized certifying organization. CAUTION: An indicated
problem with linearity of the instrument during calibration
as result from contamination of the SRM or calibrating
agent as the container becomes depleted. It is therefore
recommended that the SRM or «nWhy*ing agent be dis-
carded when less than five grams remain in the container.
8JJ Calibration Procedure—Analyze, as samples, por-
tions of us SRM, reference coal, or calibrating agnxt chosen
to represent the level of carbon, hydrogen, and nitrogen in
the samples to be tested, tf not required by the characteristics
of the instrumental system, use the "as-determined" caibon,
hydrogen, and nitrogen values for calibration. These values
must have been catailatud previously from the certified "dry
basis" carbon, hydrogen, and nitrogen raises and residual
moisture determined using either Test Methods D 3174 or
D5142. Continue analyzing until the results from five
consecutive determinations M within the repeatability in-
terval (see 122.1) of these test methods. Calibrate the
instrument according to the manufacturer's instructions
using these values. Analyze, as samples, two SRMs reference
coals or calibrating agents that bracket the range of values to
be tested. The results obtained for these samples must br-
wixhia the sated predaios limits of the SRM, reference coal,
or calihfiting agent, or the calibration procedure must be
repeated Records for all calibrations must be is accordance
with Guide D 4621.
833 Periodit Calibration Verification and Rtcalibra-
tion—Is accacdaaoB with Guide D 4621, analyze • control
sample on a periodic basis. Results obtained Sot the control
sample mat be within established limits, or all results
obtained since the last toceessftil control check must be
iqceted and the calibration procedure repeated
9. Procedure
9.1 Analyse * test specimen of the analysis sample in
accordance with the manufacturer's instructions.
N-328
-------
0 DD 5373
10. Calculation
10.1 Calculate the concentrations of carbon, hydrogen,
and nitrogen, oo the appropriate sample basis, as follows
,.G*£xW0
^^fecret
A » % of the aaalyte,
£ - detector response for that analyte,
C " unit mass per detector response estihMwl for the
analyte during calibration, aixi
D - mass of test specimen, g.
Tbe calculations can be provided automatically by the
instrumental system used for these test methods.
11. Export
1M Report results from the carbon, hydrogen, and ni-
trogen determinations on any of the several common hoses
that. differ solely with respect to moisture. Procedures for
converting the as-determined concentrations to the other
bases ire specified in Practices D 317$ end D 3180.
12. Precision and Bias
12.1 These test methods are highly dependent on the
calibration of the equipment
122 The precision of these test methods for the determi-
nation of carbon, hydrogen, and nitrogen was calculated
from data obtained from coal and coke with the following
concentration ranges; caibon (dry-bass) from 48.6 to
90.6 %, hydrogen (dry-basis) from 0.14 to 5.16 %, tad
nitrogen (dry-basis) from 0.69 to 1,57 %.
1221 Repeatability—Tbe difference, in absolute value,
between two test results, conducted on portions of the same
analysis sample, in the same laboratory, by the same
operator, using the same apparatus, shall not exceed the
repeatability interval /(r) in more than 5 % of such paired
values (95 % confidence kvd). When such a difference is
TABLE 1 Mp—tobCay and NapreduefeBBy
XOiyBoli
m
«fl)
Catm
0M
iit
Hy&iDBWi
Q.»
njc
Wrogn
0.11
8,17
found to exceed the repeatability interval, there if reason to
question one, or both, of the test results. The rejxatabiBxy
intervals for caibon, hydrogen, and nitrogen are gives is
TaMe 1.
1112 ficamiik—Duplicate analyses for action exhibited
values of 73.26 and 73.62 %. Tbe absolute difference be-
tween the two test results is 0J6 %. Since this value does not
exceed the /(«-} value of 0.64 %, these duplicate analyses are
acceptable at the 95 % confidence level
1213 RtprodudbUity—Thz difference, in absolute value,
between the overages of duplicate determinations conducted
in different laboratories on representative samples prepared
from the same bulk sample after reducing to 100 % through
a 250 Mm (No. 60 U.SA. Standard Sieve Series) neve shall
ncrt exceed the reproducibility internal l(R) in more than
5 % of such paired values (95 X confidence kvd). When
such a difference is fbnnd to exceed the reproducibility
interval, there is reason to question one, or both, of the test
results. Tbe reproducibility intervals for carbon, hydrogen,
and nitrogen are given in TaUe 1.
12.2.4 Exmrqsle—Duplicate analysis for hydrogen in one
laboratory revealed aa average value of 5.15 %, and a value
of 4.93 % was obtained in a £fierent laboratory. The
difference between tbe different laboratory value is 0.22 %.
Since the laboratory difference is less than the I(R% the two
laboratory results are acceptable at the 95 X confidence
leveL
123 Bias—Bias is eliminated when the apparatus is
calibrated property against certified reference standards.
Proper calibration includes comparison of test data on
NISTT SRM 1632 or other reagents and materials that have
certified carbon, hydrogen, and nitrogen values.
Th»AmvicarSt>d«ytafTmtbig*xlummltlHakmimfmtfcfianmp»ainga»<*IUtyattairpm$ntiighmm*imdlnaiimetton
with tny torn mtcuonn In thlt twxJwd. Owo of Mi iMM *! aw nffutly mMad CM dfnr*t*k*) el tt» Mftfly el my micfi
pmrttrtym, mdM 0/weft aim mpnmNtf.
TTjuMird it tub/tg » miahn m any Urn bf U» mptmMbto ttcMctl tomMm mid immt b» rmipita *my Ik* yaw wni
yaursommant»*«»tiM(»6«0MrftrwiMxt#tM«andtn«orforaMtan*fttNinrcl»
and ttnvld da tekiiwdlo ASTUNmdgumon. Your oorrrntratt wM ne*Km emtuleenMmmkm *» m—togoMmrmpem&m
fchnktl commetM, wftre* yw m*y «un£ f you IM aitf jour cr aomRwn Am* M neaMatf * Mr tearing jnu onto )W
vfewi lamm ta tht ASTU Canmttm an Sttndardt, 100 Btn Itmtmtxir OWw, ItW Comhahoc*m, PA 1943B.
44
-------
Obsignation: E 711 - 87
AMERICAN SOCIETY FOR TESTINS AND M.MATK RIALS
WW Race SU PKSmMpIM. P*. W10J03
ItapriMBdfcwn the Annual Books! ASTM Standards, a. Ccpyrtgrn ASTM
H net Mad ki the cumr* contoirad Mm. wll appear ir in Dta nasi edition.
Standard Test Method for
GROSS CALORIFIC VALUE < OF REFUSE-DERIVED FUEL BY
THE BOMB CALORIMETER11
Thb nandand it haned under the fctrd desjnation E 71 i: the oinuraber immediately foDowiag the des%>oties ^ of
original adoption of. in the case ef rrvmtm, the year of lail revuii boil A number in paieitthnes indicate! the year of tot teapproval
A sipencritx epukm it) indicates an editorial cfcaase lincc the lalaB revisoa or reapproval.
mm aMiOpC
1.1 This test method covers the determination
of the grass calorific value of a prepared analysis
sample of solid forms of refuse-derived fiiel
(RDF) by the bomb calorimeter method.
1.2 This standard may involve hazardous ma-
terials, operations, and equipment. This standard
does not purport to address all of the safety prob-
lems associated with its use. Ft is the responsibil-
ity of the user ofthis standard to establish appro-
priate safety and health practices and determine
the applicability of regulatory limitations prior to
use. For specific cautionary and precautionary
statements see 6.10 and Section 8.
2. Referenced Documents
2.1 ASTM Standards:
D1193 Specification for Reagent Water1
D3177 Test Method for Total Sulfur in the
Analysis Sample of Coal and Coke*
E I Specification for ASTM Thermometers*
E 180 Practice for Determining the Precision
Data of ASTM Methods for Analysis and
Testing of Industrial Chemicals'
E 773 Test Methods for Total Sulfur in the
Analysis Sample of Refuse-Derived Fuel*
E 790 Test Method for Residual Moisture in
a Refuse-Derived Fuel Analysis Sample*
E 829 Method of Preparing RDF-3 Labors,
toty Samples for Analysis*
3. Terminology
3.1 Definitions-.
3.1.1 calorific value—the heat of combustion
of a unit quantity of a substance. It may be
expressed in joules per gram (J/g), British ther-
mal units per pound (Btu/Ib), or calories per
gram (cal/g) when required.
Not* I—The unit equivalents are is follows:
I Btu (International Table) — 1055.06 absolute
1 Calorie (International TaWe) - 4.1868 absolute
joule#
I Btu/Ib - 2.326 J/g
1.1 Btu/lb • 1.0 cal/g
3.1-2 grass calorific value—the heat produced
by combustion of a unit quantity of solid fuel, at
constant volume, in an oxygen bomb calorimeter
under specified conditions such that all water in
the products remains in liquid form.
3.1.3 net calorific value—a lower value cal-
culated from the gross calorific value. It is equiv-
alent to the heat produced by combustion of a
unit quantity of solid fuel at a constant pressure
of one atmosphere, under the assumption that
all water in the products remains in the form of
vapor.
3.2 Descriptions of Terms Specific to This
Met hod: •
3.2.1 calorimeter—describes the bomb, the
vessel with stirrer, and the water in which the
bomb is immersed.
3.2.2 energy equivalent—the energy required
to raise the temperature (Note 2) of the calorim-
eter system l*C (or I *F> per gram of sample. This
is the number that is multiplied by the corrected
temperature rise in degrees and divided by the
sample weight in grams to give the gross calorific
value after thermochemical corrections have
been applied.
¦This toi method ii wader the jueiadietiaa of ASTM Com-
mittee E-31 aa IUmmiicc Recovery and m the direct reapoesiMS-
ity of Sttbcommiuee E 31,01 on Energy.
CXvmtt edition approved Aug. 2a, IW7. PuMWwJ October
1*7.
*Ammt Book
-------
#
Nori 1—Temperature change is measured in ther-
mal units. Temperature changes may also be recorded
in electromotive force, ohms, or other units when other
tjfws kM' temperature sensor* are used. Consistent units
must he used in both the standardization and actual
calorific determination. Time is expressed in minutes.
Weights are measured in grams.
3.2.3 refuse-derived fuels—solid forms of re-
fuse-derived fuels from which appropriate ana-
lytical samples mav be prepared are defined as
follows in ASTM STPSS2'
RDF-1—Wastes used as a fuel in as-discarded
form with only bulky wastes removed.
RDF-2—Wastes processed to coarse particle
size with or without ferrous metal separa-
tion.
RDF-3—Combustible waste fraction pro-
cessed to particle sizes. 95 ^ passing 2-in.
square screening.
RDF-4—Combustible waste fraction proc-
essed into powder form. 95 *c passing 10-
mesh screening.
RDF-5—Combustible waste fraction densifted
'compressed! into the form of pellets, slugs,
cubettes. or briquettes.
4. Summary of Test Method
4.1 Calorific value is determined in this
method b% burning a weighed analysis sample in
an oxygen bomb calorimeter under controlled
conditions. The calorific value is computed from
temperature observations made before and after
combustion, taking proper allowance for ther-
mometer and therm ochemica! corrections.
Either isothermal or adiabatic calorimeter jackets
ma> be used.
5. Significance and Use
5.1 The calorific value, or heat of combustion,
is a measure of the energy available from a fuel.
Knowledge of this value is essential in assessing
the commercial worth of the fuel and to provide
the basis of contract between producer and user.
6. Apparatus
6,1 7 est R'ftm—The apparatus should be op-
ci.iu.-u .i. « .wi.. ui «rea free of drafts that can
be kept at a reasonably uniform temperature and
humidity for the time required for the determi-
nation. The apparatus should be shielded from
direct sunlight and radiation from other sources.
< onirollcd mom temperature and humidity are
desirable.
6711
6.2 Oxygen Bomb, constructed of materials
that are not affected by the combustion process
or products sufficiently to introduce measurable
heat input or alteration of end products. If the
bomb is lined with platinum or gold, all openings
shall be sealed to prevent combustion products
from reaching the base metal. The bomb shall be
designed so that all liquid combustion products
can be completely recovered by washing the inner
surfaces. There shall be no gas leakage during a
test. The bomb shall be capable of withstanding
a hydrostatic pressure test to 21 MPa (3000 psig)
at room temperature without stressing any part
beyond its elastic limit.
6.3 Calorimeter, made of metal (preferably
copper or brass) with a tamish-resistant coating
and with all outer surfaces highly polished. Its
size shall be such that the bomb will be com-
pletely immersed in water when the calorimeter
is assembled. It shall have a device for stirring
the water thoroughly and at a uniform rate, but
with minimum heat input. Continuous stirring
for 10 min shall not raise the calorimeter tem-
perature more than 0.01*C <0.02*F) starting with
identical temperatures in the calorimeter, room,
and jacket. The immersed portion of the stirrer
shall be coupled to the outside through a material
of low heat conductivity.
6.4 Jacket-—The calorimeter shall be com-
pletely enclosed within a stirred water jacket and
supported so that its sides, top. and bottom are
approximately 10 mm from the jacket walls. The
jacket may be arranged so as to remain at con-
stant temperature or with provisions for rapidly
adjusting the jacket temperature to equal that of
the calorimeter for adiabatic operation. It shall
be constructed so that any water evaporating
from the jacket will not condense on the calorim-
eter.
6.5 Thermometers—Temperatures in. the
calorimeter and jacket shall be measured with
the following thermometers or combinations
thereof;
6.5.1 Mercury-in-Glast Thermometers. con-
forming to the requirements for Thermometers
116*C or I J7*C {S6*F or 5?*F> as prescribed in
Specification E 1. Other thermometers of equal
or better accuracy are satisfactory. These ther-
mometers shall be tested for accuracy against a
known standard (preferably by the National Bu-
" Thr\auru\ tm Resource Rtemtrr TrrmimJw. JSTU STP
ASTM. !»8J. p 72.
N-33^1
-------
E 711
reau of Standards) at intervals no greater than
2.0*C <3.6*F) over the entire graduated scale. The
maximum difference in correction between any
two test points shall not be more than 0.02*C
(0.04T).
6.5.2 Beckmeum Differential ' Thermometer,
having a range of approximately 6*C is 0.01 *C
subdivisions reading upward and conforming to
the requirements for Thermometer !IS*C, as
prescribed in Specification E I. Each of these
thermometer shall be tested for accuracy against
a known standard at intervals no larger than PC
over the entire graduated scale. The maximum
difference between any two test points shall not
be more than 0.02*C.
' 6.5.3 Calorimetric-Type Platinum Resistance
Thermometer, 25tested for accuracy against a
known standard.
6.5.4 Other Thermometers—A high precision
electronic thermometer employing balanced
thermistors or a quartz thermometer may be
used, provided the temperature rise indication is
accurate within ±0.003*C per I *C rise.
6.6 * Thermometer Accessories—A magnifier is
required for reading mercury-in-glass thermom-
eters to one tenth of the smallest scale division.
This shall have a lens and holder designed so as
to introduce no significant errors due to parallax.
A Wheatstone bridge and galvanometer capable
of measuring resistance to 0.0001 0 me necessary
for use with resistance thermometers.
6.7 Sample Holder—Samples shall be burned
in an open crucible of platinum, quartz, or ac-
ceptable base-metal alloy. Base-metal alloy cru-
cibles are acceptable if after a few preliminary
firings the weight does not change significantly
between
6.8 Firing Wire shall be 100 mm of No. 34 B
& S nickel-chromium alloy wire or 100 mm of
No. 34 B & S iron wire. Equivalent platinum or
palladium wire may be used provided constant
ignition
energy
is supplied, or measured, and
appropriate corrections made.
6.9 Firing Circuit—A 6 to 16-V alternating or
direct current Is required for ignition purposes
with an ammeter or pilot light in the circuit to
indicate when current is flowing. A stepdown
transformer connected to an alternating current
lighting circuit or batteries may be used.
6.10 CAUTION: The ignition circuit switch
shall be of momentary double-contact type, nor-
mally open, except when held dosed by the op-
erator. The switch should be dep rased only 'oag
• enough to fire the bomb.
7. Reagents
7.1 Purity vf Reagents—Reagent grade chem-
icals shall be used in all tests. Unless otherwise
indicated, it is intended that an reagents shall
conform to the specifications of ihe Committee
on Analytical Rei«ents of the American Chemi-
cal Society, where such specifications are avail-
able." Other grades may be used, provided it is
first ascertained that the reagent is of sufficiently
high purity to permit its use without lessening
the accuracy of the determination.
7.2 Purify of Water—Unless otherwise indi-
cated, references to water shall be understood to
mean reagent water. Type III, conforming to
Specification D 1193.
7.3 Benzoic Acid. Standard {CtHsCOOH)—
Use National Bureau of Standards SRM (Stan-
dard Reference Material) benzoic acid. The crys-
tals shall be pelletized before use. Commercially
prepared pellets may be used provided they are
made from National Bureau of Standards ben-
zoic acid. The value of heat of combustion of
benzoic acid, for use in the calibration calcula-
tions, shall be in accordance with the value listed
in the National Bureau of Standards certificate
issued with the standard.
7.4 Methyl Orange. Methyl Red. or Methyl
Purple Indicator may be used to titrate the acid
formed in the combustion. The indicator selected
shall be used consistently in both calibrations
and calorific determinations.
7.5 Oxygen, free of combustible matter. Oxy
gen manufactured from liquid air. guaranteed to
be greater than 99.5 % pure, will meet this re-
quirement Oxygen made by the electrolytic pro-
cess may contain a small amount of hydrogen
rendering it unfit without purification.
7.6 Sodium Carbonate. Standard Solution
- |0.34 W)—One milUlitre of this solution should
be equivalent to 20.0 J in the nitric acid (HNO})
titration. Dissolve 18.02 g of anhydrous sodium
< carbonate (NazCQ») in water and dilute to 1 L.
The NaiCO) should be previously dried for 24 b
'"IUmqbm OmUcbIs, Arnenan Cbesucfc! fon Ttij Spccift-
• «aUoM."A«i.amkalSac_ W«buck».DCFbrmHHtiom
• — *» it Of WIMMI H—d by tbt Aamian Oreniari
i Ran, D. Van Namaad Ox. hit. New YoA. NY. and the
• ""ft ImimI **
N-laf2
-------
at 105*C. Tlie buret used for the HNOj titration
shall be of such accuracy that estimations lo 0.1
mL can be made. A more dilute standard solu-
tion may be used for higher sensitivity.
8. Precautions
8.1 Due to the origins of RDF in municipal
waste, common sense dictates that some precau-
tions should be observed when conducting tests
on the samples. Recommended hygienic prac-
tices include use of gloves when handling RDF
and washing hands before eating or smoking.
8.2 The following precautions are recom-
mended for safe calorimeter operation:
8.2. i The weight of solid ftiel sample and the
pressure of the oxygen admitted to the bomb
must not exceed the bomb manufacturer's rec-
ommendations.
8.2.2 Bomb parts should be inspected care-
fully after each use. Threads on the main closure
should be checked frequently for wear. The bomb
should be returned to the manufacturer occasion-
ally for inspection and possibly proof of firing.
8.2.3 The oxygen supply cylinder should be
equipped With an approved type of safety device,
such as a reducing valve, in addition to the needle
valve and pressure gage used in regulating the
oxygen feed to the bomb. Valves, gages, and
gaskets must meet industry safety codes. Suitable
reducing valves and adaptors for 2 to 3.5-MPa
(300 to 500-psig) discharge pressure are obtaina-
ble from commercial sources of compressed gas
equipment. The pressure gage shall be checked
periodically for accuracy.
8.2.4 During ignition of a sample, the opera-
tor shall not permit any portion or his body to
extend over the calorimeter. —
9. Sampling*
9.1 RDF products are frequently nonhomo-
geneous. For this reason significant care should
be exercised to obtain a representative laboratory
sample for the RDF lot to be characterized.
9.2 The sampling method for this procedure
should be based on agreement between the in-
volved parties.
9.3 The laboratory sample must be air-dried
pass a 0.5-mra screen
as described In Method E 829.
!0.
10.1 Determine the energy equivalent of the
calorimeter 2s the average of a series of ten
E 711
individual runs, made over a period of not less
than 3 days or more than 5 days. To be accept-
able, the standard deviation of the series shall be
6.9 ki/*C (6.5 Btu/*C) or less (tee Appendix XI,
Table X1). For this purpose, any individual run
may be discarded only if there is evidence indi-
cating incomplete combustion. If this limit is not
met, repeat the entire series until a aeries is
obtained with a standard deviation below the
acceptable limit
10.2 The weights of the pellets of benzoic acid
in each series should be regulated to yield the
same temperature rise as that obtained with the
various samples tested in the individual labora-
tories The usual range of weight is 0.9 to 1.3 g.
Make each determination in accordance with the
procedure described in Section 11, and compute
the corrected temperature rise, T, as described in
12.1. Determine the corrections for HNOj and
Tiring wire as described in 12.2 and substitute
into the following equation:
£¦» ((+ ft + ft + e*l x t
where;
E «¦ energy equivalent, J/*C.
H » heat of combustion of benzoic acid, as stated
in the National Bureau of Standards certif-
icate, J/g,
g «¦ weight of benzoic acid. g.
t « corrected temperature rise, *C,
e, — titration correction, J,
e.% - fuse wire correction, J, and
e4 ¦ correction for ignition energy if measured
and corrected for, J,
10.3 Standardization tests should be repeated
after changing any part of the calorimeter and
occasionally as a check on both calorimeter and
operating technique.
II. Procedure
11.1 Weight of Sample—Thoroughly mix the
analysts sample of solid fuel in the sample bottle,
taking care that the heavies and lights (fluff) are
distributed in the sample (Note 3). Carefully
weigh approximately I g of the sample directly
into the crucible in which it is to be burned or
into a tared weighing scoop from which the sam-
ple is transferred to the crucible. Weigh the sam-
ple to the nearest 0.1 mg. Some form of compac-
* ASTM Subcommittee C3S.0I i» cumntly in the process or
developing procedures for lampJir* RDF-J and the preparation
of an analyst (ample. The chairman of OS.Ot should tie
contacted for detail*.
44 .
N-333
-------
#
tion may be necessary to ensure satisfactory ig-
nition and complete combustion.
Note 5—In the event segregation or the heavies and
lights cannot be avoided, attempt to remove sample
from the bottle in such a way that a representative
ample is transferred.
Note 4—Perform the residual moisture determina-
tion of the sample simultaneously using Test Method
E790.
11.2 Water in Bomb—Add 1.0 raL of water
to the bomb by a pipet. Before adding this water,
rinse the bomb, and drain the excess water, and
leave undried.
11.3 Firing Wire—Connect a measured
length of firing wire to the ignition terminals with
enough slack to allow the firing wire to maintain
contact with the sample.
11.4 Oxygen—Chaige the bomb with oxygen
to a consistent pressure between 20 and 30 atm
(2.03 and 3.04 MPa). This pressure must remain
the same for each calibration and for each calor-
ific determination. It by accident, the oxygen
introduced into the bomb should exceed the
specified pressure, do not proceed with the com-
bustion. Detach the filling connection and ex-
haust the bomb in the usual manner. Discard
this sample.
11.5 Calorimeter Water—It is recommended
that calorimeter water temperature be adjusted
before weighing as follows:
11.5.1 Isothermal Jacket Method, 1.6 to 2.0*C
<3.0 to 3.5*F) below jacket temperature (Note 4).
11.5.2 Adiabatir Jacket Method, 1.0 to 1.4*C
(2.0 to 2.5*F) below room temperature.
Note 5—This initial adjustment will ensure a final
temperature slightly above that of the jacket for calo-
— rimeters having an energy equivalent of approximately
10 200 J/K. <2430 cal/*C"). Some operators prefer a
lower initial temperature so that the final temperature
is tfightly below that of the jacket. This procedure is
acceptable, provided H is used in all tests, including
standardization. Use the same amount (±03 g) of water
in the calorimeter vessel for each test and for calibre*
tion. The amount of water (2000 g is usual) can be
mo* satisfactorily determined by weighing the calorim-
eter vend and water together on a balancr The water
may be measured vol u metrical Jy If it is always mea-
sured at the same temperature. Tap water may be
satis&ctory for use in calorimeter bucket.
11.6 Observations, isothermal Jacket
Method—Assemble the calorimeter in the jacket
and stall the stirrer. Allow 5 min for attainment
of equilibrium: then record the calorimeter tem-
peratures (Note 6) at 1-min intervals for 5 min,
Fire die charge at the start of the sixth minute
E711
and record the time and temperature, T*. Add to
this temperature 60 % of the expected tempera-
ture rise, and record the lime «•. which the eO %
point is reached (Note 5). After the rapid-rise
period (about 4 to 5 min), record temperatures
at 1-rain intervals on the minute until the differ-
ence between successive readings has been con-
stant for 5 min.
Note 6—Use a magnifier and estimate all readings
(except those during the rapid rise period) to the nearest
0.002*C (0.005"F) when using ASTM Bomb Calorim-
eter Thermometer S6C (56FJ. Estimate Beckmann ther-
mometer readings to die nearest 0.00 IX". Tap mercu-
rial thermometers with a pencil just before reading to
avoid errors caused by mercury sticking lo the wails of
the capillary.
Not® 1—When the approximate expected rue is
unknown, the time at which the temperature reaches
60* of the total can be determined by recording tem-
peratures at 45.60, 75, 90, and 105 s after firing and
interpolating.
11.7 Observations. Adiabatic Jacket
Method—-Assemble the calorimeter in the jacket
and start the stirrer. Adjust the jacket tempera-
ture to be equal to or slightly lower than the
calorimeter, and run for 5 mm to obtain equilib-
rium. Adjust the jacket temperature to match the
calorimeter with ±0.01*C (0.02*F) and hold for
3 min. Record the initial temperature (Note 6)
and fire the charge. Adjust the jacket temperature
to match that of the calorimeter during the period
of roe. keeping the two temperatures as nearly
equal as possible during the rapid rise, and ad-
justing to within ±0.0rC (0.02*F) when ap-
proaching the final equilibrium temperature.
Take calorimeter readings at l-min intervals un-
til the same temperature is observed in three
successive readings. Record this as the final tem-
perature. Do not record time intervals since they
are not critical in the adiabatic method.
11.8 Analysis of Bomb Contents—Remove
the bomb and release die pressure at a uniform
rate, in such a way that the operation will require
not less than I min. Examine the bomb interior
and discard the test if unburaed sample or sooty
deposits are found. GeefuHy wash the interior of
the bomb including the capsule with distilled or
dekmized water containing the titration indicator
until the washings are free of acid. Collect the
wadhings in a beaker and titrate the washings
with standard carbonate solution. Remove and
measure or weigh the combined pieces of un-
burned firing wire, and subtract from the original
length or weight to determine the wire consumed
S i
N-334
-------
#
in firing. Determine the sulfur content of the
sample by any of the procedures described In
Test Methods E 775.
12. Calculations
12.1 Temperature Rise in Isothermal Jacket
Calorimeter—Using data obtained as prescribed
In 11.6, compute the temperature rise, T, in an
isothermal jacket calorimeter as follows:
T- Tt-Tm- r,(b -a)- r*c - b)
where:
T — corrected temperature rise,
a —time of firing,
b *¦ time (to nearest 0,1 min) when the temper-
ature rise reaches 60 % of total,
c •— time at beginning of period in which the
rate of temperature change with lime has
become constant {after combustion),
T. — temperature at time of firing, corrected for
thermometer error (Note 7),
7V «* temperature at time c corrected for ther-
mometer error (Note 7),
r, -rate (temperature units per minute) at
which temperature was rising during 5-min
period before firing, and
r2 «¦ rate (temperature units per minute) at
which temperature was rising during the 5-
min period after time c. If the temperature
is falling. r2 is negative and the quantity r2
(c — b) is positive.
12.2 Temperature Rise in Adiabiatic Jacket
Calorimeter—Using data obtained as prescribed
in 11,7 compute the corrected temperature rise, .
T, as follows:
r- Tr~ r.
where:
T -= corrected temperature rise, *C or *F,
T„ »initial temperature when charge was fired,
corrected for thermometer error (Note 8),
and
7} — final temperature corrected for thermome-
ter error.
Note 8—With all mercury-in-glass thermometers, it
il necesriry to make the following corrections if the
total heat value is altered by 12 J/g or more. This
represents a change of 0.001 *C (0.00ZT) in a calorim-
eter using approjumately 2000 g of water. The correc-
tions mciuoe ine calibration correction as stated on the
calibration certificate, the setting correction for Beck-
man thermometers according to the directions fur-
nished by th? calibration authority, and the correction
for emergent stem. Directions for these corrections are
given in Appendix X2.
E711
12-3 Thermochemical Corrections (Appendix '
X3)—Compute the following for each test:
e, - correction for the heat of formation of
HN03. J. Each millilitre of standard alkali
is equivalent to 20.0 J.
— correction for heat of formation of HjSQ*.
J
• 55.2 x percent of sulfur in sample x weight
of sample, g.
*3 — correction for beat of combustion of firing
wire, J (Note 10)
— 9.6 J/cna or 5980 l/g for No. 34 B & S gage
ChromelC
— 11.3 J/cm or 7330 J/g for No. 34 B & S
iron wire.
e* — correction for ignition energy of platinum
or palladium if measured and corrected for.
Note 9—There is bo correction for platinum or
palladium wire, provided the ignition energy is con-
12.4 Calorific Value:
12.4.1 Calculate the gross calorific value
(gross heat of combustion) as follows:
H, - [<7*£) - - rj/g
where:
H, ¦» gross calorific value, J/g.
T — corrected temperature rise as calculated in
12.1 or 12.2, *C or *F, consistent with the
water equivalent value,
E * energy equivalent (see Section 10),
et, ei, e* e* - corrections as prescribed in
12.3, and
g -= weight of sample, g.
12.4.2 Calculate the net calorific value (net
heat of combustion) as follows:
23.96 (H x 9)
where;
Hi «¦ net calorific value (net heat of combustion).
J/8,
H% — gross calorific value (gross beat of combus*
tion), J/g, and
H »total hydrogen, %.
13. Precision and Bias"
13.1 Precision—The standard deviations of
individual determinations, in Btu/lb, are:
"Supporting data are ivailaMc on loan from ASTM Head-
quartets. Request RR:E3S-I000.
66
N-335
-------
#
1711
Within-
Betweeo-
Average
' laboratory
laboratories
HHV.J:
6400
27.1
IJS.I
3200
4i,«
239.4
HHV-2:
7900
32J
111.0
7400
3S.1
227.1
HHV.3:
9700
111.3
290.4
Aweiage
9500
9300
Wlthin-
labmaiory
992
40S
Between-
lebomiories
2492
67,6
13.2 These precisic.: zzlr-
an intcriaboratory study conducted in accord-
ance with Practice E 180.
APPENMDIXES
(Nonmandatory? Information)
XI. CAICULATION OF STANDARD DEVIATIOONS FOR CALORIMETER STANDARDIZATION
XI.I The example given in Table XI.I illustrates orimeter standardizations,
she method of calculating standard deviations for cal-
TABLE X1.1 ft—<¦>< i Dr»krim»» for Cthriailir
Standardization
Number
Column A A
Water r
- Equivafeneiu.
(Btu/Ib) >) x
(mTO )
Column B
Code to
4400
(Column
A-4400)
Column C
(Column
1
44(2
12
144
2
4407
7
49
3
4411
15
22S
4
4408
g
64
5
4404
4
16
6
4406
6
36
7
4409
9
¦ 1
a
4410
10
100
9
4412
12
144
10
4409
9
• I
Sunt
53
535
Avenge-.H- */i0 - (92/1/10) ~ 4400 - 4409
Variance Column C - - (Column B f/n/n - I - 940 -
10.4
Standard deviation. s - Variirianee - 10.4 - 3.22
* 1» itm example the values a of water equivalent we typical
for a. calorimeter "il usocfo thai the water aquivafent
multiplied fay the temperature e rise io *C/s of Mtnple will give
the calorific value of the saatplete in Brn/Tb.
X2. THERMOMETffER CORRECTIONS
X2.1 It is necessary to make the following correc-
tions in the event they result in an equivalent chance
of 0.001 *C or more.
X2.I.I Calibration Correction shall be made in ac-
cordance with the calibration certificate Aimislusd by
the calibration authority.
XX 1.2 Sating Correction is necessary for the Beck,
maun thermometer. It shall be made in aocotdance
with the directions furnished by the calibration author-
ity.
XX 1.3 Differential Emergent Stem Correction—
Tl* calculation depends upon the way the thermometer
was calibrated and how it is used. The following two
conditions are possible:
fa) Thermometers Calibrated in Total Immersion
and Used in Partial Immersion—This emergent stem
correction is made as follows;
Correction « JT(4 - /,)(!, * /, - L ~ T)
where:
K - 0.00016 for thermometers calibrated in *C
0.00009 for thermometers calibrated in *F.
77
N-336
-------
E 711
L m scale reading to which the thermometer was im-
mersed.
T ¦» mean temperature of emergent stem.
/, * initial temperature reading, and
t, - final temperature reading.
Ncrn X2.I: Example—Suppose the.-point L, to
which the thermometer was immersed , was 16*C; its
initial reading. f„ was 24.12TC. its final reading, («, was
27.876*C, the mean temperature of the emergent stem,
T, was 26*C,
then:
Differential stem correction
-0.00016 (28 - 24) (28 +24 -16 - 26)
¦ +0.006*C
0) Thermometers Calibrated and Used in Partial
Immersion but a a Different Temperature than the
Calibration Temperature—This emergent stem correc-
tion is made as follows:
Correction -*(/,-j«) (*, - f*)
K — 0.00016 for thermometen calibrated in *C
0.00009 for thermometers calibrated in *F,
4 «¦ initial temperature reading.
It - final temperature reading.
I, - observed stem temperature, and
I* — stem temperature at wfuch the thermometer was
calibrated.
Note X2J2: Example—Suppose the initial reading.
U. was SOT, the final reading, u, was 86*F. and that the
observed stem temperature, /i, was 82*F, and the cali-
bration temperature, t\ was 72*F; then:
Differentia] stem correction
- 0.00009 (16 - 90X82 - 72)
-0.003-F
X3. THERMOCHEMHICAL CORRECTIONS
X3.I Heat of Formation of Nitric Acid—A correc-
tion (,p.3?l.
X4. REPORTING RESU1JLTS IN OTHER UNITS
X4.1 Reporting Results in British Thermal Units
(Btu) per Found- -The gross calorific value can be ex-
pressed Id British thermal units by using the thermo-
chemical correction factors in Table X4.1 and the water
equivalent expressed in (Btu/Ib) x (g/*C).
88
N-337
-------
©> E7t1
TABLE X4.I Tlii«*eclworfaeal Catmtkm factor* (Units hi
BTHU)
Correction
Multipii-
cation Factor r
Multiply by
«% tHNOi)
10.3
ml of 0JS4 s NajCOj «>
nWiSCW
23.7
BBUQIi
% at wlfur hi tample timet
of temple In gnms
n (fuse wire)
-4.1 or
on of No. JtaiSme
Ctoontel Cwire
25 TO
weight (4) of Oiwmrf C wire
<%t ($) of trcui wife
Tke American St nittyftr Testing and Material* takes no posithmm respecting Ike validity ofamy paten; rights asserted in cum wrturn
with any item mentioned m this standard. Users of thin standard arare c.xpretsly advised that determination of the validity ofany such
patent rights, and the risk of infringement ofsuch rights, are entirrl.tiy their am responsibility.
This standard Is subject to revision at any time by the mpoasihfhle technical committee and must he reviewed every fire years and
tf m* revised, either reappmved or withdrawn. Ytmr comments atare invited either far revision of this standard or for additional
standards and should he addressed to ASThi Headquarters. Ytmr r comments mill receive rarrfi.d nmsideratnm at a meeting t>f the
responsible technical committee, which you may attend. If you feel ri that ymtr comments have not received a fair hearing you should
make your views known to the .4STM Committee an Standards. 191916 Race Sr.. Philadelphia, FA 19103.
9 »
N-338
-------
D—ignatton: E 830 - 87
AMERICAN SOCIETY FOR TESTING AND MATir*«IA».S
1B16 Raea St.. PhiadalpNa. 1%. 19103
napctm»d torn tha Annual Book of ASTM Standards, Cofepyright ASTM
H not Uatad in thm cwtm comtMflad toda*. wW appear In tt tlw nwt edition
Standard Test Method for
ASH IN THE ANALYSIS SAMPLLE OF REFUSE-DERIVED FUEL1
This standard is isued under the fiaed dcsignaltoo E130; the numbcucr iraraediatriy foOowiaf the dengnation indicates the year of
original adoption or. in tbecaaeoTievbion. the year of last revision. A A Bomber in paneMhcaea indicate* the yoBroflaat rwpprwaL
A superscript cpsilon <«) indicates an editorial chance snce the last icwviiian or reapprova).
1. Scope
1.1 This ten method covers determination of
the ash content in the analysis sample of refuse-
derived fuel (RDF). The results obtained can be
applied as the weight percent ash in the proxi-
mate analysis and in the ultimate analysis.
1.2 The values stated in acceptable metric
units are to be regarded as standard. Hie values
given in parentheses are for information only.
13 This standard may involve hazardous ma-
terials, operations, and equipment. This standard
does not purport to address all of the safety prob-
lems cssociated with its use. It is the responsibil-
ity of the user of this standard to establish appro-
priate safety and health practices and determine
the applicability of regulatcry limitations prior to
use. For specific precautionary statements see
Section 6.
1 Referenced Documents
2.1 ASTM Standards:
E 180 Practice for Determining the Precision
Data of ASTM Methods for Analysis and
Testing of Industrial Chemicals3
E 790 Test Method for Residual Moisture in
a Refuse-Derived Fuel Analysis Sample1
E 829 Method of Preparing RDF-3 Labora-
tory Samples for Analysis5
3. Description ofTerm Specific to This Standard
3.1 refuse-derived fuel—Solid forms of refuse-
derived fuels from which appropriate analytical
samples may be prepared are defined as follows
i* 5.
* Annual Book cf ASTM Standards 11.04.
* Thrtaurtts am Kxtomce **rowv Terminology. ASTM STP
8XJ2. ASTM. 1983. p. 72.
I
N-339
-------
EE 830
flow below ihe suggested mini mum without adversely
affecting results of the ash determination.
6.2 Porcelain Capsules, about 22 mm (V* in.)
in depth, and 44 mm (1 V« in.) in diameter, or
similar containers.
Nor* 2—Weighing bottles of borosilicalc glass may
be safely used without deformation of ioftening at
temperatures of 600*C or less.
7. Precautions
7.1 Due to the origins or RDF in municipal
waste, common sense dictates that some precau-
tions should be observed when conducting tests
on the samples. Recommended hygienic prac-
tices include use of gloves when handling RDF;
wearing dust masks (NIOSH-approved type), es-
pecially while milling RDF samples; conducting
tests under a negative pressure hood when pos-
sible; and washing hands before eating or smok-
ing.
8. Sampling
8.1 The laboratory sample shall be obtained
in accordance with sampling methods developed
for materials of similar physical form.
8.2 The laboratory sample must be air-dried
and particle size reduced to pass a 0.5-mm screen
as described in Method E 829.
9. Procedure
9.1 After thoroughly mixing the analysis sam-
ple analysis sample to provide the best possible
mix of heavy fines with the milled fluff, transfer
approximately 1 g of the sample to a tared,
previously fired container (weighed to the nearest
0.1 mg) with a scoop or spatula. Quickly weigh
sample and container to the nearest 0.1 mg. As
an alternate method use the dried analysis sample
from the residual moisture determination. See
Test Method E 790.
9.2 Place the uncovered container containing
the sample in the furnace at low temperature and
gradually heat to ignition at such a rate as to
avoid mechanical loss from too rapid expulsion
of volatile matter.
8.3 Finish the ignition to constant weight 9±
0.001 g/h) at 575 ± 25*C. It may be determined
that a constant weight can be routinely estab-
lished by allowing a sample to ash within the
prescribed temperature range for a set period of
time.
Nora J—Experience has shown that panicles of
glass and sand tend to sinter to each other and also to
p porcelain crucibles at temperatures close to 615'C, If
I* laboratory conditions necessitate maintaining ennsist-
e ency in the maximum furnace temperature usai ;b- ash
U tests of other fuels, the ignition may be finished to
c constant weight (±0,001 g/h) at c temperature cf 725
a * 25*C. If this option is invoked it should Hr also noted
U that prolonged exposure to high temperatures may
a actually result in changes in weight due to possible
c chemical reactions.
9.4 Cool in a desiccator over desbcam and
» weigh as soon as possible after the container and
a ash reach the temperature of the area in which
v weighing is performed.
110. Calculations
10.1 Calculate the ash percent in the analysis
s sample as follows:
Ash as-determined. % » HA — B}/C] x 100
% where;
/ A « weight of container and ash residue, g.
IB — weight of empty container, g, and
C C ¦» weight of ash analysis sample, g (includes
residual moisture).
"10.2 Use the numerical moisture value estab-
1 lished by Test Method E 790 for converting ash
( data on the as-determined basts to the dry basis.
I 11. Report
11.1 Difficulty may be experienced in secur-
i ing satisfactory check determinations of ash in
t the same or different laboratories for RDF rich
i in heavy fines. This is caused by siliceous matter
s such as glass and sand as well as a wide variety
c of other particles of different densities entrained
i in the milled RDF in nonuniform strata. When
s such a condition Is anticipated or encountered, a
I paired set of determinations should be made, and
t the results reported as an average. If one deter-
l mination of a paired set is accidentally ruined,
i another pair must be run. An off or unusual
" value does not constitute a ruined determination.
1 In such cases, an additional set of duplicate de-
t terminations should be run and all values re-
I ported as an average of the two sets.
: 12. Precision aad Bias
12.1 Pretixion;
12.1.1 The standard deviations of individual
i determinations in percent absolute are as follows;
Typical A' »i—i.
Value.«
20.0
Within-
Laboortory. %
0.6
Between-
Laboratories. %
I.J
2 :
N-340
-------
# Et830
12,1,2 These precision estimates are based on 12.2 Bias—The bias of this test method can-
an interiaboratory study conducted in accord- noot be determined due to the lack of a recognized
ance with Practice E 180. ststandard reference material.
The American Society.far Testing and Materials takei no pasltkm reretpectlng the validity ofany patent rights asserted in ftmntr/n m
with any item mentioned in this standard. Users if Mi standard are eieqiras/r advised that determinant* if the mlidit r nf any stick
patent rights, and the ritk of infringement tf tuck rights. mre entirety ththeir tmn responsibility
This standard is sitftject to revision at any time by the resptmsMr it technical committee and must he reviewed every five years and .
(f m» revised, either reapprtnted tw vAthdmwn. Ytmr comments are r invited either for reviiUm vf this standard or for additional
standards and should he addressed to ASTM Headquarters Your etmmments will metre cartful camidemitm at a meeting if the
responsible technical ctxnmittec. which yint may attend. If you feel ththat your comments have not received a fair heating you should
make ytmr tleuv knmrn to the ASTM Committee tm Standards. 1916 6 Race St.. Philadelphia. FA 1910S.
3
N-341
-------
Designation: E 897 - 68
nmem soaeiv *on icsima «vo matim *l i
_ . < A!rrv
Standard Test Method for
Volatile Matter In the Analysis SSample of Refuse-Derive f r^c!1
1. Scope
i.l This test method covets the determination of the
percentage of gaseous products, exclusive of moisture vapor,
In the analysis sample which is released under specific
conditions of the test The knowledge of the volatile matter
contest assists in predicting burning characteristics of RDF.
iJ This test method nay be applicable to any waste
materia! from which a laboratory analysis sample can be
prepared
1J Tius standard may myohe hazardous materials, oper-
ations, ami equipment. This standard does not purport to
address all of the safety problems associated with its use. It is
the responsibility of the user of this standard to establish
appropriate safety end health practices and determine the
applicability of regulatory limitations prior to use.
Tfctt rtmdaM » Jsucd uader «h# B*»i itmfmlkm EW7; the ivmrnber miwuliad; faOowim tbe dcriguliea iadkatn t*tr ;t*r of
origiMl •doptim or, ia She aw rffrtwa. A* jm of 1M i?»»o«or. A mats hi pvnOcta indicates tie yar «TIm itapprovti \
¦vern^ («) iKSata ta «dH«^ etaa«( iocc te IM ic imio^ir inppra«tL
4. Summary «fTest Method
4.1 Volatue matter is determined by the ioss
in weight resulting from heating refuse-derived fuel under
i^jdly-ccnooUed conditions. The measured weight loss,
corrected for moisture as determined in Test Method E 790,
establishes the volatile matter content
5. Apparatus
5.1 Platinum or Fused Quartz Cruc'ble. with closely
fitting cover. The crucible shall be of not less than 10 nor
more than 20 mL capacity, sot less than 23 nor more than
35 mm in diameto, and not less than 30 nor more than 35
mm in height
5.2 Vertical Electric Tube Furnace—The furnace may be
of the form shown in Fig. 1. It shall be regulated to maintain
a temperature of950 ± 20*C in the crucible, as measured by
a thermocouple positioned in the furnace.
•» nwu8
6.1 Due to the origins of RDF m munkipt] waste,
common sense dictates that precautions should be observed
when conducting tests on the samples. Recommended hy-
gienic practices include use of gloves when handling RDF,
wearing dust masks (NTOSH-approved type), especially while
mining RDF samples, conducting tests under: a negative-
pressure hood when possible, and washing hands before
eating or smoking.
Not* I r«
mixed air-dried analysis RDF sample in a weighed crucible,
dose with a com (Note 2% place on a platinum or
Nkhrome-wiie support and insert directly into the furnace
chamber, which shall be maintained at a temperature of 9 JO
± 20*C Lower the crucible immediately to the 9S0*C zone.
Regulation of tbe temperature to within the prescribed limits
ia critical. After the more rapid discharge of volatile matter
has subsided as drawn by disappearance of the luminous
flame, inspect the crucibte to verify that the Hd is still seated.
If necessaiy, reseat the hd to guard against the admission of
air into the crucible. Do this as rapidly as possible ty raising
the cratible to the top of the furnace dumber, repo^tios the
M to more perfectly seal the crucible, then lower immedi-
ately back to the 950*C zone.
Documents
2.1 ASTM Standards:
E 180 Practice for Determining the Precisian Data of
ASTM Methods fat Analysis and Testing of industrial
Chemicals2
E 790 Test Method for Residual Moisture in a Refuse-
Derived Fuel Analysis Sample3
E 829 Test Method for Preparing RDF Laboratory Sam-
ples for Analysis3
3. Definition
3.1 rrfuse^lerivcd fuel (RDF):
RDF-1—Waste used as a fuel in as-discarded form.
RDF-2—Waste processed to coarse particle size with or
without ferrous metal separation.
RDF-3—shredded fiid derived from municipal sofid
waste (MSW) that has been processed to remove metal, glass,
nH other inorganics. This mawjai h« a puffVi* such
that 95 weight % passes through a 24b. square mesh screes.
RDF-4~-Combustibk waste processed into powder
fbnn—95 weight % passing a iO-mesh screen,
RDF—5—-Combustible waste densified (compressed) into
the form of pellets, dugs, cubettes or briquettes.
RDF-6—-Combustible waste processed into liquid fueL
RDF-7 —Combustible waste processed into gaseous fiuL
¦ nil Ml mahod ii tmtar the jmMfcrioa of ASTM C«—riimt D-M a
Wm Mauftmx and it tbe direct iopoa4fci8t)r ai Subcoowmnt* OKI) on
Oftiwart Toeta*
Ohm wtoim Much IS, i9St MW May ittt, OripsaRy
iwhltil iilwllW-t2.ua snwoMt «fe»o« 8 »T - C.
'*mm**>okifAm/S>u+Hb. Vol ISJK.
aktfASm Jt»ad»irtf. Vol IUH.
Nor* 2—The earn dmiH It doadjr mouth so dm die carbon
depost from tte rtfiue derived (Ud doe* not bora a*«y from tbe
1 1
N-342
-------
# EE897
7.2 After heating for a total of exactly 7 mla, remove the
erucibk from tbe furnace and, without disturbing the cover,
allow it to cool on < metal cooling block. Weigh as soon as
cold (Note 3). The percentage loss of weight minus the
perrrntagr moisture is accordance with Test Method E 790
is the volatile matter. •
NOTE 3—To e*w»e uniformity of wuit»,tfceeofiliaiperioa*«lM
be kqrt oon«ua *od ihoald not be pcok>n«aJ beyond ISmin.
S. Calculation
8.! Calculate the percentage of volatile matter on an ¦as-
determined" bass* as follows
lOoj-M.,
where:
A ' - weight of sample used, g,
B - weight of sample after heating, g. tad
Mlm/i • moisture (as-determined), %.
9. aid Bin
9.1 Precision:
9.1.1 The standard deviation of individual detenninatkms,
in percent absolute, is as Mows:
Typical Avenge Value, M *
Wlthin-LibGiatoiy, 0.7 %
Between-Labocaieriea, 11 ft
9.1 J The precision estimates is 8.1.1 are based on as
interfabomary study conducted in accadance with Practice
E 180.
92 Bias:
9.2.1 Hie bias of this test method has not been detenniaed.
9,22 Precision estimates an based on A5TM Report No.
RR;E 18-1000 which describes the preliminary testing and
round-rebut tests.4
*$H)|Wtua dab ac naWfc sa Ion tea A5TM Bait Mn faqaal
ML-t M-I00C.
!^^nwtoiSee«)r Kir T«si»v «ntf ItewM ate JwpoMiortiin M*p«eaav«M wMHly HwMMeamKtton
wlit try Ktm mmtame In cm Mmtottl, Umn m ft* aandvtl * «r» vprmt*/ wMmq mm towmmnm d m t*kOy at mtf midI
pmWJ rfgna, MS wC mm Or IRrflpnM V fOCn rfgnu, mw wuuvy IflVr mtfKKWmKKf.
Th* tand*tihivt>t*ct to rMX>rr to* trrttmrHpemtatf actinic* common fin *xt
mtWT—xxvtrntvwtMmn roue comma w* I* Immewtfmr tot m*iimetm*»namilerlri*aioiw/$m>amt*
imf I'lli'm ifiUMMn' III ITTIf Ifmliam Vmmummn irtfmemhmcaiwMawMwifa •*. »—n.
Kcftoic*eatmum, tmiefi youmjfaoantf. rywlmutmyor ereanimm Immaammtma• fc* >a/sncutt imm )«ar
ttmrn Known to B» AS7V Ceiiwnmm on S&ndirtb, ISrflRao*£r&. PMMapMi, M 19103.
22
N-343
-------
Designation: E 849 - 88
*mmmca* aocirrv rem rtiiM «ms iw-rwu
plpled.
3.10 sample dt*isim—^be process of extracting a smaller
si sample ftom a sample so thai the representative properties of
ttthe larger sample are retained. During this process it is
•(assumed that no change in particle size or other characteristics
o< occurs.
3.11 sample prtparation~4ht process that indudes drying,
stsize reduction, division, and mixing of a laboratory sample
fcfcr the purpose of obtaining as unbiased analysis cample.
3.12 sample redmton-^&tt process whereby sample par-
tatide site is reduced without change in sample weight
3.13 significant fats—any loss that introduces a bias in
fiifiaal results that is of appreciable importance to concerned
p parties.
44. SmaaryofT«t Method
4.1 This test method is based on the Uas in weight of RDF
ilia an air atmosphere under cootrofled conditions of temper-
a amre, time, and air flow.
4J2 The laboratory sample is air-dried to near equilibrium
* with the atmosphere in the area where division and reduction
* wiS take pbce. The residual moisture determination is made
it ia a hated, Ibrced-cimilation oven, undo' rigidly defined
e ccoditioas.
1
W.'Jdd
-------
EC949
43 Use total moisture is calculated from losses in m•
drying and tie residual moisture as shewn in Section 11.
5. Significance and Use
5.1 The collection and treatment ofthe sample as specified
herein is intended for the specific purpose of deterainmt the
total moisture in a laboratory sample of RDF.
52 This test method is available as the netted for
determination of total moisture unless alternative techniques
or modifications have been agreed upon by involved patties.
6. Appanos
6.1 Air Dry Moisture:
6.1.1 Drying Oven—A larys chamber mechanical draft
oven capable of maintaining a controlled temperature in die
range of 25 to 40*G Air changes should be at the rate of 1 to
4 chances per minute. Air flow thould be baffled to prevent
samples from being blown out of the sample containers.
6.1.2 Drying Pan—A nos-cornxfing pan or mesh basket
to be used for holding the sample during air drying operations.
6.1.3 Balance (Laboratory Sample}—A balance of suffi-
cient capacity to weigh the sample and container with a
sensitivity of 0.5 g.
62 Sample Reduction:
6.2. i Mill—A mill operating on the principle of catling or
shearing action shall be used for sample panicle size reduc-
tion. It shall have the capability to regulate the particle size
of the final product by means of either interchangeable
screens or mill adjustments. The mill shall be endosed and
should generate a minimum amount of heat during the
miling process to minimize the potential for loss of moisture.
The final product shall pass through a 0.5 mm or smaller
screen into a receiver integral with the mill Access should be
provided so that die mill can be cleaned quickly and easily
between samples.
6.3 Residual Moisture:
6.3.1 Drying Oven-
£3.1.1 Refm: Type—The oven shall be so constructs! as
to have a uniform temperature within the specimen chamber,
have a minimum excess air volume, and be capable of
constant temperature regulation a: 107 ± TC. Provision shall
be made for renewing the preheated air in the oven at die
lite of two to four times a minute, with the intake air dried
by passing it through a desccant An oven similar to the one
Qhistxatcd in Fig. 1, Moisture Oven, of Test Method D 3173
is suitable.
6.3.1.2 Routine Type—A dicing oven of either the me-
chanical or natural drcolaiiao type which is capable of con-
stant uniform temperature within the specimen chamber
regulated at 10? ± 3*C
Note !—Either type ofovea nay be awd for routine dexnniiiatioQt.
Hcwr*r, tbe refercr-type e*ea shall be used to resolve dUkrmca
between determinations,
H % Cnrminm—A convenient form that allows the ash
determination to be made on the same sample is a porcelain
22 mm in depth and 44 mm in diameter or a fused
silica capsule of similar shape. This shall be used with a well-
fittiag f_'.; eating or smoking.
7-2 Laboratory sample hanging fee performed ty
- trained personnel. AS operations shall be done as rapidly as
; possible to avoid sample moisture changes due to atmospheric
i exposure.
7.3 At dl times RDF samples should be protected from
- moisture change due to exposure to rain, snow and sun, or
• contact with absorbent materials.
7.4 Since heavy fine particles tend to segregate rapidly in
the RDF analysis sample, the analyst should exercise care to
; assure that the analysis sample is well mixed prior to perform-
: ing the residual moisture determination.
7.5 When the residual moisture is to be used for As
i determination of total moisture, special care shall be taken
' to avoid any change in sample moisture between the comple-
¦ tk>n of air drying and analysis ft* residual moisture. It is
: recommended that the delay between sample preparation and
- the determination of residual moisture be a maximum of 72
i h.
7.6 Samples should be transported to the laboratory and
: analyzed as soon as possible. If any sample handling step
i involves an extended time period, the sample and container
i should be weighed before and after the process to determine
: any weight gain or loss. This weight gain or loss shall be
i included in the calculation of moisture content.
7.7 Force-feeding of the sample through the mill can over-
I load the motor. An overload can cause rapid heating of the
i rotor and mill chamber with possible loss of residual mois-
-) tare.
! S. Sampling (Note 2)
8.1 RDF products are frequently nonhomogeaeous. For
¦ this reason, care should be exercised to obtain a representative
t sample from the RDF lot to be characterized.
82 The sampling method for this procedure should be
¦ based on agreement between the involved parties.
8.3 For this procedure the laboratory sample sfae will
normally not wVwH 2 kg with some variation possible de-
: pending on the laboratory equipment available.
8J.1 Due to the heterogeneous nature of RDF, dividing a
laboratory sample to a very stsaD size analysis sample may
result iii non-representative results. Since milling operations
mix the sample as well as reduce particle size, laboratory
2 !
N-345
-------
£8949
samples should not he divided before the initial preparation
steps ha Ye been completed.
Nora 2—ASTM Subcommittee E3S.01 it currently in the proces of
devetopinj a procedure for sampling RDF. Tic efeainsuui of E3S.0I
muia be contacted ibr details.
9. Sample Preparation
9.1 The principles, terms, organization and preparation
procedures as established ia Method E 829 dull apply to the
handling and preparation of RDF for determination of total
moisture by the two-stage method,
92 This procedure provides for using an air-drying oven
to equilibrate laboratory sample moisture prior to reduction
in size or amount and a moisture oven for determination of
residual moisture on the air-dried analysis sample.
93 The laboratory sample must be air dried and particle
size reduced to pass a 0.5 mm screen as described in Method
E 829, for the residual moisture (second stage) of the total
moisture determination.
10. Procedure
10,1 Air Drying Laboratory Sample:
10.1.1 Weigh the entire laboratory sample into a tared air-
drying pan. Use more than one pan if necessary. If a very
fine mesh type of drying pan is used, size the mesh such that
the sample will not be lost through it Sample depth in the
drying pan shall be no greater than 10 an (4 in) and any
lumps of sample shall be broken up.
10.1.2 Air dry the sample at 10 to 15% above ambient,
but sot greater than 40*C until the weight loss is less than
0.1 % of the sample weight per hour. Normally, allow die
sample to air dry for a set time period such as overnight or
24 b. To speed the drying stage, stir the sample cucMy
while avoiding loss of sample (Note 3).
Nome 3—'Tie aktfiidwBeGf the forced draft air drying eves ibould
be Owed prior w dactiMy W minimize laboratory connmhartop by
atremsiaed RDF dun.
10.1.3 At the end of the air drying period, cod the sample
to room temperature and weigh. Protect die sample from
contamination and loss during the cool-down process but do
not place in a desiccator. Calculate air dry moisture toss
percent in accordance with Section 11.
10.1.4 Separate, weigh, and bold non-mfllables for farther
clarification and use for analysis if necessary (Note 4). Mill
die remainder of the sample in accordance with Method
E829. .
10.1 J The calculation for the decimal percent of mm*
milkhles {NAf) is.
•[If We»*llt *" of nop-mfflables
" Weight in gnmi of air-drwd sample
Not* 4—Noo-milUhlo we thaae ctattriab whkfc *01 not pm
tftnwgfc the Boflinj jcrwa, or nay fcmur the aiMina separates, or
t bolla.
102 Residue! Moisture an Air-Dried 4/uJysit Sanpt*-
10.2.1 Heat the empty containers and covers under the
c conditiooi at which the sample n
t or cover on the container, coot over a desiccant ibr about 15
I to 20 min, and weigh. Mix the sample, if cecessary, ard cEp
c out with a spoon or spatula from the sample bottle approxi-
i mately t g of the sample. Put the ample quickly into the
c container, cover and weigh at once (Note 5).
Nan 3—K wei|tti«bottfci wife ik-^Qovm a» not
t be wcewy to preheit the majeure twjjrm container oor » descale
r ItlRErdiytag.
10.22 Remove die cover and place in a desiccator. Quickly
I place the uncovered container into ac ovea preheated to 107
r ± 3*C through which is passed a current of dry air. Ctase the
i oven at opce and heat for 1 h. Open the oven, remove, cover
t the container quickly, and cool is a desiccator over desiccant.
1 Weigh die sample Mid container as soot* as cooled to room
t temperature.
1 11. Calculation
11.1 The air dry moisture. A,» calculated as foL'owj;
,oo
* where:
/. A «¦ air diy moisture, %,
i residual moisture, %,
& S — grams of analysis sample used,
IB « grams of sample after heating at 10TC, and
f NM " dedmal percent of non-mfllables as determined in
10.1.5.
11.3 Calculate the percent total moisture, M, in the labo-
rs ratory sample, as follows:
it (100 — A)
too
nwhere:
A M «total moisture, %,
I* ¦ residual moiaare,*, and
AA * air dry moisture, %
112. PredsliM aid Bias
12.1 Precision and Was has not been determined
ThtMmtem Sockty tor TooUng wti MMvMt fctav no ponttaff tovoopoc^ig Ml vtttsRy of onfp
•tt o/tf Boot mtftk/nKt Ai Mi tttn&td. Utot% of Mi MVNtvtf mi #i BKptoo&y imMmnI thot t
pouttt rtgfn, m*9m ifift of tnMnffttntnt of ousti oroototofr oonnotpofio&Ry»
i * tfw * **T **h
Ifen MMMnf fc autyKf 90 & Ottf fl
ottif tBtppf^oodofWfOoiPKtttL, YflurconMsntowiAMftMCKf oOtf Mr PMMofi §f MtoflOnMnf or tot ¦cHUom' tfwnMrtli
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itomtSMCommm** W$mm$U*********
3
N-346
-------
N-7
pH and Temperature
N-347
-------
pH VALUE (4500-H* yElactrometric Method
4500-H+ pH VALUE*
4-65
4500-H + A.
t. Principles "•
Measurement of pH is one of the most Important and fre-
quently used tests in water chemistry. Practically every phase of
water supply and wastewater treatment, e.g., acid-base neutral-
ization, water softening, precipitation, coagulation, disinfection,
and corrosion control, is pH-dependeot. pH is used in alkalinity
and carbon dioxide measurements and many other acid-base
equilibria. At a given temperature the intensity of the acidic or
basic character of a solution is indicated by pH or hydrogen ion
activity. Alkalinity and acidity are the acid- and base-neutralizing
capacities of a water and usually are expressed as milligrams
CaCO, per liter. Buffer capacity is the amount of strong acid or
base, usually expressed in moles per liter, needed to change the
pH value of a 1-L sample by 1 unit. pH as defined by Sorenson1
is -log [H*J; it is the "intensity" factor of acidity. Pure water
is very slightly ionized and at equilibrium the ion product is
(H*][OH*] - X.
- 1.01 x 10-" at 2TC (1)
and
fH-1 - [OH-1
- 1.005 x 10-'
where
[H*] «= activity of hydrogen ions, molest,
(OH " I = activity of hydroxyl ions, motes/]., and
K. m ion product of water.
Because of ionic interactions in all but very dilute solutions,
it is necessary to use the "activity" of as ion and not its molar
concentration. Use of the term pH assumes that the activity of
* Approved bj> Stndard Methods Cbmaiuee, 1990.
Introduction
the hydrogen ion, «„~, is being considered. The approximate
equivalence to molarity, (H*| can be presumed only in very
dilute solutions (ionic strength <0.1).
A logarithmic scale is convenient for expressing a wide range
of ionic activities. Equation 1 is logarithoruc form and corrected
to reflect activity is:
+ (-fog.««oH-) - » (2)
or
pH + pOH - pA'„
where:
pHt - logio e„- and
pOH • kjglea0H".
Equation 2 states that as pH increases pOH decreases corre-
spondingly and vice versa because pK, is constant for a given
temperature. At 2S*C, pH 7,0 is neutral, the activities of the
hydrogen and hydroxyl ions are equal, and each corresponds to
an approximate activity of 10*' moies/L. The neutral point is
temperature-dependent and is pH 7,5 at 0*C and pH 6.5 at S0°C.
The pH value of a highly dilute solution is apprcxima.eiy the
same as the negative common logarithm of the hydrogen ion
concentration. Natural waters usually have pH values in the range
of 4 to 9, and most are slightly basic because of the presence of
bicarbonates and carbonates of the alkali and alkaline eartfe met-
als.
2. Reference
1. Sorehson, S, 1909. t/ber die Messung ucd die Bedeucurig de: Was-
jentoffionen Koozentration bei Enrvmatischen Proiessen. Bwchrrr
Z. 21:131.
t p dwigiHt* -k>tM of * sutsber
4500-H- B. Electrometric Method
1. General Discussion
a. Principle: The basic principle of electrometric pH meas-
urement is determination of the activity of the hydrogen ions by
potentiometric measurement using a standard hydrogen elec-
trode and a reference electrode. The hydrogen electrode consists
of a platinum electrode across which hydrogen gas is bubbled at
a pressure of 101 kPa. Because of difficulty in its use and the
potential for poisoning die hydrogen electrode, the glass elec-
trode commonly is used. The electromotive force (emf) produced
in the glass electrode system varies linearly with pH. "litis linear
relationship is described by plotting the measured emf against
the pH of different buffers. Sample pH is determined by ex-
trapolation.
Because single ion activities such as oH- cannot be measured
pH is defined operationally on a potentiomeme scale. The pf-
measuriag instrument is calibrated potenaometricaliy with ai
indicating (glass) electrode and a reference electrode using Na
tioaal Institute of Standards and Technology (N1ST) buffers ha>
kg assigned values so that:
pH, - - ioglsaH •
N-348
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TEMPERATURE {2550)/Laboratory and Field Methods
2-59
2550 TEMPERATURE*
2550 A. introduction
Temperature readings arc used id the calculation of various
forms of alkalinity, in studies of saturation and stability with
respect to calcium carbonate, in the calculation of salinity, and
• Approved by Standard Methods Committee, 1W3.
in general laboratory operations. In Itanological studies, water
temperatures as a function of depth often are required. Elevated
temperatures resulting from discbarges of heated water may have
significant ecological impact. Identification of source of water
supply, such as deep wells, often is possible by temperature
measurements alone. Industrial plants often require data on water
temperature for process use ot heat-transmission calculations.
2550 B. Laboratory and Field Methods
1. laboratory and Other Non-Depth Temperature
Measurements
Normally, temperature measurements may be made with any
good mercury-filled Celsius thermometer. As a minimum, the
thermometer should have a scale marked for every 0.1*C, with
markings etched on the capillary glass. The thermometer should
have a minimal thermal capacity to permit rapid equilibration.
Periodically check the thermometer against a precision ther-
mometer certified by the National Institute of Standards and
Technology (NIST, formerly National Bureau of Standards)*
that is used with its certificate and correction chart. For field
operations use a thermometer having a metal case to prevent
breakage.
Thermometers are calibrated for total immersion or partial
immersion. One calibrated for total immersion must be com-
pletely immersed to the depth of the etched circle around the
stem just below the scale level.
2. Depth Temperature Measurements
Depth temperature tequired for limnologicaJ studies may be
measured with a reversing thermometer, thennophone, or ther-
mistor. The thermistor is must convenient and accurate; how-
ever, higher cost may preclude its use. Calibrate any temperature
measurement devices with a NIST-certified thermometer before
field use. Make readings with the thermometer or device im-
mereed is water Song enough to permit complete equilibration.
Report results to the nearest 0.1 or 1.0*C, depending on need.
The thermometer commonly used for depth measurements is
of the reversing type. It often is mounted on the sample collection
apparatus so that a water sample may be obtained simultane-
ously. Correct readings of reversing thermometers for changes
due to differences between temperature at reversal and temper-
ature at time of reading. Calculate as follows:
tT>
(V - ,) (r ¦» v0)
3 +
K
(T
i) (v + y»)
+ L
• ^i»ie eomnrwrriaJ tLrnnometers may ht as much t» 3*C is error.
where:
AT « correction to be added algebraically to uncorrected leading,
V - uncorrected reading at reversal,
t — temperature at which thermometer is read,
Vs m volume of small bulb end of capillary up to 0*C graduation,
K ¦ constant depending on relative thermal expansion ol mercury
and glass (usual value of K ¦ 6100), and
L « calibration correction of thermometer depending on T.
If series observations are made it is convenient to prepare
graphs for a thermometer to obtain AT from any values of V
and l
3. Bibliography
Wawin, H.F. 4 G.C. Whipple. 1895 The thennophone—A new in-
strument for determining temperatures. Mass. Inst. Ttehnol. Quart
8:125.
SvEjwaup, H.V., M.W. Johnson A R.H. Fleming. 1942. The Oceans.
Prentice-Hall, Inc., Englewood Gifts, N.J.
Amejucan Society for Testing and Materials. 1949. Standard
Specifications for ASTM Thermometers. No. E1-S8, ASTM, Phil-
adelphia, Pa.
Ree, W.R. 1953. Thermistors for depth thermometry. J, Amer. Water
Works Aooe. 45:259.
N-349
-------
2-60
PHYSICAL & AGGREGATE PROPERTIES (2000)
2560 PARTICLE COUNTING AND SIZE DISTRIBUTION (PROPOSED)*
2560 A, Introduction
1. Genera! Discussion
Particles are ubiquitous is natural waters and in-water and
wastewater treatment streams. Particle counting and size distri-
bution analysis can help to determine the makeup of natural
waters, treatment plant influent, process water, and finished water.
Similarly, it can aid in designing treatment processes, making
derisions about changes in operations, and/or determining pro-
cess efficiency. Methods for measuring particle size distribution
included iierein depend on electronic measurement devices be-
cause manual methods are likely to be too stew for routine anal-
ysis'. However, when particle size analysis is to include size dis-
tribution of large (>500-^un) aggregates, use direct microscopic
counting and sizing. Principles of various types of instruments
capable of producing both size and number concentration infor-
mation on particulate dispersions are included. Unless explicitly
stated otherwise, the term "size distribution" means an absolute
size distribution, i.e., one that includes the number concentration
or count.
In most particle-counting instruments, particles pass though a
sensing zone where they are measured individually; the only
exception included is the static type of light-scattering instru-
ment. Instruments create an electronic pulse (voltage, current,
or resistance) that is proportional to a characteristic size of the
particle. The instrument responses (pulse height, width, or area)
are classified by magnitude and counted in each class to yield
the panicle size distribution.
2. Selection of Method
Three instrument types are included; electrical sensing zone
instruments, light-blockage instruments, and light-scattering
instruments.
Select instrument consistent with expected use of the particle
size analysis. Instruments vary in the particle characteristic being
sensed, lower and upper size limits of detection, degree of res-
olution of the size distribution, particle number concentration
range that aui be measured accurately, amount of shear to which
a sample is subjected before measurement, amount of sample prep-
aration, operator skill required, and the ease with which data can
be obtained and manipulated into the desired forms. See Sections
2560B.1, C.l, and D.l, and manufacturers* literature for infor-
mation on characteristics of each type of instrumentation.
Some instruments can be set up for either continuous-flow or
batch sampling. Others can be used only for batch analysis. For
instruments usable in both modes, check that no systematic dif-
ferences in particle size distributions occur between continuous-
flow measurements and batch samples taken at or near the intake
point for continuous-Dow samples.
* Approved by Standard Method* Coomincc, 1993.
3. Sample Collection and Handling
a. Beach Samples: Use extreme care in obtaining, handling,
and preparing batch samples to avoid changing total particle
count and size distribution.
Choose representative times and locations for sampling. En-
sure that particles are not subjected to greater physical forces
during collection than in their natural setting Collect samples
from a body of water with submerged vessels to minimize tur-
bulence and bubble entrainment. If sampling from particular
depths, nse standard samplers designed for that purpose. For
flowing systems, make sure that the velocity into the opening of
the sampling device is the same u that of the flowing stream
(isokinetic sampling) and that the opening diameter is at least
50 times as large as the particles to be measured. For sampling
from a tap, let water flow slowly and continuously down the side
of the collection vessel.
Minimize particle contamination from the air, dilution water
(or, for electrical sensing zone instruments, electrolyte solution)
(see f 4 below), and any vessel or glassware that comes in contact
with the sample. Minimize exposure to air by keeping sample in
a closed container and by minimizing time between sampling and
analysis.
Preferably use glass bottles and other vessels with bottle cap
liners of TEE.
Dean all glassware scrupulously by automatic dishwashing,
vigorous hand brushing, and/or ultrasonication. Rinse glassware
immediately before use with particle-free water. Between sam-
ples, rinse any part of the instrument that comes in contact with
samples with either dean water or the upcoming sample. Alter-
natively, run multiple replicates and discard the first results
To avoid breakup of aggregates of particles or floes, sample
and make dilutions very slowly using wide-bore pipets. needles,
or other sampling devices; cut off pipet ties ;o avoid high ve-
locities at the entrance. If sample dilution is required, add sample
to dilution water, not vice vena, by submerging the pipe! tip m
the dilution water and releasing sample slowly. Use minimum
intensity and duration of mixing adequate to dilute the sus-
pension into the dilution water. Avoid mechanical stirrer* inside
the sample or ultrasonication. Simultaneously gently rotate and
partially invert entire sample in a closed bottle. Use cylin-
drical dilution bottles to avoid sharp corners. Leave less than
approximately 25% air space during mixing. To avoid sedimen-
tation, make measurements immediately after mixing. Do not
mix during measurement unless absolutely necessary to prevent
sedimentation.
Most surface and ground waters contain relatively stable par-
tides that aggregate slowly. Particle size distributee? in biolog-
ically active waters or waters that have been created with co-
agulants is more likely to change over short time periods. To
minimize flocculation, minimise time between sampling and
measurement. In highly flocculent systems, maximum holding
time should be only a few minutes; for more stable samples, a
few hours may be acceptable. Dilution slows floceulation kinetics
N-350
-------
N-8
CO Protocol
(See EPA Reference Method 10A, CFR 40, Part 60
N-351
-------
N-9
C02 and 02 Protocols
(See EPA Reference Method 3A, CFR 40, Part 60
N-352
-------
N-10
Composite Sampling
N-353
-------
Designation: D 6051 - 96
AMEItGAIf SOOETf pon 7E5TINQ AMC MATEHMJI
iQO Sarf Hvfccr f>- Ww* Cowctioduvv M tft<2l
ftwMM *wn W* ***¦< So* A3TM Standard Gopyn?* *ami
Standard Guide for
Composite Sampling and Fietdd Subsampling for
Environmental Waste Managenment Activities1
Tl*
tion ofisapp.Qpriate sampling equipment, sample collection n
procedures ar collection ofa representative specimen from a a
sample, or atitisrical interpretation of resultant data andd
devices designed to dynamically sample process waste®
stream It also does sot provide sufficient infonnition too
statistically design an optimized sampling plan, or determine*
the number of samples to collect or calculate the optimum n
number of samples to composite to achieve specified datata
quality objectives (see Practise D 3792). Standard procedures s
for planning waste sampling activities are addressed in Guide te
D4687.
1J The sample mixing and subsampling procedures d&-&-
scribed in this guide are considered inappropriate for samplesa
to be analyzed for volatile organic compounds. VolatOek
organka are typically lost througi volatilization during lg
SMBpk collection, shippsg fw^ Iibotstory SBznptelc
preparation unless specialized procedures are seed. Thete
enhanced mixing described in this guide is expected to cause*
significant Tf— of volatile constituents. Specialized pfooo*o>
duxes ihould be used for compositing samples for detennin*-*-
tion of voices such as combining directly into aifthtnolol
(see Practice D 4547).
1,4 ThU standard does not purport to address all qftMit
safety conctms, (f any, associated with Its we. Jt 6 thdm
responsibility tf tie user this standard to establish appro*-
priate safety end health practices and determine the appttava-
bility « jnrhifirHnn aiASTU Oiwliw D-W at
I li tkft tfbvct fHposcdflty ofSatecMsUswD^4«Ot 0§'
Obbbc cAtott Dkl !0» 19N.
•kfASTUStrndm*. V« MA
*¦1—f net if MTU ftwiir*. V«l 94Jt.
MniMrfima tfASTHSmtimli. V# UiX.
N-354
-------
# ID 8051
dares for a sample
» The bold/** Bum ben is patei lifer to « B* ct ittmam u Ife* tad at
of contaminant standard
deviation cannot be calculated from one composite sample.
However, the precision of a single composite sample may be
estimated when there are data to show the relationship
between the precision of the individual samples that com-
prise the composite sample and that of the composite
sample. The precision (standard deviation) of the composite
simple is approximately the precision of the individual
samples divided by the square root of the number of
individual —rnpv* in the composite.
6.4 Example /—An example of how a single composite
sample can be used for decision-making purposes is given
here. Assume a regulatory limit of 1 mg/kg and a standard
deviation of (15 mg/kg for the individual samplfa If tile
concentration of a site is estimated to be atoond 0.6 mg/kg,
how many inffividual samples should be composited to have
relatively high confidence that the true concentration does
not exceed the regalataty limit when only one composite
sample is used? Assuming the composite is well mixed, then
the precision of a composite is a taction of the number of
samples as follows:
Number of l*Hvi Cfespabi srOwCoapoateSUBffc
fcU
COS
&23
CJ2
ft»
Thus, if six samples are included in a composite, the
composite concentration of 0.6 mg/kg is two standard
deviations below the regulatory HmiL Therefore, if the
composite concentration is actually observed to be in the
neighborhood of 0.6 mg/kg. we can be reasonably confident
(approximately 95 X) that the concentration of the site is
bdow the regtdaiaiy Emit, using only one composite sample.
6J Example 2—.Another trample is when the standard
deviation of the individual samples in the previous example
is relatively small, aay 0.1 mg/kg. Then the standard devia-
tion of a composite of 6 individual samples is 0.04 mg/kg
VI. 1 mg/kg divided by the square root of6» 0.04 m&frg), a
very small number relative to the regulatory fimit of 1
«ng/lrg. In this case, simple comparison of the composite
concentration to the regulatory limit is often quit* adequate
for decision-making purposes.
: 2
N-355
-------
(> D 6051
6.5.1 The effectiveness of compositing depends on this
relative magnitude of sampling and analytical error. Wham
sampling uncertainty is high relative to analytical error (as is Is
usually assumed tc be the case) compositing is very effectivsvc
la improving precision. If analytical earns are high idativsve
titers, jample i* itiu**.! *&•, C4«»cU*
6J52 Because composting is a physical avenging processes,
composite samples tend to be more normally distributedsd
than the individual samples. The normalising effect it is
fteqnently an advantage since calculation of means, standardrd
deviations and confidence intervals generally assume thdw
data are normally distributed. Although environmental isks-
idue data are commonly non-normally distributed, com-n-
ponting often leads to approximate normality and avoids thche
seed to transform the data.
&5J The spatial design of the compositing scheme can bebe
Important Depending upon the locations from which thihe
indroshul samples are collected and composited, compositeies
can be used to determine spatial variability or improve thche
precision of the parameter being tstimatftl. Inures 1 and 2 2
represent a site divided into four ceOs. Composite all sampteles
with the same number together. The stapling approach it in
Fig. I is similar to sample random sampling, except they amre
sow composite sampler Each composite sample in this caaase
is a representative sample of fee entire site, eliminators
ceH-to-cell variability, and leads to increased precision iiin
estimating the mean concentration of the site. If there is a •
need to estimate the cell-to-cell variability, then the approackch
in Fig. 2 is suitable. In addition, if the precision of estimatin>ag
the mean concentration of the ceQ is needed, muW(d{de
composite samples should be collected from that celL
6.6 Effect on Cost Reduction—Because the composhdte
«"wrt"« yield a more precise mean estimate than the samme
number of individual samples, there is the potential fofor
substantial cost saving Given the higher precision asweintmnd
with composite samples, the number of compoete samplaks
required to achieve a specified precision is smaller titan th*at
requited for individual samples. This oost saving opportunitiity
is especially pronounced when the oost of sample aplysis a k
high relative to the cost of compositing
analyzing.
6.7 Mat Container/Hot Spot Identification and Retestinjng
Schemes—Samples can be combined to determine whethAer
aa individual sample exceeds a specified Unit as long as ththe
actios lout is relatively high compared with the tcaimal
detection Emit and the average sample concentration. DOa»
pending on the difficulty and probability of having t to
icwmpte, it may be desirable to retain a spit of the discretete
—£br possible analysis depending on'the
results from die composite sample. ;
1 2
4 3
4 3
2 1
4 2
3 1
1 4
2 3
1 1
1 1
2 i
2 2
3 *
3 3
4 4
4 4 !
HQ. 1 Esanptovf CaMpedhaAonMaatto
Ml 2 barapla of Within CH Cempe«Mng
6.8 Example 3—One hundred drums are to be examined
to determine whether the concentration ofPCBs exceeds 50
mgfl®. Assume the detectica limit is 3 at&kg and most
drums have non-detectable levels. Composting samples
from ten drams for analysis would permit determining tha'
none of the drums in the composite exceed SO mg/kg as long
as the concentration of the composite is <5 mg/kg. If the
detected concentration is >5 mg/kg. one or more drums ma>
exceed SO mg/kl and additional analyses of the individua
drams are required to identify any hot drura(s). The max-
imum number of samples that can theoretically be com-
posited and still detect a hot sampk is the Emit of concerr
divided by the actual detection limit (for example, SO mg/lq
~ 5 mg/kg - 10).
6S Example 4—Assume background levels of dioxin azr
non detectable, and the analytical detection Emit is 1 jig/Vj
and the action level is SO jig/kg. The site is systematically
gridded (the most efficient sampling design for detectinj
randomly distributed hot spots} using aa appropriate design
and cores to a depth of 10 cm are coBected. Coco posit
sampks an collected since analytical costs for dioxin tr
high. Ia theory, groups of up to SO samples could b
composited and If the resultant concentiation were <
pg/kg, aH samples represented in the composite should b
below SO Jtg/kg. If the contaminant concentiation is >
Hg'kg. one or more ipots may exist that exceed SO jig/kg i
the axea covered by the oonsposte sample ahhmngh th
praise location and areal extent would not be know
without further «»mpKng gad analyses. Compositing fewf
aunties would probably be more practical, however.
6.9.1 The relative efficiency of comporting individu
samples to detect a hot spot depends on the probability of
"hot? dlsucte sampk being used to form a camped
sample. According to Gamer ct aL (1), if to probability a
be wtimsfrf as low, say I %, the optimum number
samples to composite is about ten, which would result in
oost saving of aboot SO % (assuming there is no detcctii
Btnit problem). When the probability of coDectisg a sami
from a hot spot rises to 10 X, the optimal number of samp
to composite is 4, which results la a 40 * cost savings. By t
time the pobabiiity of sampling a hot spot rises to 40
tew is no eost benefit to compositing. Other resampling a
testing schema are posible and may lead to somew]
different rent saving
7. IJmfhrttnns of Coayosita Sampling
7.1 Use principal imitations of sample compositing
valve the loss of the discrete information contained h
mnA the potential for (SlutSss of the conta
nants in a tartifflft wills howe
N-356
-------
# CO 6051
in that case, the dilation factor can be used to the
murimiim number of samples that can be composited. The
Mtowing situations may not lend themselves to costef-
festive compositing:
7.1.1 When the integrity of individual sample values
change because of compositing, for example, chemical inter-
action occurs between constituents in the. samples being
combined or voMes are lost during tmaring,
7.L2 Where the composite sample cannot be property 1
nixed and subsampled or the whole composite sample
cannot be analyzed,
7.1 J When the goal is to detect hotspots and a large
proportion of the samples are expected to test positive for an
attribute, compositing and retestiag schemes may not be cost
... jw». — ~—
CilCWIVft,
7.1.4 When analytical costs are km relative to sampfisg
costs (for example, in situ field portable X-ay fluorescence
takes only 30 s with no sample {separation so analytical
coestemple are very low), and
7.1.5 When regulations specify that a grab sample must be
collected (usually a composite sample cowering a limited area
is stiil preferred from 2 «taw/f|mint}
8. Sample Mbdng Procedures
8.1 Prior to sarnie mixing, project-specific instructions
should be followed regarding sample collection, which may
include removal of extraneous sample material* such as
twigs, grass, rocks, etc. If samples are sieved or large mate-
rials are removed, it may be necessary to record the mass of
materials removed for later estimation of contaminant
concentration in the original sample. According to particu-
late sampling theory (4,5) the following sample masses are
adwpiate to represent the corresponding maximum size
particles in the sample with a relative standard deviation of
15%.
£»mpie Maa, f
S
SO
too
300
1000
JOOO
Miuruns taiele J
ttlTO
CU7
m»
0l7»
IjD
13
8.1.1 frequently it is necessary to mix an individual or
composite sample and obtain a representative subsample(s)
for transport to the analytical laboratory. This occurs when
multiple containers of the identical material are desired (for
eajmple, separate sample jan for metals, semivolatOe or-
pnics, etc. are desired) or when the original sample (or
composite sample) size is greater than accepted by the
laboratory. Even when the original sample volume is accept-
able, it may be desirable to thoroughly mix the sample prior
to transport to as analytical laboratory. However, some
samples that have been well mixed in the field may segregate
during shipment to the laboratory,
8.1.2 A laboratory typically collects a 0.5 to 30 g specimen
(100 g for some extraction tests) from the sample for
it&ruy&j*. iptxuacM are irequeatly collected from the surface
material in the container or after minimal mixing. Such
procedures are inadequate to obtain a small representative
apecuntn trots » 100 to 300 g sample. Special mixing and
BUbsamplisg procedures are necessary to obtain a represen-
tative subsample unless the sample is already homogenous.
• Held mixing should be considered essential tmless it is '
: taown that the sample in the container i» homogeneous or il
is known that the laboratory wiE homogenize the sample and
collect a representative specimen. To help ensure that an
i unbiased and precise specimen is collected, the analytical
laboratory should be provided instructions (preferably with
I the sample shipment) on homogenizing and obtaining •
specimen for analysis. Few laboratories Mow good sample
' homogenizing and specimen collection practices. To meet
> both sampling and analytical objectives, field and analytical
personnel, and the end-Bser of the data most be aware of the
t laboratories standard practices for framing, mmng, and
1 obtaining a apenarn or specify sods yactkes with fee
—mpi* shipment
8.1.3 ToavcadsobsamptingitsiiybepaMtfeletoeomects
: small sample (or composite samples) directly into the sample
container that is ddivered to the laboratory (Castlon: small
sample sizes may result in bias by exd&dmg large particles).
WhUe no field mixing and subsampling is needed as long as
' the tabcwUMy homogenizes the sample, it may be advisable
to mix such samples anyway (see 1.1.2).
8.1.4 Soil, sediment, sludge and waste samples collected
for purgeabk/volatile organic compounds* analyses should
not be mixed and subsampled using procedures described in
tins guide but other specialized procedures such as com-
bining samples directly into methanol (see Practice D <547)
may be appropriate. -
8.LS A significant problem with analyzing very small
samples is that the smaller the volume oT sample actually ex-
tracted or analyzed, the i«n' representative that t1* may
be unless thoroughly mixed/homogenized and subsampled.
Therefore, sample oompositisg without thorough mixing can
nullify the potential benefits of compositing.
8.1.6 Met&oda that may be applicable to field mixing,
depending on the matrix, include hand mixing in a pan,
sieving, particle size reduction, kneading, etc. For highly
heterogeneous waste such as municipal re&se, field commi-
nution (pis ding) may be needed. Some of these methods
may be inappropriate if trace levels of contamination are a
primary concern. The use of disposable ^(|im|iiiwhi for
mixing sbouM be considered to mittimize field decontamina-
tion problems. Held personnel should use care to ensure that
samples do net become contaminated during the sampling,
miring MnA mHwwpKwg pTOCCSS.
8.1.7 Once a sample has been collected, it may have to be
split into separate containers for different analyses. A true
split of so3, sediment, or sludge samples nay be difficult to
accomplish under leld conditions.
8.1.8 The following are some common methods for
mixing soils, tiadges, etc. While it is not always possible to
determine thai a —wipfc is adequately """t. following
standard procedures and observing sample texture, color,
particle distribution are practical methods. While
materials cannot be homogenized, following the
procedures in Section 9 will help ensure that a representative
subsample is collected. Under certain conditions, some of
the procedures Oat follow are applicable when trace level
contaminants are of concern.
8,1.8.1 Fan Mixing/Quartering—One common method
of mixing is referred to as quartering. Place the material in a
glass or stainless steel sample pan and divide into quarters.
44
N-357
-------
5 D 6051
Mix each quarter separately, then mix aO quarters into thae
center of the pan. Repeat this procedure several times untiM
the sample is adequately mixed (usually a minimum of threese
repetitions). If round bowls are used for sample _mixing,&
Hnrate mixing is achieved by stinins the matfrial ia a a
circular fashioa and occasionally turning the material over, i
8.1.8.2 Mixing Square—Combine samples through a a
Boo-oontamioating screen into aa appropriate dean miring ig
container. Mix is the container aad pour onto a 1 metrew
aquare of aon-contaminating material Rich at plastic forx
metals analyses or polytetiafluorcethylene for organics. RoUJI
the sample backward and forward on the sheet while le
alternately lifting aad releasing opposite side corners of thete
sheet This is appropriate for flowable granular materials (S).).
V polytetrafluoroethylene sheeting is used, (his procedure re
ctnrM be acceptable for trace level contaminants.
8.1 JL3 Kneading—Place the ample ia a aos-contami-i-
aating bag aad knead as is bread making to mix the sample, e.
This may be appropriate for viscous or day-like materials. HTf
a non-contaminating bag is used, this approach would be*
yr^iiuW- fgr trace level contaminants.
8.1.8.4 Sieving and Mixing—I! a laboratory requires a a
small spreimca (1 to 30 g) or if less than a specific particle le
¦ze is required, disruption of aggregated partides or sieving, j,
or both, followed by mixing may be needed. Sieving allows*
only those particles below a dtsired sek to pass through the e
sieve into a mining pm for subsequent mixing and d
subsampling into containers. Sieving works best with rela-1-
tively dry granular Sieving and the exclusion of>f
large paitHrs can result ia very biased results aad should d
only be conducted when designed into a sampling plan.
8.I.8J Particle Size Reduction—When partide .size re- >¦
(taction is appropriate and trace contaminants are of con-t-
cera, no»centamiaatiag tnifrriah compatible with objec- >
tives should be used (for example^ glass, ceramic, stainless a
steel). Other materials may be acceptable it trace levels of if
Hwn miiitiiH are not a concern. The reduction method caa a
be as simple as using a hammer to break apart large pieces s
into smaller pieces that are either acceptable to the labors-
tory or that can pass through a sieve, Thh method of
reduction creates a great tieai of fine nia^.ial which may or
may not be included to the staph
-------
D 6(5051
AO. 4 Afcwm* Scoop MutaampfkieTtcialqM
1««1
FIG. 0 tUtb Gtfct SubibMR^Ung T*cfenk|iM
swaths its collected until the subsample container is fuH
Multiple containers ore filled by rearranging the remaining
material and collecting swaths as just described
9.U Ahanate Scoop-—The volume of material required
for fining sample containers is compared to the volume of
the mixed sample Scoops of mixed material are placed in
the sample containers) or are discarded, ikal is, three scoops
are
-------
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-------
APPENDJXO
List of Project^Participants
-------
O-l
MSD Participants
Mike Heitz
On-Site Coordinator
Metropolitan Sewer District
1600 Gest Street
Cincinnati, Ohio 45204
(513)244-5137
(513) 244-5145 (fax)
O-l
-------
0-2
USEPA Participants
Gene Grumpier
ESD Program Manager
Office of Air Quality Planning and Standards (OAQPS)
U.S. Environmental Protection Agency
Emissions Standards Division (ESD)
Mail Drop 13
Research Triangle Park, North Carolina 27711
(919) 541-0881
crumpler.gene@epa,gov
C. E. (Gene) Riley
EMB Work Assignment Manager
Office of Air Quality Planning and Standards (OAQPS)
U.S. Environmental Protection Agency
Emissions Measurement Center (EMC)
Mail Drop 19
Research Triangle Park, North Carolina 27711
(919)541-5239
(919) 541-1039 (fax)
rilev.gene@epa.gov
0-2
-------
0-3
Battelle Participants
Anthony Wisbith
Work Assignment Leader
Battelle
505 King Avenue
Columbus, Ohio 43201
(614) 424-5481
(614) 424-3638 (fax)
Battelle
505 King Avenue
Columbus, Ohio 43201
(614)424-4194
(No longer with Battelle)
Susan Abbgy
QA Officer
wisbith@battelle.org
Karen Lesniak
Laboratory Coordinator
Battelle
505 King Avenue
Columbus, Ohio 43201
(614) 424-4028
(614) 424-3638 (fax)
lesnia'kk@battelle.org
Mary Scbrock
Battelle Extraction Laboratory Manager
HRGC/HRMS Laboratory Manager
Battelle
505 King Avenue
Columbus, Ohio 43201
(614)424-4976
(614) 424-3638 (fax)
schrockm@battel1e.org
Brian Canterbury
Laboratory Sampling Technician
Battelle
505 King Avenue
Columbus, Ohio 43201
(614)424-7849
(614) 424-3638 (fax)
canterburvb@battelle.org
0-3
-------
0-4
ETS Participants
Andrew Hetz
Field Team Leader
ETS, Inc.
1401 Municipal Road
Roanoke, Virginia 24012-1409
(540) 265-0004
(540) 265-0131 (fax)
Sharon Winemiller
Quality Assurance Coordinator
ETS, Inc.
1401 Municipal Road
Roanoke, Virginia 24012-1409
(540) 265-0004
(540) 265-0131 (fax)
W. Tony Underwood
CEM Coordinator
ETS, Inc.
1401 Municipal Road
Roanoke, Virginia 24012-1409
(540) 265-0004
(540)265-0131 (fax)
Chawn B, Duty
Testing Team Member
ETS, Inc.
1401 Municipal Road
Roanoke, Virginia 24012-1409
(540) 265-0004
Frank P. Craighead
Testing Team Member
ETS, Inc.
1401 Municipal Road
Roanoke, Virginia 24012-1409
(540) 265-0004
0-4
-------
I
I
1 0-5
Pacific Environmental Participants
Dennis Falgout
Process Engineer
Pacific Environmental Services, Inc.
560 Hemdon Parkway
Heradon, Virginia 20170
(703)471-8383
(703) 471-8296 (fax)
0-5
-------
0-6
T&E Lab Participants
Paul Kefauver
Operations Manager
U.S. EPA T&E Facility
1600 Gest Street
Cincinnati, Ohio 45204
(513) 569-7057
(513) 569-7707 (fax)
Robin Richardson
Laboratory Coordinator
U.S. EPA T&E Facility
1600 Gest Street
Cincinnati, Ohio 45204
(513)569-7057
(513) 569-7707 (fax)
0-6
-------
0-7
Quanterra Environmental Services
Participants
Patrick Rainey
Laboratory Manager
Quanterra Environmental Services
880 Riverside Parkway
West Sacramento, California 95605
(916)374-4411
(916)372-7768 (fax)
0-7
-------
APPENDIX PJp
Post Test Summaiy;
-------
p-1
Post Test Summary Report
P-1
-------
For Review and Approval
Project NO G46900S-0B
Approved KB Rigga
Name
arafty^j/y 08/24/99
AS Wisbith
KB Riggs
J Ferg
HMO
Prcj«ct Piles
Craft 09/24/99
Seat Via: 2" Class Hail
August 25, 1999
Mr. C.E. Riley
U.S. Environmental Protection Agency
Emission Measurement Center
MD-19
Research Triangle Park, North Carolina 27711
Dear Gene;
Contract No. 68-D-99-0Q9
Work Assignment WA 1-05
As per your request, we are submitting the attached post test summary report for the above work
assignment. This report meets the requirements of Section 7.3 of the Site-Specific Test Plan for
this task. Also attached are the field logs for the same test.
If you have any questions regarding this report, please call me at (614) 424-5481 to discuss.
Sincerely,
Anthony S. Wisbith
WA 1-05 Work Assignment Leader
Battelle
ASW:llg
cc: Ms. Kathy Weant (letter only)
-------
POST-TEST SUMMARY REPORT
Sewage Sludge Incinerator Test Program
Work Assignment WA 1-05
EPA Contract No. 68-D-99-009
August 25,1999
A Site-Specific Test Plan (SSTP) was prepared for the test program performed on the
sewage sludge incinerator located at the Metropolitan Sewer District in Cincinnati, Ohio.
The field test was conducted on July 18-23,1999. Deviations from the SSTP were
expected to occur, due to unforeseen problems with the test location or with the actual
sampling. A section of the SSTP (Section 7.3) discussed the submittal of a test
deviation letter report to detail all deviations from the SSTP. There were a total of five
(5) deviations from the SSTP. The following details the five deviations from the SSTP
which occurred during the field test.
The first deviation from the SSTP occurred on July 19,1999 at 1100. This deviation
involved the audit gases from the facility total hydrocarbon analyzer. Section 6.2.2 of
the SSTP stated that a cylinder gas audit (CGA) would be performed on the
hydrocarbon analyzer prior to and following the test program, in accordance with the
procedures of 40 CFR 60, Appendix F, Section 5.1.2. The procedure requires the total
hydrocarbon analyzer to be challenged with two audit gases of known concentrations,
a high calibration gas of 150 to 180 ppm and a low calibration gas of 60 to 90 ppm
would be used to challenge the analyzer.
The deviation from the SSTP involved the high calibration gas. Due to availability, a
high gas of 124.6 ppm was used to challenge the total hydrocarbon analyzer, which
does not fall within the stated range. This deviation was approved by the EPA WAM,
C.E. (Gene) Riley of USEPA's Office of Air Quality Planning and Standards (OAQPS)
since
the total hydrocarbon analyzer used the low end of their electronic span, making the
lower gas acceptable.
The second deviation from the SSTP occurred on July 19,1999 at 1530. This deviation
involved the span of the carbon monoxide (CO) continuous analyzer. Section 5.1.1.6 of
the SSTP states that the range of the CO analyzer would be 0-3000 ppnv
Mike Heiiz of the Cincinnati MSD stated that spikes of CO to over 10,000 ppm are
possible during normal operation. ETS had calibration gases onsite which could raise
trie Lijjuuiiisnidt span to 6000 ppm. A calibration gas of 9556 ppm was shipped
overnight from the ETS office in Roanoke, Virginia to the Cincinnati MSD to allow for
linearis determinations of up to 10,000 ppm, if the 6000 span was exceeded during
P-3
-------
testing. The CO analyzer was calibrated to a span of 6000 ppm for all subsequent
sampling, and the 6000 span was never exceeded. '
The third deviation from the SSTP occurred on July 20,1999 at 0830. The deviation
ir.vclved the proof blanking procedures. Preliminary flowrate provided t;\':.z fzzZ^
indicated that the sampling'train should be equipped with a nozzle with a internal
diameter of 0.218 inches. Proof Blank #1 was performed on the glassware to be used
in the sampling, including this nozzle. On the morning of the initial day of sampling,
preliminary flowrate measurements indicated that the nozzle diameter needed to be
0.250 inches to maintain isokinetics and achieve the desired sampling volumes during
the preset 360 sampling duration. Since all nozzles were cleaned identically and
concurrently, and since the nozzles were similar in size, the WAM accepted the Proof
Blank #1 samples were submitted with the incorrect nozzle.
The fourth deviation from the SSTP occurred on July 20,1999 at 0830. The deviation
involved the possible detection of gas stratification in the exhaust stack. Section
5.1.1.1 of the SSTP stated that sampling for carbon monoxide, oxygen, and carbon
dioxide would be conducted at a single point in the centroidal area of the duct. A gas
stratification determination was performed on July 19,1999. The single CEM system
determination indicated that gas stratification was possible in the exhaust stack. The
stratification was not proven since the single CEM system does not allow for
comparisons to a stationary CEM system which would correct for process instability.
Since the gas stratification determination proved to be inconclusive, a decision was
made to traverse the CEM sampling probe using the same traverse points as the
modified method 5 sampling train incorporated as detailed in Section 5.1.1.1 of the
SSTP,
The fifth and final deviation from the SSTP occurred on July 20,1999 at 1230. This
deviation involved the failure to meet leak checking criteria as stated in the SSTP.
Section 5.1.1.5 of the SSTP stated that leak checks will be performed prior to initiating
sampling, during each port change, and at the conclusion of each test run. The leak
checks would be considered acceptable if a leak rate of less than 0.02 ftVmin is
observed at the highest vacuum recorded during the sampling run. If the leak check is
not acceptable, the WAM will be notified, and a decision whether to keep the sampling
run, continue the run, or repeat the run will be made.
At the.port change of the first sampling run, the leak check was not deemed to be
acceptable. 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 a total of four sampling runs
were performed, so that three valid sampling runs were available for laboratory
analyses.
The discussion above details all deviations from the SSTP submitted for review prior to
the test program. All other methodology and QA/QC procedures were performed as
detailed in the SSTP.
P-4
-------
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-------
TEST LOG
Metropolitan Sewer District
Sewage Sludge Incinerator
Cincinnati, Ohio
Test
Location
Activity
Test Parameter(s)
Date
Start
Time.
End
Time
MSD
CEMS
Pre-Test Cylinder
Gas Audit
Total Hydrocarbons
7/19/99
1100
1130
Outlet
Stack Inlet
Cyclonic Flow
Check/Preliminary
Ftowrate
Flowrate
1430
1530
Outlet
Stack
ETS RM Response
Time
CO/CO^O,
143b
1545
Outlet
Stack
Stratification Check
CO/COj/Oj
1540
1630
Sample
Recovery
Laboratory
Reagent Blanks
' CopianarPCBs
Dioxins/Furans
PAHs
1530
1700
Sample
Recovery
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Proof Blank #1
CopianarPCBs .
Dioxins/Furans
PAHs
1700
2000
Stack
Outlet
MSD-MM5-R1
CopianarPCBs
Dioxins/Furans
PAHs
7/20/99
0930
1230
Stack
Outlet
MSD-CEMS-R1
CO/COj/Oa
0930
1230
Stack
Outlet
MSD-MM5-R2
CopianarPCBs
Dioxins/Furans
PAHs
1500
2130
Stack
Outlet
MSD-CEMS-R2
C01C0J02
1500
2130
P-9
-------
TEST LOG
. Metropolitan Sewer District
Sewage Sludge Incinerator
Cincinnati, Ohio
Test
Location
Activity
Test Parameters)
Date
Start
Time
End
Time
Sample
Recovery
Laboratory
Proof Blank #2
CoplanarPCBs
Dioxins/Furans
PAHs
7/21/99
0700;
0900
Stack
-Outlet
MSD-MM5-R3
CoplanarPCBs
Dioxins/Furans
PAHs
1015
1635
~ Stack
Outlet
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C0fC0J02
1015
1635
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Outlet
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Dioxins/Furans
PAHs
1015
1430
ETS
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CEMS Gas Audit
CO/CO^Oj
7/22/99
0710
0740
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Outlet
MSD-MM5-R4
CoplanarPCBs
Dioxins/Furans
PAHs
0815
1435
Stack
Outlet
MSD-CEMS-R4
CO/COj/Oj
0815
1435
MSD
OEMS
Post-Test Cylinder
Gas Audit
Total Hydrocarbons
1430
1515
Stack
Outlet
Post-Test Meter
Box Audit
Critical Orifice
1500
1610
P-10
-------
P-2
QAPP Amendment Records
p-11
-------
For Review sad Approval
Project So G003S35-03 (3X90!
Home
Initial* I Date
Originator
k LesniiJc
MA I
Concurrence
T Wisbith
jtS»7r I ¦fr
Concurrence
Approved
K3 Riggs
i r]nh
iBttCTal Distribution
T Wisbith
X Leeniak
Project files
BMO
August 11,1999
Mr. C. E. Riley
Office of Air Quality Planning and
Standards (OAQFS)
U.S. Environmental Protection Agency
Emissions Measurement Center
Mail Drop 19
Research Triangle Park, NC 27711
Contract No. 68-D-99-009
Work Assignment WA1-05
Dear MJr, Riley:
Enclosed please find five Quality Assurance Project Plan (QAPP) Amendment Records for your approval and
signature. Copies of these forms were faxed to you on the above date. Please return these forms after they have
been approved so that I may include them in the final report Also included are completed copies of the QAPP
Amendment Records from the field for your records.
If you have any questions regarding these forms, please call me at (614) 424-5481 to discuss. Thank you for your
continued assistance.
Sincerely,
Anthony S. Wisbith
WA 1-05 Work Assignment Leader
Battelle
ASW:kl
Enc.
P-12
-------
Qomlity Auurance Project Plan^- .
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Qualijv Assurance frojecl Plan
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QUALITY ASSURANCE PROJECT PLAN AMENDMENT RECORD
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Signatures
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P-23
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Quality Assurance Project Plan
Project No.: Smugly- £
Section No.: _jr T' I
Revision No: CP- O
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qappo^n,:
QUALITY ASSURANCE PROJECT PLAN AMENDMENT RECORD
QAPP Title/Date: Sewage. SUxd^ 1Tnf^wfcira.fw Mfchrgpal, —
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P-3
SSTP Amendment Records
P-25
-------
Site Specific Test Plan
Project No.: * , „
Section No.: Ae.*. A S T# 4t& •*/ >7
Revision No: O./l
Date: ¦¦ jr- & - -»-y 7-/6-9f
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Initiator (if other than WAM)Date 5f/ ?> ¥4
P-26
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W %* I/' SL
Samplt Container
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lo 1 2 m/L
75 It Archived
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Sample
Container 3
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Toluene
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Figure 5-8. Flow Chart for Extraction of Front Half of Sample Train
-------
Sample Container
5
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to
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analyila
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E Archive-] I
7
-------
P-4
Corrective Action Reports
P-29
-------
Corrective Action Report
Project No. 500:7
Date: fit aay.
Page _/_ of 7
CORRECTIVE ACTION REPORT
(CAR)
Description of problem: Ai a . /\ $ fi irm m i ndspL
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Signatures: ^
Analyst: CL^i ElZJjr^ Date: 0%-%$-$? _
LaboratoryManager/Coordinatoif AAn... ^AxmA. ; Date: _
Battelle QA/QC Officer /%. /7^***a Date: 2&-1 f
BattelleWorkAssignmentLeader:SDate: £' +C"? f
P-30
-------
Corrective Action Report
Project No.:
Date: V"* J )-***»
Page: _J, of_<
CORRECTIVE ACTION REPORT
(CAR)
Description of problem: ~ ?«*.+<- £** Of ^ng-
S^c .T.'c >- /*<«»* a.-v/ fqv*-. I 0* b* fcc>
r*i pre.
Action Taken: f'w*_ | #-£ /*1<. /"V7 (krS*y?)
Battel le Work Assignment Leader Date:
-------
Corrective Action Report
Project No:
Date;
CORRECTIVE ACTION REPORT
(CAR)
Description of problem: 8 f>fc O^/ f .'^ tA. J ^ (
WUj finuMs^ |M?t\ Ai<, Cf^^" U~^)C .
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Laboratory Manager/Coordinator..,
iinator. )hOJ l~fj Date: 2
BatteUe QA/QC Officer:3>. Date: 9~f~9f
Battelle Work Assignment Leader, Dm:_±zZ2-£j-
P-32
-------
Description of problem:
Corrective Action Report
Project No.: pJ-cms
Date; W-- -«VS
Page: \ of \
CORRECTIVE ACTION REPORT
(CAR)
Si W»*jr fa 2.3 A/<- C
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Action Taken: D'^'^ A*" w*/c/Ait-jr/^ oA
Signatures: ^^-^7 __
Analyst ' /"•< >•-* \— Date; ^C""- 7 f*K
Laboratory Manager/Coordinator: Date:
BattelleQA/QC Officer: Date:
Battelle Work Assignment Leader: ^ Date: f 7~ 7"~ 'f ¥
P-33
-------
Corrective Action Report
Project No.; G+it&IC 'U
U-U.t A /fl fUt_ Ar^g^t-
£>f ^Vu^iv/ca >£<><- A/ .fri*. /?HL-iy.'/<•¦<• . /~L.
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Slgna^.: Dale
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BattelleOA/OCOfficer ^ 'IOiZa/*, ) Date ^~/~??
Battelle Work Assignment Leader Date: 7" ? $
P-34
-------
Corrective Action Report
ProjectNo^:
Date: k~" g )
Page:
CORRECTIVE ACTION REPORT
(CAR)
Description of problem: TKC. 1f\i ^ th"•
4Lii. T«%x tVbic 1- c* Ait ¦*<«
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Laboratory Manager/Coordinator: srYjj s^V Date
Battelle QA'QC Officer:^ Date p^
Battelle Work Assignment Leader: Date: ^ 7 ~ ? f
P-35
-------
Corrective Action Report
Project No.:Q pilo) MxW6~J 0 cs„n-up
.fhdOtilJLLOL-
Signatures: r
Analyst: ~
Laboratory Manager/Coordinator: ^
Battelle QA/QC Officer: ^
Battelle Work Assignment Leader^X^. ^Sg«.r>
Date
Date:
Sf' "it *1 \
~-7-4"?
Date: fr~/~g_L
Date- 7- f f
P-36
-------
Description of problem:
Corrective Action Report
Project No :
Date: fr'S? •«>«.
Page: _j of J
CORRECTIVE ACTION REPORT
(CAR)
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Laboratory Manager/Coordtnatory^y1'^ i 1^. ^ 0 Date: $-"1
BattelleQA/QC Officer: Date: / zif
Battelle Work Assignment Leader:. Date:
-------
Corrective Action Report
Project No.: i
Date: ^r-
Page:_L_of_i_
CORRECTIVE ACTION REPORT
(CAR)
Description of problem: ^ *- ^ +4 *
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Date:
Date:
Da-,. ?~Mf
Battelle Work Assignment Leader: sSS Date:.
i?-? O "
P-38
-------
Corrective Action Rqpoit
Project No,
Date: Sj-h im Ja/ k 9 t^WT
Page i of j
CORRECTIVE ACTION REPORT
(CAR)
Description of problem: cikt 10 gjVVicL (L^/Kjh'ru^s
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BattelleQA/'QCOfficer; R. (krjfctZt} Date: f- J- ff
Battelk Work Assignment Leader:" Date: ¥'7—? 7
P-39
-------
P-5
QA Officer Site Visit Checklist
i
i
I
J
i
P-40
-------
MSD Sewage Sludge Incinerator Plant
Site Visit Checklist
QA Officer.
Work Assignment
•Manager
Date
QirtiM
QUALITY SYSTEM DOCUMENTATION
Is there an approved quality
assurance project plan
(QAPP) for the project and
has it been reviewed by all
appropriate personnel?
Is a copy of the QAPP
maintained at the field site?
Is the design and conduct
of the project as is specified
in the QAPP?
Are there deviations from
the QAPP?
How are any deviations
from the QAPP noted?
Briefly describe how
calibration and other QC
data are documented.
Does the calibration
documentation show that
calibrations are being
performed at the required
frequency and in the
required manner?
Are the standard data forms
dated?
11M - ttpplCWut QLOh.
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Page 1
P-41
-------
MSD Sewage Sludge Incinerator Plant
Site Visit Checklist
'
Is the person who recorded
the data identified on the
form?
L
/<5i
-------
MSD Sewage Sludge Incinerator Plant
Site Visit Checklist
Is each project team
member appropriately
outfitted with safety gear?
Are project personnel
adequately trained for their
safely during the
performance of the project?
Who is authorized to halt
emissions testing in the
event of a health or safety
hazard?
¦S*pLhs\
ijMV
lljiAJ
CORRECTIVE ACTION PROCEDURES
Are there established
procedures for corrective
actions when the data
quality indicator goals (e.g.
out-of-control calibration
data) are not met?
Are the corrective action
procedures consistent with
the QAPP?
Have any such corrective.
actions been taken?
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IIII akd t-Q ¦
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Page 3
P-43
-------
MSD Sewage Sludge Incinerator Plant
Site Visit Checklist
Notes:
Page 4
P-44
-------
TECHNICAL REPORT DATA
tPlease read instructions on reverse before completing)
1 REPORT NO 2
EPA-4 54/R-00-03 8d
3. RECIPIENTS ACCESSION NO
4 TITLE AND SUBTTTLE
Source Characterization For Sewage Sludge Incinerators
Final Emissions Report, Volume III of III, Appendix K - Appendix P
Metropolitan Sewer District (MSD) Mill Creek Wastewater Treatment Plant
Cincinnati, Ohio
5. REPORT DATE
Septembsr 2000
6 PERFORMING ORGANIZATION CODE
x AtrmoaiSi
Clyde E. Riley, USEPA Anthony S. Wisbith, Battelle
Jeffery A. Ferg, 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.
U. 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 AMD 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
polvchlorinated 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 Plan: 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 Il-Appendices A-J; Volume Ill-
Appendices K-P; and a Data Quality Assessment Report.
.17. KEY WORDS AND DOCUMENT ANALYSIS
i. DESCRIPTORS
b IDENTIFIERS/OPEN ENDED TERMS
c. COSATt
Field/Group
PCBs
PAHs
Dioxins/furans
Air Pollution control
is. distribution statement
Release Unlimited
19. SECURITY CLASS (Repot)
Unclassified
21 NO. OF
PAGES
20. SECURITY CLASS (Page)
Unclassified
22 PRICE
KPA Form 2220-1
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