United States Office of Air Quality EPA-340/1 -85-013a
Environmental Protection Planning and Standards December 1985
Agency Washington DC 20460
Stationary Source Compliance Series
&ER& Technical
Assistance
Document for
Monitoring Total
Reduced Sulfur
(TRS) from
Kraft Pulp Mills
-------
EPA-340/1-85-013a
Technical Assistance Document for
Monitoring Total Reduced Sulfur (TRS)
from Kraft Pulp Mills
Prepared by
William T Winberry, Jr
Engineering-Science
501 Willard Street
Durham, North Carolina 27701
Contract No 68-02-3960
Work Assignment No 53
EPA Project Manager John Busik
EPA Work Assignment Manager Sonya M Stelmack
U.S. ENVIRONMENTAL PROTECTION AGENCY
Stationary Source Compliance Division
Office of Air Quality Planning and Standards
Washington, D C. 20460
December 1985
-------
DISCLAIMER
This report was furnished to the Environmental Protection Agency by
Engineering-Science, 501 Willard Street, Durham, N. C., 27701 in fulfill-
ment of Contract No. 68-02-3960, Work Assignment No. 53. The opinions,
findings, and conclusions expressed are those of the author and not
necessarily those of the U. S. Environmental Protection Agency. Mention
of company or product names is not to be considered as an endorsement by
the Environmental Protection Agency.
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT
3 RECIPIENT'S ACCESSION NO
4. TITLE AND SUBTITLE
Technical Assistance Document for Monitorina
Reduced Sulfur (TRS) from Kraft Pulp Mills
6. PERFORMING ORGANIZATION CODE
7 AUTHOR
-------
ACKNOWLEDGEMENTS
Engineering-Science expresses appreciation to Sonya Stelmack,
Ken Malmberg, and Mark Slegler of the Stationary Source Compliance Divi-
sion, Technical Support Branch of the U. S. Environmental Protection
Agency, Washington, D. C. and Phil Schwindt, U. S. Environmental
Protection Agency, Region VI, Dallas, Texas for their active interest
in the project, timely suggestions, and support of this report. In
particular, appreciation is given to Ashok Jain of the National Council
of The Paper Industry for Air and Stream Improvement, Inc. for his thorough
review and helpful comments to the preliminary draft of this manuscript.
Appreciation is also given to Joyce Warren of Engineering-Science for
her patience in typing and editing this manuscript.
Finally, appreciation is given to the U. S. Environmental Protection
Agency, Air Pollution Training Institute (APTI), Manpower and Technical
Information Branch, for their support with many of the graphics displayed
in this manuscript.
-------
11
-------
TABLE OF CONTENTS
Chapter
Topic
Page No,
1.0
2.0
3.0
4.0
FIGURES
TABLES
FORWARD
TOTAL REDUCED SULFUR
1.1 Introduction
1.2 Oxidation States of Sulfur
1.3 Terminology
1.3.1 Hydrogen Sul fide (H2S)
1.3.2 Methyl Mercaptan (CHaSH)
1.3.3 Dimethyl Sulfide (CHa^S and Dimethyl
Disulfide (CH3)2S2
PULP MILLS
2.1 Production of Paper
2.1.1 Kraft (Sulfate) Process
2.1.2 Sulfite Process
2.1.3 Neutral Sulfite Semi chemical (NSSC)
2.2 Pulp Mill Population
2.3 Kraft Pulp Mill Emissions
2.3.1 Components of Kraft Pulp Mill Odor
2.3.2 Effects
2.3.2.1 Human
2.3.2.2 Sociological
2.3.2.3 Vegetation
2.3.2.4 Economic
2.4 Limiting Emissions
2.5 Summary
REGULATIONS
3.1 The Clean Air Act and Its Amendments
3.2 Continuous Emission Monitoring Basis In the Clean
Air Act
3.3 Federal Register and Code of Federal Regulations
3.4 Federal Register, October 6, 1975
3.4.1 Existing Sources Regulations (40 CFR 51)
3.4.2 New Source Performance Standard Regulations
(40 CFR 60)
3.5 Standard of Performance for Kraft Pulp Mills -
Subpart BB
CONTROL AGENCY CEM INSPECTION PROGRAM
4.1 Introduction
xii
XV
xviii
-1
-1
-1
-2
-3
-3
1-3
2-1
2-1
2-1
2-4
2-5
2-6
2-15
2-15
2-18
2-18
2-20
2-20
2-21
2-22
2-23
3-1
3-1
3-3
3-7
3-13
3-21
3-26
3-31
4-1
4-1
iii
-------
TABLE OF CONTENTS (continued)
Chapter
Top i c
Page No,
4.2
4.3
Control Agency Compliance Program
Control Agency Administrative Review Activities -
Phase I, II, III
4-1
4-4
4.3.1 Phase I - Regulatory Review of Source
Application/Permit
4.3.1.1 General Information
4.3.1.2 Management Control System (MCS)
4.3.1.3 Standard Operating Procedure (SOP)
Manual
4.3.1.4 Quality Assurance Program
4.3.2 Phase II - Performance Testing of Installed
Continuous Emission Monitoring System
4.3.3 Phase III - Regulatory Approval of Installed
Continuous Emission Monitoring System
4.4 Control Agency Inspection Review Activities - Level I,
II.
4.4
III and IV
1
Control
4.4.1.1
I
Agency Records Review - Level
Basic Facility Information
4.4.1.2 Pollution Control Equipment and
Other Relevant Equipment Data
4.4.1.3 Regulations, Reporting Requirements,
and Limitations
4.4.1.3.1 Previous Inspection Reports
4.4.1.3.2 Compliance History
4.4.1.3.3 Excess Emission Reports
4.4.2 Source Records and Continuous Emission
Monitoring System Review - Level II
4.4.2.1 Office Complex
4.4.2.2 Control Room
4.4.2.2.1 Data Recorder/Data
Processor
4.4.2.2.2 Analyzer
4.4.2.2.3 Calibration System
4.4.2.3 Control Device
4.4.2.4 CEM Interface System
4.4.2.4.1 Sample Conditioning System
4.4.2.4.2 Probe/Extraction System
4.4.2.5 Closing Conference
Source Continuous Emission Monitoring System
Calibration Error Determination - Level III
Source Continuous Emission Monitoring System
Performance Specification Re-Evaluation -
Level IV
4.4.3
4.4.4
5.0
MONITORING SYSTEM INSTRUMENTATION
"EnIntroduction
5.2 Continuous Emissiom Monitoring System
5.2.1 TRS Extractive System Components
4-4
4-6
4-6
4-6
4-8
4-8
4-8
4-9
4-9
4-10
4-10
4-10
4-11
4-11
4-11
4-12
4-15
4-17
4-17
4-17
4-18
4-18
4-19
4-19
4-19
4-19
4-20
4-20
5-1
5-1
5-5
5-5
IV
-------
TABLE OF CONTENTS (continued)
Chapter Topic Page No.
5.2.1.1 Particulate Filtration Device 5-5
5.2.1.2 Stack Probe 5-8
5.2.1.3 Sample Line 5-8
5.2.1.3.1 Materials of Construction 5-9
5.2.1.3.2 Heat Resistance 5-11
5.2.1.3.3 Sample Interaction 5-11
5.2.1.3.4 Size and Length of Sample
Line 5-12
5.2.1.3.5 Cost 5-14
5.2.2 Conditioning System 5-15
5.2.2.1 Moisture Removal 5-15
5.2.2.1.1 Condensation 5-15
5.2.2.1.2 Permeation Dryer 5-16
5.2.2.2 S02 Separation Devices 5-17
5.2.2.2.1 Wet S02 Scrubbers 5-17
5.2.2.2.2 Dry Bed Scrubbers 5-18
5.2.2.3 TRS Oxidizer 5-18
5.2.2.3.1 Oxygen Concentration in
Gas Sample 5-19
5.2.2.3.? Furnace Time and Temperature 5-19
5.2.2.4 Pumps 5-20
5.2.2.4.1 Positive Displacement Pumps 5-20
5.2.2.4.2 Centrifugal Pump 5-22
5.2.2.4.3 Air Driven Eductor 5-22
5.2.3 Detector Systems 5-14
5.2.3.1 Electrochemical Transducers 5-25
5.2.3.2 Fluorescence Detection 5-26
5.2.3.3 Flame Photometric Detection 5-28
5.2.3.4 Coulometric Detection 5-30
5.2.3.5 Gas Chromatography Detection 5-32
5.2.3.5.1 Carrier Gas 5-32
5.2.3.5.2 Injection Port 5-33
5.2.3.5.3 Chromatographic Column 5-33
5.2.4 Data Handling System 5-34
5.2.4.1 Emissions Corrected to a Percent
Oxygen 5-34
5.2.4.2 Moisture Correction 5-35
5.3 Commercially Available Total Reduced Sulfur
Continuous Emission Monitors 5-36
5.3.1 Candel Industries Limited 5-41
5.3.1.1 Probe/Conditioning System 5-42
5.3.1.2 S02 Scrubber and TRS Converter 5-42
5.3.1.3 Electrochemical Sensor 5-42
5.3.2 Charlton Technology Model CM-6000 Continuous
TRS Monitoring System 5-43
5.3.2.1 Probe/Conditioning System 5-44
5.3.2.2 Sample Transport Line 5-45
5.3.2.3 Instrumentation Module 5-45
-------
TABLE OF CONTENTS (continued)
Chapter
5.3.3
5.3.4
5.3.5
5.3.6
5.3.7
5.3.8
5.3.9
5.3.10
Topic Page No.
Columbia Scientific Industries
5.3.3.1 Conditioning/Dilution System
5.3.3.2 CSI Analyzer
Tracer Atlas, Inc. Total Reduced Sulfur
Conti nuous Measurement System
5.3.4.1 Sample Acquisition and Conditioning
System
5.3.4.2 Sample Measurement System
Lear Siegler Continuous TRS Monitoring System
5.3.5.1 Probe and Primary Filter Assembly
5.3.5.2 Sample Transport Line
5.3.5.3 Sample Drier
5.3.5.4 Thermal Oxidation Furnace
5.3.5.5 Gas Prime Movers
5.3.5.6 Dual Beam Differential S02 Analyzer
5.3.5.7 Microprocessor Controller
Theta Sensors, Inc. Model 7600 TRS Monitor
5.3.6.1 Sample Probe
5.3.6.2 Sample Pump
5.3.6.3 Sample Line
5.3.6.4 Sulfur Dioxide Scrubber
5.3.6.5 TRS Oxidizer
5.3.6.6 Detector
5.3.6.7 Oxygen and Sulfur Dioxide Analyzer
5.3.6.8 Data Logging
ITT-Barton Titrator
5.3.7.1 Probe Module
5.3.7.2 Sampling Module
5.3.7.3 Titration Module
Western Research TRS CEM
5.3.8.1 Probe/Conditioning System
5.3.8.2 Analyzer
5.3.8.3 Remote Output
Sampling Technology Incorporated TRS CEM System
5.3.9.1 Probe/Conditioning System
5.3.9.2 Dilution Control Assembly
5.3.9.3 Sulfur Dioxide Scrubber
5.3.9.4 Thermal Oxidizer
5.3.9.5 Analyzer
5.3.9.6 Data System
Bendix Total Reduced Sulfur Analyzer
5.3.10.1 Probe/Conditioning System
5.3.10.2 Support Assembly
5.3.10.3 Sample Transport System
5.3.10.4 Analyzer System
5.3.10.5 System Control
5-46
5-47
5-49
5-50
5-50
5-50
5-52
5-53
5-53
5-53
5-53
5-54
5-54
5-54
5-55
5-55
5-55
5-55
5-56
5-56
5-57
5-57
5-57
5-57
5-58
5-59
5-59
5-63
5-64
5-64
5-67
5-68
5-68
5-71
5-72
5-72
5-72
5-73
5-74
5-76
5-80
5-80
5-80
5-83
vi
-------
TABLE OF CONTENTS (continued)
Chapter Topic Page No.
5.4 Commercially Available Oxygen Continuous Emission
Monitors 5-84
5.4.1 Introduction 5-84
5.4.2 Oxygen Analytical Techniques 5-86
5.4.2.1 Electrochemical Transducers 5-86
5.4.2.2 Electrocatalytic Technique 5-88
5.4.2.3 Paramagnetic Technique 5-89
5.4.2.3.1 Magneto-Dynamic Technique 5-90
5.4.2.3.2 Magnetic Wind Technique 5-91
6.0 GENERATION OF STANDARD TEST ATMOSPHERES 6-1
"6TIIntroduction6-1
6.2 Dynamic Calibration Systems 6-1
6.2.1 Permeation Tubes 6-1
6.2.1.1 Permeation Tube Construction 6-2
6.2.1.1.1 FEP Teflon* Permeation Tubes 6-4
6.2.1.1.2 TFE Teflon® Permeation Tubes 6-4
6.2.1.2 Permeation Tube Rate 6-5
6.2.1.3 Permeation Tube Availability 6-7
6.2.1.3.1 National Bureau of Standards 6-7
(NBS - SRMs)
6.2.1.3.2 Commercial Tubes
Availability 6-8
6.2.1.4 Other Permeation Devices: Vials - 6-11
6.2.2 Gas Cylinder Dilution System 6-12
6.3 Static Calibration Systems 6-16
6.3.1 Cylinder Gas Concentration 6-16
6.3.2 Cylinder Gas Problems 6-17
6.3.2.1 Cylinder Material 6-18
6.3.2.2 Cylinder Gas Stability 6-19
6.3.3 Cylinder Gas Certification Techniques 6-20
6.3.3.1 National Bureau of Standards (NBS)
Standard Reference Materials (SRMs) 6-20
6.3.3.2 Certified Reference Materials (CRMs) 6-22
6.3.3.2.1 Preparation of CRMs 6-22
6.3.3.2.2 Demonstration of Homogeneity
and Stability 6-22
6.3.3.2.3 Batch Analysis 6-23
6.3.3.2.4 Audit by an Independent Lab 6-23
6.3.3.2.5 Review of Procedures and
Analytical Data by NBS 6-23
6.3.3.2.6 Availability of CRMs 6-23
6.3.3.3 Environmental Protection Agency (EPA)
Protocol No. 1 Gases 6-25
6.3.3.3.1 Concentration Determination 6-25
6.4 Verification of Cylinder Gas Concentration 6-26
vn
-------
TABLE OF CONTENTS (continued)
Chapter
Topic
Page No.
6.4.1 Certification of Sulfur Dioxide (S02) Cylinder
Gas
6.4.2 Certification of Hydrogen Sulfide (H2S)
Cylinder Gas
7.0 COMPARATIVE STUDIES OF TRS MONITORS
771 Introduction
7.2 NCASI Evaluation of TRS Detectors - Study #1
7.2.1 Test Configuration
7.2.2 Conditioning System Evaluation to Pass Reduced
Sulfur Compounds
7.2.3 Sampling System Response Time
7.2.4 Detector Accuracy and Zero/Calibration Drift
7.2.4.1 Accuracy Determination
7.2.4.2 Zero and Span Drift Determination
7.2.5 Test Results Summary
7.3 NCASI Evaluation of TRS Detectors - Study #2
7.3.1 Introduction
7.3.2 Test Program
7.3.2.1 Laboratory Evaluation
7.3.2.2 Field Evaluation
7.3.3 Test Results Summary
8.0 THE REFERENCE METHOD
£l7l Introduction
8.2 Federal Reference Method 16
8.2.1 Reference Method 16 Sampling System
8.2.1.1 Probe/502 Scrubber System
8.2.1.2 Sample Line/Pump
8.2.1.3 Dilution System
8.2.1.4 Analytical System
8.2.1.5 Calibration System
8.2.1.5.1 Flow System
8.2.1.5.2 Constant Temperature Bath
8.2.2 Sample Extraction
8.2.2.1 Pretest Procedure (Section 7.0)
8.2.2.2 Calibration of Sampling Train
(Section 8.0)
8.2.2.2.1 Calibration of Analysis
System
8.2.2.2.2 Dilution System Calibration
8.2.2.3 Sampling and Analysis Procedure
(Section 9.0)
8.2.3 Post-test Procedures (Section 10.0)
6-27
6-32
7-1
7-1
7-1
7-1
7-3
7-3
7-4
7-4
7-5
7-5
7-5
7-5
7-7
7-7
7-8
7-10
8-1
8-1
8-3
8-5
8-5
8-5
8-5
8-5
8-5
8-6
8-6
8-6
8-6
8-7
8-10
8-14
8-14
8-14
viii
-------
TABLE OF CONTENTS (continued)
Chapter Topic Page No.
8.3 Proposed Federal Reference Method 16A, June 18, 1981
8.3.1
8.3.2
8.3.3
8.3.4
Introduction
Train Configuration
Propposed Reference Method 16A Bias Evaluation
8.3.3.1 Probe Angle Evaluation
8.3.3.2 External Filter Evaluation
8.3.3.3 Sample Train Purge Evaluation
8.3.3.4 Scrubber Solution pH Evaluation
8.3.3.5 H2S Filter Retention Check
Recommended Design Change to Proposed Reference
Method 16A
8.4 Promulgated Federal Reference Method 16A, March 8, 1985
8.4.1
8.4.2
8.4.3
Introduction
Promulgated Train Configuration
Sampling Protocol
8.4.3.1 Train Preparation
8.4.3.1.1 Optional Pre-Test Leak Check
8.4.3.1.2 System Performance Check
8.4.3.2 Sampling Activities
8.4.3.3 Post-Test Activities
8.4.3.3.1 Post-test Leak Check
8.4.3.3.2 Sample Recovery Test
8.4.3.3.3 Sample Analysis
8.4.3.4 Calculations
8-16
8-16
8-16
8-18
8-19
8-19
8-20
8-21
8-21
8-22
8-23
8-23
8-23
8-23
8-26
8-26
8-27
8-28
8-28
8-28
8-28
8-28
8-28
8.5 Comparative Testing of Method 16 (Gas Chromatography) 8-30
and Proposed FR Method 16A (Wet Chemical)
8.5.1 Introduction 8-30
8.5.2 Test Configuration 8-30
8.5.3 Test Results 8-31
8.5.3.1 H2S Certified Test Gas Mixture 8-31
8.5.3.2 Kraft Recovery Furnace Test 8-32
9.0 PERFORMANCE SPECIFICATION TEST 9-1
TJ7IIntroduction 9-1
9.2 Performance Specification Test 5 9-4
9.2.1 Reference to PST2 9-4
9.2.2 Definition of TRS CEM System 9-4
9.2.3 Span Value Definition 9-5
9.2.4 TRS CEM Installation and Measurement Location 9-5
9.2.4.1 Stratification Determination 9-6
9.2.4.2 Traverse Points Location 9-6
9.2.5 Performance and Equipment Specification 9-7
9.2.5.1 Calibration Drift 9-7
9.2.5.2 Accuracy (Relative) 9-9
-------
TABLE OF CONTENTS (continued)
Chapter Topic Page No.
9.3 Performance Specification Test 3 - Specification & Test 9-14
Procedures For 02 and C02 Continuous Emission Monitoring
Systems
9.3.1 Introduction 9-14
9.3.2 Regulatory Changes 9-15
9.3.3 Interpretation of Performance Specification 9-17
Test 3
9.3.3.1 Principle and Application 9-17
9.3.3.2 Apparatus 9-17
9.3.3.3 Definitions 9-17
9.3.3.4 Installation Specification 9-18
9.3.3.5 Continuous Monitoring System 9-18
Performance Specifications
9.3.3.5.1 Accuracy (Relative) 9-19
9.3.3.5.2 Calibration Drift Test 9-19
9.3.3.6 Calculations, Data Analysis and
Reporting 9-20
10.0
11.0
EXCESS
10.1
10.2
10.3
EMISSION REPORTS
Introduction
Standardized Excess Emission Report
Excess Emission Agency Review Process
10.3.1 Phase 1 - Initial EER Review
10.3.2 Phase 2 - Targeting of Follow Up Action
10.3.3 Phase 3 - Follow Up Activity
QUALITY ASSURANCE/QUALITY CONTROL
11.1
11.2
11.3
Introduction
U. S. EPA, Proposed Appendix F, Procedure 1
11.2.1 Quality Control (QC)
11.2.2 Quality Assurance (QA)
11.2.3 Reporting
Source Quality Assurance Program
11.3.1 Introduction
11.3.2 Source Quality Assurance Program
11.3.2.1 Introduction
11.3.2.2 Quality Assurance Overview
11.3.2.3 Organization and Individual
Responsibility
11.3.2.4 Quality Assurance/Quality Control
11.3.2.5 Data Validation and Reporting
11.3.2.6 Operation and Maintenance Program
11.3.2.6.1 Routine Maintenance
11.3.2.6.2 Preventative Maintenance
11.3.2.7 Quality Assurance Audits
11.3.2.7.1 Dynamic Audits
11.3.2.7.2 Federal Reference
Method 16
11.3.2.7.3 Portable H2S CEMs
10-1
10-1
10-2
10-13
10-13
10-14
10-14
11-1
11-1
11-2
11-4
11-4
11-7
11-7
11-7
11-11
11-13
11-13
11-14
11-20
11-23
11-23
11-27
11-27
11-27
11-30
11-30
11-31
-------
TABLE OF CONTENTS (continued)
Chapter Topic Page No,
11.3.2.8 Recordkeeping 11-32
11.3.2.8.1 Logbooks 11-32
11.3.2.8.2 Calibration Forms 11-32
11.3.2.8.3 Precision Assessment Forms 11-36
11.3.2.8.4 Audit Forms 11-36
11.4 Control Agency Quality Assurance/Quality Control 11-37
Activities
11.4.1 Introduction 11-37
11.4.2 Control Agency QA Activities Involving the 11-38
Phase Program
11.4.2.1 Phase I OA Activities 11-38
11.4.2.2 Phase II QA Activities 11-38
11.4.2.3 Phase III OA Activities 11-38
11.4.3 QA Activities Associated With Control Agency
Level Program 11-39
11.4.3.1 Level I QA Activities 11-39
11.4.3.2 Level II QA Activities 11-39
11.4.3.3 Level III QA Activities 11-40
11.4.3.3.1 Permeation Tube Audit
System 11-40
11.4.3.3.2 Gas Cylinder Audit
System 11-41
11.4.3.4 Level IV QA Activities 11-46
12.0 EQUIPMENT SELECTION 12-1
T2TIIntroduction 12-1
12.2 Vendor List 12-1
12.2.1 Gas Manufacturers 12-1
12.2.2 Oxygen Analyzers (03) 12-2
12.2.3 Hydrogen Sulfide Analyzers (HgS) 12-3
12.2.4 Condenser (Refrigerated Moisture) 12-4
12.2.5 Pumps 12-4
12.2.6 Combustion Tube (Quartz) for Thermal Oxidation 12-4
Oven
12.2.7 Filter 12-5
12.2.8 Scrubbers - Teflon® Continuous and Batch S02 12-5
12.2.9 Thermal Oxidation Oven 12-5
12.2.10 Air Bath for Teflon Permeation Tubes 12-5
12.2.11 Aspirator (Teflon*) and Aspirated Gas Sampler 12-6
12.2.12 Dynamic Gas Analyzer Calibration 12-6
12.2.13 Gas Permeation Tubes 12-6
12.2.14 Sample Conditioner Systems 12-7
12.2.15 Probes 12-8
12.2.16 Stack Testing Equipment (Impingers, Sampling
Train, Meter Box Assembly) 12-8
12.2.17 Heat Trace Lines 12-9
12.2.18 Pressure Gauges and Manometers 12-9
12.2.19 Regulators 12-9
xi
-------
TABLE OF CONTENTS (continued)
Chapter
Topic
Page No,
13.0
14.0
12.2.20
12.2.21
12.2.22
12.2.23
12.2.24
12.2.25
12.2.26
12.2.27
12.2.28
12.2.29
12.2.30
12.2.31
BIBLIOGRAPHY
INDEX
Flowmeters, Rotameters
Flowmeters, Mass
Pumps, Diaphragm
Pumps, Sampling
Valves, Metering
Valves, Needle
Carbon Dioxide and Carbon Monoxide Analyzers
Fittings
Flow Controllers
Portable Gas Chromatographs
SOg Analyzers
TRS CEM Systems
12-9
12-9
12-10
12-11
12-11
12-12
12-12
12-13
12-14
12-14
12-14
12-15
13-1
14-1
xii
-------
LIST OF FIGURES
Figure No. Topic Page No.
1.1 Elemental Sulfur 1-1
2.1 Kraft Pulp Mill Operation 2-2
2.2 Simplified Diagram of the Papermaking Process 2-5
2.3 Major Emission Points Within the Pulp Mill 2-16
3.1 Federal Register, October 6, 1975 3-13
3.2 Standards of Performance - Kraft Pulp Mills 3-31
4.1 Counter Flow Approach 4-14
5.1 Source Emission Monitoring Systems 5-1
5.2 Subsystems of a TRS Continuous Emission Monitoring
System 5-4
5.3 In-Stack Internal Filter Configuration 5-6
5.4 In-Stack External Filter Configuration 5-6
5.5 Use of a Baffle Rate (V-Bar) and Sheath on a
Lime Kiln Application 5-7
5.6 Recovery Furnace TRS Sampling Probe Utilizing a
Porous Filter and a Baffle Plate 5-7
5.7 Application of Inertial Filter as Part of a
Sampling Probe Assembly 5-8
5.8 Umbilical Assembly 5-8
5.9 Flow Rates vs. Pressure Drop for Various Sample
Lines Sizes 5-13
5.10 Use of an Air Cooled Double Vortex Condenser in a
TRS CEM System 5-15
5.11 Permeation Dryer Technique 5-16
5.12 "Batch" S02 Scrubber 5-18
5.13 "Continuous" SOg Scrubber 5-18
5.14 Heated Quartz Tube TRS Oxidizer 5-19
5.15 Positive Displacement Pump Characteristics 5-20
5.16 Reciprocating Pump 5-21
5.17 Diaphragm Pump 5-21
5.18 Centrifugal Pump 5-22
5.19 Air Driven Eductor 5-23
5.20 Electrochemical Transducer 5-25
5.21 Fluorescence Spectroscopy 5-26
5.22 Absorption/Fluorescence Spectrum for the S02
Molecule 5-27
5.23 Flame Photometric Spectroscopy 5-28
5.24 Coulometric Technique 5-30
5.25 Typical GC System 5-32
5.26 Chromatographic Column 5-33
5.27 GC Chromatogram 5-34
5.28 Candel Industries TRS System 5-41
5.29 Probe/Conditioning System 5-42
5.30 Polarographic Principle 5-43
5.31 Charlton Technology Model CM-6000 TRS System 5-44
5.32 Probe/Conditioning System 5-45
5.33 Charlton Technology TRS Instrument Rack 5-46
5.34 CSI Dilution Probe 5-47
xiii
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LIST OF FIGURES (continued)
Figure No. Topic Page No.
5.35 Fine Filter/Critical Orifice of CSI Dilution Probe 5-47
5.36 Secondary Nozzle of CSI Dilution Probe 5-48
5.37 CSI Flame Photometric Detector 5-49
5.38 Sample Measurement System - Impregnated Lead
Acetate Paper 5-51
5.39 Lear Siegler TRS CEM System 5-52
5.40 ITT- Barton Titrator 5-57
5.41 ITT-Barton Probe/Extractive System 5-60
5.42 ITT-Barton Sampling Module 5-61
5.43 ITT-Barton Titration Module 5-62
5.44 Western Research TRS CEM System 5-63
5.45 Western Research Probe/Conditioning System 5-64
5.46 Western Research Analyzer System 5-65
5.47 Typical Chromatogram from Western Research TRS
CEM System 5-66
5.48 Western Research TRS CEM System Remote Output
System 5-67
5.49 STI Probe Configuration 5-69
5.50 STI TRS Conditional System 5-69
5.51 STI Heat Exchanger/Condenser Assembly 5-70
5.52 STI Analyzer Rack 5-73
5.53 Bendix Total Reduced Sulfur Analyzer System 5-75
5.54 Bendix Probe/Conditioning Assembly 5-76
5.55 Bendix Inertial Filter Assembly 5-77
5.56 Bendix Sample/Extraction System 5-78
5.57 Bendix Conditioning System 5-79
5.58 Bendix Analyzer Rack Assembly 5-81
5.59 Bendix TRS Chromatogram 5-83
5.60 Electrochemical Transducer 5-86
5.61 Electrocatalytic Technique 5-88
5.62 Magneto-Dynamic Technique 5-90
5.63 Magnetic Wind Technique 5-91
6.1 Construction of a Typical Permeation Tube 6-3
6.2 Automated Weighing Unit to Determine Weight Loss
of a Permeation Tube 6-5
6.3 Stripchart Readout of Automated Weighing Unit for
Permeation Rates 6-6
6.4 Typical Permeation Calibration System 6-7
6.5 Permeation Tube Information 6-8
6.6 Construction of a Permeation Vial 6-11
6.7 Single Dilution System 6-13
6.8 Construction of a Typical Rotameter 6-13
6.9 Forces Acting on a Float 6-14
6.10 Orifice Meter 6-15
6.11 Typical Orifice Meter Calibration Curve 6-15
6.12 Stability of Nitric Oxide in a Pre-Treated Gas
Cylinder with Decreasing Pressure 6-19
xiv
-------
LIST OF FIGURES (continued)
Figure No. Topic Page No.
6.13 S02 Cylinder Gas Certification Set-up 6-28
6.14 SO? Analysis Set-up 6-29
6.15 HgS Cylinder Gas Certification Set-up 6-32
7.1 Common Extraction System Used in the NCASI Detector
Evaluation 7-2
7.2 Sampling Maniforld Configuration Leading to
Individual Detectors 7-2
8.1 Federal Reference Method 16 Analytical
Configuration 8-1
8.2 Federal Reference Method 16 Sections 8-3
8.3 Typical Permeation Tube System 8-8
8.4 Certification of Permeation Tubes 8-9
8.5 Calibration of Analyzer and Dilution System 8-10
8.6 Typical GC Chromatogram 8-10
8.7 Gas Chromatography Calibration Curve 8-11
8.8 Gas Chromatography Field Calibration Data Sheet 8-13
8.9 Dilution System Calibration Verification 8-14
8.10 Sample Line Loss Determination 8-15
8.11 Proposed Federal Reference Method 16A Sample Train
Configuration 8-J7
8.12 50 mm Heated Teflon® Filter Holder 8-19
8.13 Promulgated Federal Reference Method 16A Sampling
Train Configuration 8-24
8.14 Optional Pre-test Leak Check 8-26
8.15 Field Dilution System 8-27
11.1 QA/OC Assessment 11-1
11.2 Data Assessment Report (DAR) - Continuous
Emission Monitoring (CEM) for Total Reduced
Sulfur (TRS) 11-8
11.3 Source Specific Quality Assurance Program 1 -11
11.4 Personnel Flow Chart Within Source OA Program 1 -18
11.5 Control Chart for Daily Zero/Span Checks 1 -21
11.6 Source Specific Troubleshooting Guide 1 -25
11.7 Source Trouble Report/Work Request 1 -26
11.8 Control Agency Phase Diagram 1 -37
11.9 Control Agency Level Diagram 1 -37
11.10 Typical Permeation Tube Audit System 11-41
11.11 Gas Cylinder Audit System 11-42
11.12 Use of Matched Rotameters in a Control Agency Gas
Cylinder Audit System 11-43
11.13 Use of Critical Orifice in a Control Agency QA
Audit System 11-44
11.14 Portable Test Atmosphere Generating Device 11-45
11.15 Internal Schematic of Portable Test Atmosphere
Generator 11-46
xv
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LIST OF TABLES
Table No. Subject Page No,
1.1 Formulas and Names of Important Sulfur Compounds
and Ions 1-2
2.1 Pulp Mill Population 2-6
2.2 Location of Pulp Mills in the United States 2-7
2.3 Pulp Mill Population Per State 2-12
2.4 State Location of Pulp Mills 2-13
2.5 Regional Location of Pulp Mills 2-14
2.6 Typical Emissions Concentrations for Sulfur
Compounds from Kraft Pulp Mills 2-17
2.7 Effects of Hydrogen Sulfide Inhalation on Humans 2-19
2.8 Time in Minutes Until 50 Percent Injury To Exposed
Plant Surfaces at 1,500,00 vg/rn3 Hydrogen Sulfide 2-21
2.9 Hydrogen Sulfide Ambient Air Quality Standards 2-22
3.1 Regulations Under the Clean Air Act 3-5
3.2 Federal Register Entries Applicable to Continuous
Emission Monitoring 3-8
3.3 Existing State Regulations Addressing Pulp Mills 3-15
3.4 Kraft Pulp Mills Affected by NSPS Regulations 3-19
3.5 NSPS Sources Requiring Continuous Emission
Monitoring 3-30
3.6 Subpart BB, Standards of Performance for Kraft Pulp
Mills, Pollutant Monitoring Requirements 3-32
3.7 Parameter Monitoring Requirements - Kraft Pulp
Mills 3-33
4.1 Standard Operation Procedures Manual 4-7
5.1 Principles Used in TRS Continuous Emission
Monitoring Systems 5-3
5.2 Subsystem Components of a TRS Continuous Emission
Monitoring System 5-5
5.3 Chemical Resistance of Various Materials 5-10
5.4 Maximum Continuous Operating Temperature for
Plastics 5-11
5.5 Sampling Line Lag Time 5-12
5.6 Costs of Various Sample Line Materials, Based on
100 ft. of 6.35 mm OD typing 5-14
5.7 Subdivisions of Positive Placement Pumps 5-20
5.8 Advantages/Disadvantages of Air Moving Systems 5-23
5.9 Commercially Available Total Reduced Sulfur
Continuous Emission Monitors 5-37
5.10 TRS CEM Experience Categories 5-39
5.11 Operation/Maintenance Experience of Field
Installed TRS Monitoring Systems 5-40
5.12 Standards of Performance for Kraft Pulp Mills
- Regulated Emissions Corrected to Percent Oxygen 5-85
6.1 Permeation Tube Construction 6-2
6.2 Permeation Rates for Selective Compounds 6-3
xvi
-------
LIST OF TABLES (continued)
Table No. Subject Page No.
6.3 Permeation Rates for FEP and TFE Teflon®
Permeation Tubes 6-4
6.4 Availability of NBS - SRM's for SOg 6-7
6.5 Suppliers of Certified Permeation Devices 6-10
6.6 Commercially Available Permeation Vials 6-12
6.7 Stability of Sulfur dioxide (S02) in Selective
Gas Cylinders 6-18
6.8 Gas Standards Tolerances 6-20
6.9 Available NBS-SRMs Pertinent to Kraft Pulp Mills
Regulations 6-21
6.10 Available CRMs and Their Manufacturers 6-24
7.1 NCASI Drift/Accuracy Evaluation of TRS Detectors -
Study #1 7-4
7.2 NCASI Evaluation of TRS Detectors - Study #2 7-6
7.3 NCASI Evaluation of TRS Detectors - Study #2
Laboratory Evaluation 7-9
7.4 NCASI Evaluation of TRS Detectors - Study #2
Laboratory/Field Evaluation 7-11
7.5 NCASI Relative Accuracy Test Passed 7-12
7.6 Relative Accuracy Test Results - Fraction of
Relative Accuracy Test Passed 7-12
8.1 Example Calculation 8-12
8.2 Probe Angle Evaluation 8-19
8.3 External Heated Filter Evaluation 8-20
8.4 Concentration of H2$ Determined From Each GC-FPD
Sample Injection With Calibration Gas Passing
Through Citrate Scrubber 8-21
8.5 Summary of Results Obtained from H2S Recovery
Checks on Blank Filtration Devices 8-22
8.6 Proposed and Promulgated Federal Reference
Method 16A 8-25
8.7 System Performance Specification - Proposed and
Promulgated Reference Method 16A 8-29
8.8 Method Comparison: FR Method 16 and Proposed
FR Method 16A Utilizing HgS Certified Gas Mixture 8-32
8.9 Method Comparison: FR Method 16 and Proposed FR
Method 16A Kraft Recovery Furnace 8-32
9.1 Performance Specifications for S02/NOX, 02/C02
and TRS Continuous Emission Monitoring Systems 9-2
9.2 Performance Specification Requirements - Kraft Pulp
Mills 9-3
9.3 Span Valves- Kraft Pulp Mills TRS/02 Monitors 9-5
9.4 Itinerary Involving Calibration Drift Determination 9-7
9.5 Calibration Drift Determination - Zero/Span 9-8
9.6 Performance Specification Requirements Regulatory
Changes 9-10
xvii
-------
LIST OF TABLES (continued)
Table No.
Subject
Page No.
9.7
9.8
9.9
9.10
9.11
9.12
9.13
10.1
10.2
11.1
11.2
11.3
11.4
11.5
11.6
11.7
11.8
11.9
5
3
3
Functions
- Regulatory
Performance Specification Test
Performance Specification Test
Performance Specification Test
Changes
Calibration Gas Mixture Levels
Performance Specification
Itinerary Involving Calibration Drift Determination
Field Data Sheet - Calibration Drift Determination
NSPS Sources Required to Submit Excess Emission
Reports (EERs) to Regulatory Authorities
Kraft Pulp Mill Excess Emission Reporting
Requirements
Cylinder Gas Audit Values
Responsibilities of Levels I, II and III in a
Source QA/QC Program
Source Quality Assurance Programs - Program
Participants and Responsibilities
QA/QC Activities Associated with Monitor
Precision and Accuracy
Source Quality Assurance Program - Total Reduced
Sulfur-Maintenance Timetable
Recommended Preventative Maintenance Schedule -
STI TRS CEM System
Total Reduced Sulfur - Continuous Emission
Monitoring System Logbook
Total Reduced Sulfur CEMs Problem Communication
Memo
Total Reduced Sulfur Precision Calculation Form
9-11
9-15
9-16
9-17
9-18
9-19
9-20
10-4
10-6
11-6
11-15
11-16
11-19
11-28
11-29
11-33
1 1 -34
11-35
xviii
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FORWARD
The main objective of the "Technical Assistance Document for Monitor-
ing Total Reduced Sulfur (TRS) from Kraft Pulp Mills" is to support State
and EPA personnel 1n their inspection of total reduced sulfur (TRS) con-
tinuous emission monitoring (CEM) systems. This will enable the agencies
to determine: (1) that a TRS CEM system is operating properly after initial
compliance; and (?) that emission control limits are accurately set.
An effort was made to provide information associated with all phases
of TRS CEMs with respect to EPA activities. The material was covered in
detail to provide an inspector not only with background material, but also
basic guidance necessary to conduct an organized and thorough inspection
of the TRS CEM system. In this effort, standard procedures have been developed
and presented to aid the Agency inspector. The resource package involves
three major documents. They are:
o Technical Assistance Document for Monitoring Total Reduced
Sulfur (TRS) from Kraft Pulp Mills;
o Federal Regulations; and
o Field Inspection Notebook for Monitoring Total Reduced
Sulfur (TRS) from Kraft Pulp Mills.
The Technical Assistance Document covers important topics associated
with NSPS Kraft pulp mills (40 CFR 60 Subpart BB). Background information
has been provided to aid the inspector in evaluating not only the TRS CEM,
but also source-specific quality assurance programs associated with the TRS
CEM system. More importantly, evaluation forms have been provided at the
end of the manual covering all aspects of a TRS CEM system. The manual is
organized into twelve chapters. A brief synopsis of each chapter is pro-
vided below.
o Chapter 1.0 - Total Reduced Sulfur - The regulations affecting Kraft
pulp mills are written in terms of total reduced sulfur (TRS). The objec-
tive of this chapter is to define the TRS term and to provide background
information associated with its formation.
o Chapter 2.0 - Kraft Pulp Mills - Chapter 2.0 discusses the produc-
tion of paper involving the Kraft, sulfite and neutral sulfite semichemical
(NSSC) process. Over 80% of wood pulp produced in the United States is by
the Kraft process, the major source of total reduced sulfur (TRS) emissions.
Presently, there are 391 pulp mills located within the U.S. of which one-
third are Kraft pulp mills. U.S. EPA Region IV contains the largest popu-
lation of pulp mills ( 37% ), with U.S. EPA Regions V, VI and X with equal
population ( 15% ). Characteristic emissions of the pulp industry coupled
with its status as the 10th largest industry in the U.S. has caused the
establishment of hydrogen sulfide ambient air .quality standards in an effort
to curtail gaseous emissions from pulp mills. The objective of this chapter
is to review the production of paper, sources of TRS emissions and historical
information assoicated with TRS emissions.
xix
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o Chapter 3.0 - Regulations - Through the State Implementation Plan
(SIP) and New Source Performance Standards (NSPS), Kraft pulp mills are
required to install, operate and maintain CEMs as part of their permit
conditions. Data generated from the installed CEM "...may be used directly
or indirectly for compliance determination..." as specified in 40CFR51.
Additionally, those emissions in excess of a standard are reported quarterly
to the regulatory authorities. NSPS standards for Kraft pulp mills were
promulgated in 1978 and applied to particulate and total reduced sulfur
emissions. Continuous emission monitoring was required for operations and
maintenance purposes. The objective of this chapter is to review and discuss
the regulations affecting Kraft pulp mills.
o Chapter 4.0 - Agency Inspection Program - The Agency inspection
program was designed to provide the state inspector with information to
determine a source's compliance status. Incorporating both the CEM
certification activities and on-site inspections, the example inspection
program involves a three phase and four level compliance program. The
phase process involves: (1) administrative activities addressing source
CEM application; (2) performance testing; and (3) final approval. The
level program involves: (1) on-site inspection; (2) record review; (3)
system audit; and (4) recertification procedures of the installed TRS CEM
system. Each phase and level observation indicates whether or not the
source CEM system has achieved the necessary level of compliance. This
chapter will review in detail an agency-oriented CEM program.
o Chapter 5.0 - Monitoring System Instrumentation - NSPS Kraft pulp
mills are required to monitor for operation and maintenance purposes. SIP
standards may differ. Commercially available TRS monitors are based on the
extractive technique. The main objective of an extractive system is to ex-
tract a representative sample from the source and transfer it to the de-
tector system for analysis without compromising its integrity. Common de-
tector systems employ either direct measurement of TRS ( gas chromatography)
or remove S02, oxidize the TRS to SOg and then analyze the SC<2 as TRS either
by electrochemical, fluorescent, flame photometric or coulometric technique.
The objective of this chapter is to describe most systems available on the
market for monitoring TRS emissions.
o Chapter 6.0 - Generation of Standard Test Atmospheres - The analy-
tical systems for monitoring total reduced sulfur (TRS) vary from gas chro-
matography to coulometric techniques. Varied as they are, they must all
be calibrated with a standard atmosphere of pollutant so a determination
of their precision and accuracy can be established. Calibration techniques
involving both dynamic and static calibration systems have been used routine-
ly in source monitoring. However, due to the complexity of the pollutant
(involving a combination of four separate reduced sulfur compounds), tradi- •
tional calibration techniques like the compressed gas cylinder have limited
applications. Portable permeation tube calibrators appear to be the logical
choice as part of an agency test system to generate standard test atmopshere
used during inspection and audit procedures. The objective of this chapter
is to review all systems which have the ability to generate test atmospheres
of HgS, CHsSH, (^3)2$ and (0*3)252- The strengths and weaknesses of each
method will be discussed. In addition, the correct procedure for analyzing
test gas cylinders will be investigated.
xx
-------
o Chapter 7.0 - Comparative Studies of TRS Monitors - Analytical
techniques for monitoring total reduced sulfur (TRS) from Kraft pulp mills
have traditionally been associated with wet chemical extractive methods.
Sampling normally involves extracting the gas through a probe and directing
the sample through a conditioning system with subsequent absorption in a
series of impingers. The concentration of pollutant is determined through
wet chemical analysis of the impinger content. Indeed, the majority of the
Federal Reference Methods applicable to stationary sources are based on wet
chemistry sampling and analysis. As continuous emission monitors replace wet
chemical techniques as the compliance method, the comparison between the two
is inevitable. The objective of this chapter is to review available studies
involving method comparisons of wet chemical techniques and TRS CEMs.
o Chapter 8.0 - The Reference Method - As defined in Subpart A-
General Provisions, of 40CFR60, a "Reference Method" means any method of
sampling and analyzing for an air pollutant as described in Appendix A-
Reference Methods. The Reference Methods are promulgated by EPA to pro-
vide uniform analytical methods to ensure consistency and accuracy in the
data generated. The legal authority for this action lies in Section 110,
111, 114 and 301 (a) of the Clean Air Act. Each Reference Method involves
specifications for equipment, procedures and system performance. The ob-
jective of this chapter is to discuss the specification of Federal Ref-
erence Method 16 and Federal Reference Method 16A. In particular, method
strengths and weaknesses along with required quality assurance activities
will be reviewed.
o Chapter 9.0 - Performance Specification Test - After the total re-
dueed sulfur (TRS) continuous emission monitoring (CEM) system has been
purchased and installed on the source, it must pass a Performance Specifi-
cation Test (PST). The intent of the PST is to provide the regulatory
agency an opportunity to evaluate the installed monitoring system to ensure
its initial operation. The PST is a one time certification procedure. It
is not the intent of the PST to demonstrate long term performance of the
monitoring system. Two PSTs apply to monitoring TRS from Kraft pulp mills:
o Performance Specification Test 5; and
o Performance Specification Test 3.
The objective of this chapter is to discuss both of these PSTs as
applied to Kraft pulp mills.
o Chapter 10.0 - Excess Emission Reports - EPA and many state air
pollution control agencies are rapidly expanding their programs involving
recordkeeping and reporting requirements in association with emission mon-
itoring programs and performance testing. This is due, in part, to new
regulations pertaining to new and existing sources as outlined in 40 CFR
60 and 40 CFR 51 respectively. These regulations require "installation
of monitoring equipment and performance testing..." and "for periodic re-
ports and recordkeeping of nature and magnitude of such emissions." Add-
itionally, Sections 113 and 114 of the Clean Air Act (CAA) as amended in
1977 involves the use of recordkeeping and reporting requirements as a
means of enforcement of emission standards. The objective of this chapter
is to review the regulations associated with recordkeeping and reporting
requirements for Kraft pulp mills and to recommend a standardized reporting
and agency review format.
xxi
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o Chapter 11.0 - Quality Assurance/Quality Control - The primary ob-
jective of quality assurance/quality control is to ensure that all data
collected and reported by the TRS CEM system is meaningful, precise and
accurate within a stated acceptance criteria.
As CEMs became an integral part of the enforcement activities of both
EPA and Agency programs, it became imperative that some form of continued
evaluation of the monitoring system occur to ensure its continued perform-
ance and reliability. This continued evaluation would assist EPA and the
State in establishing CEM long-term performance and reliability as part
of their data base. Consequently, QA/QC activities involve both source
and agency functions. The main objective of this chapter is to address the
QA/QC activities associated with:
o I). S. Environmental Protection Agency;
o Industry; and
o State Agency.
o Chapter 12.0 - Equipment Selection - The monitoring of total re-
duced sulfur compounds from Kraft pulp mills can be performed by either wet
chemical or continuous emission monitoring instrumentation. As will be
demonstrated in this manual, each method contains both strengths and weak-
nesses. The wet chemical techniques are simpler to use, but care must be
taken during all aspects of the procedures to ensure an accurate "value".
Likewise, continuous emissions monitors appear to provide accurate data if
an established quality assurance program is incorporated as part of the
source continuous emission monitoring program. The objective of this chap-
ter is to provide a list of vendors to the reader to assist in the selection
of a total reduced sulfur monitoring system, whether wet chemical or con-
tinuous.
o Chapter 13.0 - Bibliography - A bibliography is provided at the end
of this document. It provides a source of additional information for
those readers who may need a more extensive review.
o Chapter 14.0 - Index - The index is provided for the agency inspector
to quickly reference topics throughout the Technical Assistance Document.
To supplement this Technical Assistance Document manual, a Field Inspec-
tion Notebook has been developed. The Field Inspection Notebook is a step-
by-step procedures manual, associated with an Agency CEM program, involving
the phase and level approach in inspecting TRS CEMs. It is intended to be
used by the control agency inspectors, at the source, when evaluating a
source CEM program involving TRS monitoring systems.
Consequently, the purpose of the Technical Assistance Document and
the Field Inspection Notebook is to provide the necessary data and techni-
cal information to assist State inspectors in the evaluation of both NSPS
and SIP Kraft pulp mills with respect to TRS continuous emission monitors.
Utilization of these two documents will enable the State inspector to
make regulatory decisions based on an understanding and systematic evalu-
ation of a source CEM program.
xxii
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1.0 TOTAL REDUCED SULFUR
1.1 INTRODUCTION
In 1675, Robert Boyle Identified sulfur as an element. Sulfur is a
member of the Group VI elements of the periodic table. The other members
of the group are oxygen (02), selenium (Se), tellurium (Te) and polonium
(Po). Sulfur occurs in nature in both the free state and the combined
state and has been known for centuries. Although not very abundant (0.05
percent), sulfur is readily available because of its occurences in large
beds of the free element. These beds, usually several hundred feet below
ground, are thought to be due to bacterial decomposition of calcium sul-
fate. About 80 percent of the world's sulfur supply comes from deposits
of native sulfur in Texas and Louisiana. Other important deposits are in
the volcanic districts of Sicily, Japan and Mexico.
Sulfur occurs in the combined state, as sulfides, in the following com-
mon minerals: galena, PbS; iron pyrites, FeS2? and argentite, Ag2S. De-
posits of gypsum, CaSO^ • 2H20, is another important sulfur product. Sulfur
also occurs in the combined state in many organic substances, such as yolks
of eggs and hair.
1.2 OXIDATION STATES OF SULFUR
Elemental sulfur, in the free state, has no characteristic odor. Ele-
mental sulfur exists as a yellow crystalline rhombic solid composed of eight
(8) sulfur molecules in a ring formation, as illustrated in Figure 1.1.
Figure 1.1. Elemental Sulfur
However, as the rhombic sulfur is heated, the rhombic crystals change
to a monoclinic form which is still composed of an eight member ring, but
now has a different geometric form.
As we continue to heat the sulfur, the ring structure dissociates into
$2 molecules and the color of the vapor gradually changes from clear to
yellow. At temperatures of about 2000°C, $2 molecules dissociate in the
monoatomic vapor, S. With excess air present, the monoatomic S reacts
with 02 to form different oxidized compounds, such as S02, 503, and ^$04.
1-1
-------
Depletion of oxygen in the process causes the monoatomic S to combine
with hydrogen (H) to form reduced sulfur compounds, such as f^S, Q^SH,
(^3)2$ and (CH3J2S2- As the sulfur molecule changes, it is, in essence,
changing its ability to gain or loose electrons. Each state, therefore,
represents different "oxidation" states. Table 1.1 lists the different
"oxidation" states, formulas and names for sulfur.
TABLE 1.1
FORMULAS AND NAMES OF IMPORTANT SULFUR
COMPOUNDS AND IONS
Names
Hydrogen sulfide
Sulfide ion
(Hydrogen sulfide ion)
Sulfur
Sulfur dioxide
Sulfite ion
(Hydrogen sulfite ion)
Sulfurous acid
Sulfur trioxide
Sulfate ion
(Hydrogen sulfate ion)
Sulfuric acid
Formulas
H2S
S = (HS-)
S8
(SfiSdSpS)
SOg
S03=(HS03-)
H?S03
S03
S04=(HS04-)
H?SO/i
Electronic State
-2
0
+4
+6
Common
Name Usage
Reduced state
Neutral state
Oxidized
state
New Source Performance Standards (NSPS) address reduced sulfur limi-
tations [as H£S or total reduced sulfur (TRS)] in the following subparts:
o Subpart J - Petroleum Refineries (H2S or TRS apply only with a
reduction control system not followed by incineration);
and
o Subpart BB - Kraft Pulp Mills.
1.3 TERMINOLOGY
Subpart BB - Kraft pulp mills, are regulated for TRS emissions. (Chap-
ter 2.0 will discuss the basis for the regulations and their applicability
to Kraft pulp mills). Total reduced sulfur (TRS) is a common term used
by EPA to collectively regulate four major constituents of emissions from
Kraft pulp mills.
TRS is defined as the sum of concentrations of the following reduced
sulfur compounds present in the regulated emission point.
1-2
-------
TRS = [H2S + CH3SH + (CH3)2S + (CH3)2S2]
where:
TRS = Total reduced sulfur, in ppm, dry basis;
H2S = Hydrogen sulfide, ppm;
= Methyl mercaptan, ppm;
= Dimethyl sulfide, ppm; and
(CH3)2S2 = Dimethyl disulfide, ppm.
Early tests performed by EPA at selected Kraft pulp mills determined
that these were the major reduced sulfur emissions.
1.3.1 Hydrogen Sulfide (H?S)
Hydrogen sulfide represents the largest gaseous emission from the
Kraft process. Hydrogen sulfide is formed in the recovery furnace and in
the digester in a reducing atmosphere as the sulfur compounds in the
black liquor are volatilized and reduced. Hydrogen sulfide is a colorless
gas with an offensive odor; in fact, it is what gives rotten eggs their
offensive smell. This gas is very toxic in small quantities.
1.3.2 Methyl Mercaptan (CH.-^SH)
Methyl mercaptan is formed during the Kraft cooking and is present
in low concentrations as a dissolved gas in the black liquor. Methyl mer-
captan is formed in the digester and is primarily emitted with the digester
relief and blow.
1.3.3 Dimethyl Sulfide (CH.-QpS and Dimethyl Disulfide (CHa)ySp.
Dimethyl sulfide is primarily formed through the reaction of methyl
mercaptide ion with the methoxy-lignin component of the wood. It does
not, however, dissociate as hydrogen sulfide and methyl mercaptan do.
Major emission point within the Kraft process is the recovery system.
1-3
-------
1-4
-------
2.0 PULP MILLS
2.1 PRODUCTION OF PAPER
There are two distinct phases in the conversion of raw wood into the
finished paper product: (1) pulping of wood; and (2) production of paper
and related products from the pulp:
o Kraft (sulfate);
o sulfite; or
o neutral sulfite semi chemical (NSSC).
2.1.1 Kraft (Sulfate) Process
Bark is first removed from the logs, then the peeled logs are fed into
a machine which cuts them into chips. The chips are fed to a digester
where the lignin that binds the wood fibers is dissolved in a solution of
sodium sulfide and caustic soda. This "cooking solution" is known as the
white liquor. The caustic soda enables the breakdown of lignins, under
controlled conditions of temperature and pressure, to alcohols and acids,
thus freeing the cellulose fibers (Figure 2.1).
This hydrolysis also produces mercaptans and sulfides, which are
responsible for the malodors.
Presently, there are two types of digesters used in the pulp and
paper process; batch and continuous. In recent years, more and more of
the mills are using the continuous process rather than the batch process.
As the name implies, batch processing involves a fixed volume of woods
chips to be processed. As the breakdown of the lignin proceeds by the white
liquor, pressure builds up in the digester. It is essential that this pres-
sure be released periodically, or continuously, to control and maintain
proper operation. The uncondensibles vented during this "pressure release"
step are recovered through a heat exchanger/condenser combination. At the
end of the digestion, the contents are transferred to the blow tank.
In the continuous digester, a steady flow of wood chips is added to
the digester. Once again, white liquor and steam are added to produce
the chemical reaction. In the continuous digester configuration, the wood
chips are normally pretreated in a pre-steaming vessel where they are
wetted and deaerated.
At the bottom of the digester is a countercurrent wash zone where the
pulp-liquor mixture is washed. The spent liquor from this "cold washing"
is drawn off the bottom of the digester into a flash tank where this "black"
liquor is expanded or flashed. The flash stream from the flash tank is used
in the presteaming vessel. The uncondensibles from the stream are recovered
by a condenser. The weak black liquor from the primary flash tank is further
used in the process.
2-1
-------
ro
WIHIIJ fr»
WHITE LIQU
(NaOII * Na2S
IIIU Mtll ' '
OR SYSTEM
-^ |i||| )• » PI
WASH IMS
.^ • W
lucjiu- ni «ni/ i iniinn
JLP
ftTER
VENT GAS
{ VENT GAS NONCONOENSABLES
RECOVERY HEAVY BL
FURNACE BLACK Lit
SYSTEM LIQUOR OXIt
(OP1
-*- AIR
J .
ACK
!X?,n« MULTIPLC
'JI101* EFFECT
SJL.,! ^ EVAPORATOR
riONAL) - SYSTEM
^
' |
SMELT
lNa2C03*Na2S) | VENT GAS
1 VENT GAS 1
WATER — *-
DISSOLVING -* CONOENSA
TAM* STHIPPEfl
1ANR SYSTEM
I
GREEN LIQUOR |
(WHITE LIQUOR | AIR
(HtLYLLc IU
DIGESTER) Cl
AUSTICIZING IIMC
TANK "*
1 CALCIUM
1 . ., _ r.ARRdNATF —
TE _p_ TO TREATMENT POND
1
_^_ CONDENSATE
STREAM I
• \i
~V-^"^
ENT OAS
MUD
Figure 2.1. Kraft Pulp Mill Operation
-------
As the pressure in the digester 1s lowered, this causes the soft
woods chips to explode and mat together into a fiber pulp. The "black
liquor," due to the residual pressure, is forced into a blow tank as illus-
trated in Figure 2.1. The noncondensable gases from the digester are
either confined and treated or released to the atmosphere.
The "black liquor" is diluted in the blow tank and then is pumped to
washers where the black liquor is removed. There are presently two major
types of washers used in the industry: rotary-drum vacuum washers and
diffusion washers. Of the two, vacuum washers are the most common.
In the vacuum washer, the pulp first passes through a "knotter" where
chunks of wood not cooked in the digester are removed. The pulp is then
washed with water, counter currently, then dewatered on a vacuum filter,
and readied for processing.
Continuous diffusion washing involves depositing the pulp in a series
of screen plates, through water washing. The water leaves the wash cylinder
and flows downward to the drainage system. The residual pulp is scraped
from the screen plates and readied for processing.
In both processes, the pulp is washed counter currently to remove
the black liquor and waste wood products. From here, the pulp may be
bleached to form paper products or dried and sold as market pulp.
The remaining process involves recovering sodium and sulfur from the
spent black liquor. This is accomplished through the recovery furnace sys-
tem. There are two major types of recovery furnaces: (1) direct-contact
system and (2) indirect-contact evaporator.
In the direct-contact system, black liquor mixed with weak liquor
from the pulp washers is pumped through an oxidation tower to increase
chemical recovery and odor control. This oxidation step allows the con-
version of sodium sulfide to innocuous salts to prevent the release of
hydrogen sulfide. At this point the solids are approximately 15%.
From the oxidation tower, the liquid passes through a multi-stage
evaporator, where the solids increase to between 60-70%.
Concentration of the black liquor is necessary to facilitate combus-
tion of the dissolved organic material in the recovery furnace.
The concentrated black liquor is then sprayed into the recovery
furnace, where the organics support combustion. There are three major
purposes for burning concentrated black liquor in the recovery furnace:
(1) recover sodium and sulfur; (2)to produce steam and (3) dispose of
unwanted dissolved wood components in the liquor.
The black liquor is introduced into the furnace through spray nozzles.
Air for combustion is supplied through a forced-draft system. Part of this
air is used to maintain the reducing zone at the bottom of the furnace where
the char bed is converted from sodium sulfate and other sodium-base sulfur
compounds to sodium sulfide. The char bed is formed from the introduction
of the black liquor into the drying zone of the recovery furnace, causing
the evaporation of water and formation of dry solids which fall to the
bottom of the furnace to form the char bed.
2-3
-------
The remaining forced air is used to complete oxidation of compounds
above the char bed.
The release of heat from the combustion zone is sufficient to liquify
the char bed, allowing it to be drained from the recovery furnace into a
smelt-dissolving tank. The dissolved smelt, containing mainly sodium
sulfide, sodium sulfate and sodium carbonate, is called green liquor.
Emissions of TRS from the recovery furnace and the direct contact
evaporator can be high. Recovery furnace emissions are affected by
distribution of combustion air, concentration of black liquor solids,
spray pattern of nozzles in recovery furnace, heat content of liquor fed
and sodium sulfide concentration in the black liquor.
The smelt dissolving tank, causticizer and lime kiln are all part of
the closed-loop system of converting green liquor to white liquor. The
process begins at the smelt dissolving tank located below the recovery
furnace. Molten smelt (sodium carbonate and sodium sulfide) that accumu-
lates on the floor of the furnace is released to the tank where it dis-
solves in water to form "green liquor." This contact of smelt and
water causes large quantities of steam to be released.
From the smelt dissolving tank, the green liquor is pumped to the
causticizer where quicklime (CaO) is added to convert the sodium carbonate
(Na2 003) to sodium hydroxide (NaOH) which is then used as white liquor
in the digester process. The causticizer process involves two steps:
(1) the reaction of calcium oxide with water to form calcium hydroxide;
and (2) the reaction of CaOH with N32C03 to form NaOH plus a CaCOs pre-
cipitate. The calcium carbonate is then calcined in the lime kiln to
produce calcium oxide which is reused in the causticizer process.
The lime kiln is very important in the process. Lime mud from the
causticizer is fed to the top of the kiln. The mud is dried by combustion
of natural gas or fuel oil in a counter-current flashing. The rotating
kiln (1-2 rpm) causes the lime to proceed downward through the kiln
towards the high temperature zone (1800-2000°F). As the lime moves down
the kiln, it dries and agglomerates into small pellets and finally is
calcined to calcium oxide near the exit where the gas/oil fired burner is
located. The discharge can either be stored or put directly back into the
causticizer.
As can be seen from Figure 2.1, the majority of the process involves
recovery of spent chemicals.
2.1.2 Sulfite Process
The sulfite process is very similar to the Kraft pulping process. In
the sulfite process, sulfurous acid base solution is used to dissolve the
lignin in the wood chips rather than a caustic solution as in the Kraft
process. Additional buffering, utilizing bisulfite salts of sodium, cal-
cium, ammonia or magnesium, is required during the cooking in the digester.
The wood chips are cooked in the digester. Then the pressure is reduced
and the contents are moved to the blow tank, where the chips are defibered.
2-4
-------
The pulp is separated into two groups, the spent liquor and the pulp,
through a series of washers. The pulp is then sent to bleaching and
finally through the papermaking process.
2.1.3 Neutral Sulfite Semichemical (NSSC)
Two major aspects separate the NSSC process from either the Kraft or
sulfite processes. They are:
o The cooking liquor is a neutral solution of sodium sulfite and sodium
bicarbonate or sodium carbonate, rather than acidic or basic; and
o Only a portion of the lignin is dissolved in the digester during
cooking.
The partially cooked wood chips are further subjected to mechanical
attrition to produce the pulp. From this stage, the pulp is bleached and
processed similar to the Kraft and sulfite processes to produce paper.
In summary, of the two phases in the production of paper, the pulping
of the wood and the manufacture of the paper, the pulping process is the
larger source of air pollutants. The Kraft or sulfate pulping process
produces over 80 percent of the chemical pulp produced annually in the
United States. The remaining 20 percent of the chemical pulp is produced
by the sulfite and neutral sulfite semi-chemical (NSSC) processes. Fig-
ure 2.2 illustrates the basic process of papermaking. The pulping of wood
(utilizing the kraft, sulfite or neutral sulfite semichemical) is solely
involved in the digester aspect of papermaking.
CHIPS
WATM
DIGESTER
STEM!
WIM SOWN
FOURDRINIER
fUT
PRESSES
cum**
DRYERS
CALENDER
END
Figure 2.2. Simplified Diagram of the Papermaking Process.
2-5
-------
2.2 PULP MILL POPULATION
Since the time the first Kraft mill was built In 1891, the Industry
has grown to be the 10th largest industrial process in the United States.
Table 2.1 reflects the growth of this industry in the production of paper
over the last decade.
TABLE 2.1
PULP MILL POPULATION
Process
Kraft
Sulfite
Other*
Total
Number of Mills
1968
116
38
230
384
1984
126
26
237
389
Production
1968
29.6
3.0
3.6
36.4
Million Tons
1984
42.0
1.8
3.0
46.8
1 Other includes chemimechanical, alkaline neutral, semi-
chemical, cold soda, deinking, rag, rope, flux, bagasse
and cotton lintons pulp mills.
Review of Table 2.1 indicates a shift from the sulfite process to
the Kraft process over the previous decade.
The names and locations of currently operating pulp mills utilizing
the Kraft or sulfite process are listed in Table 2.2.
2-6
-------
TABLE 2.2
LOCATION OF PULP MILLS IN THE UNITED STATES
Company
State Name
Alabama
Container Corp. of America
Alabama River Pulp Co.
Coos a River Newsprint
Champion Paper Corp.
Gulf States Paper Corp.
Allied Paper, Inc.
Alabama Kraft Co.
International Paper Co.
Scott Paper Co.
Union Camp Corp.
James River-Dixie/Northern
MacMillan Bloedel Inc.
Hammermill Papers Group
Alaska
Louisiana-Pacific Corp.
Alaska Pulp Co., Inc.
Arizona
Southwest Forest Industries
Arkansas
Nekoosa Papers, Inc.
International Paper Co.
Georgia- Pacific Corp.
Potlatch Corp.
Arkansas Kraft Corp.
International Paper Co.
Weyerhaeuser Co.
California
Simpson Paper Co.
Louisiana-Pacific Corp.
Simpson Paper Co.
Louisiana-Pacific Corp.
Florida
St. Regis Corporation
Container Corp. of America
ITT Rayonier, Inc.
Alton Packaging Corp.
Jacksonville Kraft Paper Co.
Georgia-Pacific Corp.
Southwest Forest Industries,
Inc.
Buckeye Cellulose Corp.
St. Joe Paper Co.
Location
Brewton
Claiborne
Coos a Pines
Courtland
Demopolis
Jackson
Mahrt
Mobile
Mobile
Montgomery
Pennington
Pine Hill
Selma
Ketchikan
Sitka
Snowflake
Ashdown
Camden
Cr os sett
McGehee
Morrilton
Pine Bluff
Pine Bluff
Anderson
Antioch
Fairhaven
Samoa
Cantonment
Fernandina Beach
Fernandina Beach
Jacksonvil le
Jacksonville
Palatka
Panama City
Foley
Port St. Joe
Process
Kraft
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Sulfite
X
X
X
2-7
-------
TABLE 2.2 (Continued)
Company
State Name
Georgia
Continental Forest Industries
Brunswick Pulp & Paper Co.
Great Southern Paper Co.
ITT Rayonier, Inc.
Georgia Kraft Co.
Georgia Kraft Co.
Buckeye Cellulose Corp.
Stone Container Corp.
Interstate Paper Corp.
Gilman Paper Co.
Union Camp Corp.
Owens-Illinois Inc.
Idaho
Potlatch Corp.
Kentucky
Willamette Industries Inc.
Westvaco Corp.
Loui siana
International Paper Co.
Crown Zellerbach Corp.
Willamette Industries
Boise Southern Co.
Boise Southern Co.
Stone Container Corp.
International Paper Co.
International Paper Co.
Georgia-Pacific Corp.
International Paper Co.
Manville Forest Products Corp.
Ma i ne
Statler Tissue Co.
Scott Paper Co.
International Paper Co.
Lincoln Pulp & Paper Co., Inc.
Great Northern Paper Co.
James River Corporation
Boise Cascade Corp.
S. D. Warren Co.
Georgia-Pacific Corp.
Scott Paper Company
Location
Augusta
Brunswick
Cedar Springs
Jesup
Krannert
Macon
Oglethorpe
Port Wentworth
Riceboro
Saint Marys
Savannah
Valdosta
Lewi ston
Hawesville
Wickliffe
Bastrop
Bogalusa
Campti
De Ridder
Elizabeth
Hodge
Mansfield
Pineville
Port Hudson
Springhill
West Monroe
Augusta
Hi nek ley
Jay
Lincoln
Millinocket
Old Town
Rumford
Westbrook
Woodland
Wins low
Process
Kraft
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Sulfite
X
X
X
2-8
-------
TABLE 2.2 (Continued)
Company
State Name
Maryland
Westvaco Corp.
Michigan
Mead Corp.
S. D. Warren Co.
Minnesota
Potlatch Corp.
Boise Cascade Corp.
Mississippi
Georgia Pacific Corp.
International Paper Co.
International Paper Co.
International Paper Co.
Leaf River Forest Products,
Inc.
Montana
Champion Packaging Corp.
New Hampshire
James River Corp.
New York
Finch, Pruyn & Co., Inc.
International Paper Co.
North Carolina
Champion Paper Corp.
Weyerhaeuser Co.
01 in Corp.
Weyerhaeuser Co.
Federal Paper Board Co.
Champion Packaging Corp.
Ohio
Mead Corp.
Oklahoma
Weyerhaeuser Co.
Oregon
Willamette Industries Inc.
Crown Zellerbach Corp.
International Paper Co.
James River-Dixie/Northern
Crown Zellerbach Corp.
Publishers Paper Co.
Publishers Paper Co.
Boise Cascade Corp.
Weyerhaeuser Co.
Georgia-Pacific Corp.
Boise Cascade Corp.
Location
Luke
Escanaba
Muskegon
Cloquet
International Falls
Monti cello
Moss Point
Natchez
Vicksburg
New Augusta
Missoula
Berlin
Glens Falls
Ticonderoga
Canton
New Bern
Pisgah Forest
Plymouth
Riegelwood
Roanoke Rapids
Chillicothe
Valliant
Al ba ny
Clatskanie
Gardiner
Halsey
Lebanon
Newberg
Oregon City
Salem
Springfield
Toledo
St. Helens
Process
Kraft
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Sulfite
X
X
X
X
X
2-9
-------
TABLE 2.2 (Continued)
Company
State Name
Pennsylvania
Penntech Papers Inc.
Appleton Papers, Inc.
P. H. Glatfelter Co.
South Carolina
Bowaters Carolina Co.
Union Camp Corp.
Stone Container Corp.
International Paper Co.
Westvaco Corp.
Tennessee
Bowater Southern Paper Corp.
Location
Johnsonburg
Roaring Spring
Spring Grove
Catawba
Eastove'r
Florence
Georgetown
North Charleston
Calhoun
Tennessee River Pulp & Paper Co. Counce
Texas
St. Regis Corp.
St. Regis Corp.
Owens-Illinois, Inc.
Champion Paper Corp.
International Paper Co.
Temple-Eastex Inc.
Virginia
Westvaco Corp.
Union Camp Corp.
Stone Container Corp.
Chesapeake Corp. of
Virginia Inc.
Washington
Georgia-Pacific Corp.
Crown Zellerbach Corp.
Weyerhaeuser Co.
Scott Paper Co.
Longview Fiber Co.
Weyerhaeuser Co.
Crown Zellerbach Corp.
St. Regis Paper Co.
Boise Cascade Corp.
Scott Paper Co.
Weyerhaeuser Co.
ITT Rayonier Inc.
ITT Rayonier Inc.
Houston
Lufkin
Orange
Pasadena
Texarkana
Silsbee
Covington
Franklin
Hopewel 1
West Point
Bellingham
Camas
Cosmopolis
Everett
Longview
Longview
Port Townsend
Tacoma
Wallula
Anacortes
Everett
Hoquiam
Port Angeles
Process
Kraft
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
X
Sulfite
X
X
X
X
X
X
2-10
-------
TABLE 2.2 (Continued)
State
Company
Name
Location
Process
Kraft
Sulfite
Wisconsin
Consolidated Papers, Inc.
Wausau Paper Mills Co.
James River-Dixie/Northern
Procter & Gamble Paper
Products Co.
Thilmany Pulp & Paper Co.
Mosinee Paper Corp
Nekoosa Papers Inc.
Badger Paper Mills, Inc.
Nekoosa Papers, Inc.
Rhinelander Paper Co. Inc.
Weyerhaeuser Co.
Consolidated Papers, Inc.
Scott Paper Co.
Flambeau Paper Co.
Appleton
Brokaw
Green Bay
Green Bay
Kaukauna
Mosinee
Nekoosa
Peshtigo
Port Edwards
Rhinelander
Rothschild
Wisconsin Rapids
Oconto Falls
Park Falls
X
X
X
X
X
X
X
X
X
X
X
X
X
Table 2.3 summarizes the total number of pulp mills within each state.
Major emissions of total reduced sulfur (TRS) occur from the Kraft process,
while sulfur dioxide (S02) emissions are predominant from the sulfite process,
Other process (de-inking, defibrated wood, etc.) have minimum emissions.
TABLE 2.3
PULP MILL POPULATION PER STATE
State3
Alabama
Alaska
Arizona
Arkansas
California
Connecticut
Delaware
Florida
Georgia
Idaho
Illinois
Indiana
Iowa
Kentucky
Louisiana
Ma i ne
Maryland
Massachusetts
Michigan
Minnesota
Mississippi
Pulp
Mills
(Total )1
23
2
5
9
14
2
1
11
22
1
4
2
2
3
21
23
2
7
12
11
10
Pulp Mill Process
Kraft
13
_
1
7
4
—
-
8
12
1
_
.
_
2
11
7
1
-
2
2
5
Sulfite
-
2
_
_
_
_
_
1
-
-
_
_
_
-
—
3
-
-
-
-
-
Other2
10
_
4
2
10
2
1
2
10
-
4
2
2
1
10
13
1
7
10
9
5
Contd,
2-11
-------
TABLE 2.3 (Contd.)
PULP MILL POPULATION PER STATE
State3
Missouri
Montana
New Hampshire
New Jersey
New York
North Carolina
Ohio
Oklahoma
Oregon
Pennsylvania
Puerto Rico
South Carolina
Tennessee
Texas
Vermont
Virginia
Washington
Wisconsin
Pulp
Mills
(Total)1
1
1
4
5
17
12
11
6
26
9
1
12
13
11
2
11
23
37
Pulp Mill Process
Kraft
-
1
1
-
1
6
1
1
7
3
-
5
2
6
-
4
7
5
Sulfite
-
-
-
-
1
-
-
-
4
-
-
-
-
-
-
-
6
9
Other2
1
-
3
5
15
6
10
5
15
6
1
7
11
5
2
7
10
23
TOTAL
389
126
26
237
1-Total includes Kraft, sulfite, NSSC, de-inked, defibrated wood,
around, rags, etc., pulp processing mills.
'Includes chem-mechanical, alkaline neutral, semi-chemical, cold
soda, rag, rope, flax, bagasse and cotton linters pulp mills.
3States not listed have no pulp mills (Kansas, Connecticut, New
Mexico, Colorado, Nebraka, Rhode Island, West Virginia, North Dakota,
South Dakota, Wyoming, Utah, Nevada and Hawaii).
Table 2.4 summarizes the number of pulp mills located within each
state while Table 2.5 lists number of pulp mills per Region.
2-12
-------
TABLE 2.4
STATE LOCATION OF PULP MILLS
Location
Region I
o Maine
o New Hampshire
o Vermont
o Connecticut
o Massachusetts
o Rhode Island
Region II
o N.Y.
o N.J.
o Puerto Rico
o Virgin Islands
Region III
o Pennsylvania
o Maryland
o Virginia
o West Virginia
o Delaware
o District of Columbia
Region IV
o N.C.
o S.C.
o Georgia
o Alaska
o Mississippi
o Florida
o Tennessee
o Kentucky
Region V
o Ohio
o Indiana
o Illinois
o Wisconsin
o Minnesota
o Michigan
Region VI
o Texas
o Oklahoma
o Arkansas
o Louisiana
o New Mexico
Pulp Mills
Total
23
4
2
2
7
-
17
5
1
0
9
2
11
-
1
0
12
12
22
23
10
11
13
3
11
2
4
37
11
12
11
6
9
21
—
% of Total
5.9
1.0
0.5
0.5
1.8
0.0
4.4
1.3
0.3
0.0
2.3
0.5
2.8
0.0
0.3
0.0
3.1
3.1
5.7
5.9
2.6
2.8
3.3
0.8
2.8
0.5
1.0
9.5
2.8
3.1
2.8
1.5
2.3
5.4
0.0
Kraft Mills
Total
7
1
-
-
-
-
1
-
-
-
3
1
4
-
-
-
6
5
12
13
5
8
2
2
1
-
-
5
2
2
6
1
7
11
™
% of Total
5.6
0.8
0.0
0.0
0.0
0.0
0.8
0.0
0.0
0.0
2.4
0.8
3.2
0.0
0.0
0.0
4.8
4.0
9.5
10.3
4.0
6.3
1.6
1.6
0.8
0.0
0.0
4.0
1.6
1.6
4.8
0.8
5.6
8.7
0.0
2-13
-------
TABLE 2.4 (Continued)
STATE LOCATION OF PULP MILLS
Location
Region VII
o Kansas
o Nebraska
o Iowa
o Missouri
Region VIII
o Colorado
o North Dakota
o South Dakota
o Montana
o Wyomi ng
o Utah
Region IX
o California
o Nevada
o Hawaii
o Arizona
o American Samoa
o Guam
Region X
o Washington
o Oregon
o Idaho
o Alaska
Pulp Mills
Total
-
_
2
1
-
_
_
1
-
-
14
_
_
5
0
0
23
26
1
2
% of Total
0.0
0.0
0.5
0.3
0.0
0.0
0.0
0.3
0.0
0.0
3.6
0.0
0.0
1.3
0.0
0.0
5.9
6.7
0.3
0.5
Kraft Mills
Total
-
_
_
-
-
_
_
1
-
-
4
_
_
1
-
-
7
7
1
—
% of Total
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.8
0.0
0.0
3.2
0.0
0.0
0.8
0.0
0.0
5.6
5.6
0.8
0.0
TABLE 2.5
REGIONAL LOCATION OF PULP MILLS
U. S. EPA Region
I
II
III
IV
V
VI
VII
VIII
IX
X
Pulp Mills
Total
38
23
23
106
77
47
3
1
19
52
% of Total
9.8
5.9
5.9
27.2
19.8
12.1
0.8
0.3
4.9
13.4
Kraft Mills
Total
8
1
8
53
10
25
0
1
5
15
% of Total
6.3
0.8
6.3
42.1
7.9
19.8
0.0
0.8
4.0
11.9
2-14
-------
2.3 KRAFT PULP MILL EMISSIONS
While other industries, such as the petroleum industry, photochemical
plant complexes, coke oven plants, dye manufacturers and others have odor-
ant problems, the Kraft paper mill industry has made more people aware of
its presence due to its characteristic odors. The pulp and paper manufac-
turing is reported to be the tenth largest manufacturing industry in the
United States, accounting for nearly 4 percent of the value of all manu-
facturing. As indicated earlier, it consists of two well defined segments:
pulping and paper making. Pulping is the conversion of fibrous raw
materials such as wood, cotton, or used paper into a material suitable
for use in paper, paperboard, and building material. Wood is the dominant
source of fibers for paper production. As discussed earlier pulp is pro-
duced by two general methods: (1) mechanical pulp is produced by grinding
or shredding the wood to free the fibers; and (2) chemical pulp is produced
by cooking wood chips in chemical solutions that dissolve the lignin bind-
ing material. Air pollution emissions of the chemical pulping processes
are more significant than those of the mechanical processes.
Within the chemical pulping process, numerous sources of both gaseous
and particulate matter emissions occur. The gaseous emissions are princi-
pally hydrogen sulfide, methyl mercaptan, dimethyl sulfide, dimethyl di-
sulfide and sulfur dioxide. Because the process involves chemical diges-
tion, washing and stripping to produce the pulp and because the solutions
used within the industry are some form of sulfur, the emissions occur
throughout the process. They are all extremely odorous and are detectable
at concentrations as low as 1 part per billion (ppb). Figure 2.3 illus-
trates major emission points within the Kraft pulp mill and Table 2.5
reflects typical emission from those sources.
2.3.1 Components of Kraft Pulp Mill Odor
Hydrogen sulfide (H2S) is the most important of the four odorants.
Of the TRS (total reduced sulfur) emissions, it is the most common and the
most researched.
Hydrogen sulfide emissions originate from the breakdown of sodium sul-
fide, a component of the Kraft cooking liquor. Essentially, it is a weak
acidic gas which partially ionizes in the water-based Kraft cooking liquor.
The ionization occurs in two stages: (1) the forming of hydrosulfide; and
(2) with increasing pH, the sulfide ion forms, as indicated by the following
equation:
The black liquor in the Kraft pulping process contains a high con-
centration of dissolved sodium sulfide in a strongly alkaline solution.
If the pH were lowered, the sodium sulfide would hydrolyze to sodium hy-
drosulfide. Below pH 8, some unionized hydrogen sulfide would form as the
reaction equilibrium in the above equation moves from the right side to the
left side. At a pH of about 8.0, most hydrogen sulfide forms hydrosulfide
ions. As a result, in the Kraft pulping process, there is usually very
small amounts of hydrogen sulfide in the liquor. It is almost always pre-
sent in larger amount than the mercaptans or other sulfur compounds. When
H?S is present, other sulfur emissions may be, but if it is not present,
other sulfur emissions are unlikely.
2-15
-------
CHIPS
RELIEF
CH3SH, CH3SCH3, H2S
NONCONDENSABLES
ro
HEAT
EXCHANGER
CH3SH, CH3SCH3, H2S
NONCONDENSABLES
t
S02, S03 (FROM RECOVERY FURNACE)
H2S, CH3SH, CH3SCH3
AND HIGHER COMPOUNDS
TURPENTINE
CONTAMINATED WATER
STEAM. CONTAMINATED WATER
CONTAMINATED A H2S. AND CHoSH
-^ WATER ' L *
PULP 13% SOLIDS
SPENT AIR, CH3SCH3«-
AND CH3SSCH3
TOWER
TIC
R
1
IN
APORATOR
UJ
1
BLACK
LIQUOR
50% SOLIDS
DIRECT
CONTACT
EVAPORATOR jj"
JBLACK
WHITE
LIQUOR
Na2S
NaOli
UlQUOR70% SOLIDS*
^
SULFUR WAJER;
0,
RECOVERY
FURNACE
)XIDIZINC
ZONE
DEDUCTION
ZONE
GREEN
LIQUOR
, SMELTJ
Na2S+Na2C03
CAUSTICIZER
Figure 2.3. Major Emission Points Within The Kraft Pulp Mill
-------
TABLE 2.6
TYPICAL EMISSIONS CONCENTRATIONS FOR
SULFUR COMPOUNDS FROM KRAFT PULP MILLS
Emission Source
Recovery Furnace
No auxiliary fuel
Auxiliary fuel added
Smelter Dissolving Tank
Lime Kiln
Digester, brown stock
Washer, evaperation,
oxidation tower or
stripper system
Pollutants Concentration
ppm by Volume
Sulfur
Di oxi de
SO?
0-1200
0-1500
0-100
0-200
0-100
Hydrogen
Sulfide
H?S
0-1500
0-1500
0-75
0-250
0-1,000
Methyl
Mercaptan
CH^SH
0-200
0-200
0-2
0-100
0-10,000
Dimethyl
Sulfide
(CHsbS
0-100
0-100
0-4
0-50
100-45,000
Dimethyl
Disulfide
(CHsbS?
2-95
2-95
0-3
0-20
10-10,000
PO
I
-------
The hydrogen sulflde that does exist Is formed in the recovery fur-
nace and the lime kiln, as that is where the sulfur-containing compounds
from the black liquor or lime mud are volatilized and reduced.
Methyl mercaptan (CH3SH) is a reduced sulfur compound which is formed
during the Kraft cook by the reaction of hydrosulfide ion and the methoxy-
lignin component of the wood as illustrated in the following equation:
Lignin -OCH3 + HS~ ^ CHgSH + Lignin - (T
Methyl mercaptan will also breakdown in a water-based solution to
methyl mercaptan ion. It is reported that this dissociation is essentially
complete above a pH of 12.0. Methyl mercaptan is, therefore, present in
low concentrations as a dissolved gas in the black liquor. As the pH
decreases, additional CHsSH gas is evolved.
Methyl mercaptan is primarily emitted from the digester relief valve
during pressure release, and from the brown stock washers where the pH
of the liquor drops below the equilibrium point. Emissions decrease as
the residual concentration in the liquor diminishes.
Dimethyl Sulfide (0*3)2$ is primarily formed through the reaction of
mercaptide ion with the methoxy-lignin component of the wood:
Lignin - OCH3 + CH3S — * Lignin - 0~ + (CH3)2S
Dimethyl sulfide may also be formed by the disproportionate of
methyl mercaptan. At normal liquor temperature (150-200°F) it is highly
volatile. It does not, however, dissociate as hydrogen sulfide and methyl
mercaptan do.
Dimethyl di sulfide (Cf^gSg is formed by the oxidation of methyl mer-
captan throughout the recovery system, especially in the oxidation towers,
by the following equation:
4 CH3SH + 02 — ¥ 2 (CH3)2S2 + ?
Dimethyl di sulfide has a higher boiling point than any of the other
compounds and its retention in the liquor is therefore greater.
2.3.2 Effects
2.3.2.1 Human - The human effects of these compounds vary depending upon
concentration and depending upon the individual. While reactions to
these odors are fairly subjective, researchers agree that at sufficiently
high concentrations, the compounds are very toxic to humans.
For example, hydrogen sulfide acts as a cell and enzyme poison and
can cause irreversible changes on nerve tissue. It enters the body through
the respiratory tract, and then is transferred by the blood stream to
various body organs. When hydrogen sulfide enters the blood, it can lead
to a blockage of oxygen transfer, especially at higher concentrations.
2-18
-------
Some of the effects of hydrogen sulfide and the air concentrations
at which they occur are shown in Table 2.7.
TABLE 2.7
EFFECTS OF HYDROGEN SULFIDE INHALATION ON HUMANS
Hydrogen Sulfide
ug/m3 (ppm)
Effects
1-45 (7.2 x 10"4 - 3.2 x 10-2)
10 (7.2 x 10-3)
150 (0.10)
500 (0.40)
15,000 (10.0)
30,000 (20.0)
30,000-60,000 (20.0-40.0)
150,000 (110)
270,000-480,000 (200-350)
640,000-1,120,000 (460-810)
900,000 (650)
1,160,000-1,370,000 (840-990)
1,500,000+ (1100+)
Odor threshold. No reported
injury to health
Threshold of reflex effect on
eye sensitivity to light
Smell slightly perceptible
Smell definitely perceptible
Minimum concentration causing
eye irritation
Maximum allowable occupational
exposure for 8 hours (ACGIH
Tolerance Limit)
Strongly perceptible but not in-
tolerable smell. Minimum
concentration causing lung
irritation
Olfactory fatigue in 2-15 min-
utes; irritation of eyes and
respiratory tract after 1 hour;
death in 8 to 48 hrs.
No serious damage for 1 hour but
intense local irritation; eye
irritation in 6 to 8 minutes
Dangerous concentration after 30
minutes or less
Fatal in 30 minutes
Rapid unconsciousness, respiration
arrest, and death, possibly without
odor sensation
Immediate unconsciousness and rapid
death
2-19
-------
At concentrations over 1,120,000 yg/m3 there is practically no sensa-
tion of smell due to olfactory fatigue and death can occur quickly. Loss
of sense of smell has even been reported at concentrations of 150,000
yg/m3 after exposure time of 2 to 15 minutes.
Concentrations in and around Kraft paper mills are a lot less than
the figures mentioned above. While the Occupational Safety and Health
Administration (OSHA) has established a maximum allowable exposure concen-
tration for hydrogen sulfide of 30,000 yg/m3 and 15,000 yg/m3 for methyl
mercaptans, concentrations are usually a lot lower.
At lower concentrations human response to hydrogen sulfide varies
considerably among individuals depending upon the age and sex of the
individuals, the size of the town in which they live, and whether they
smoke. For example, the odor threshold of hydrogen sulfide varies between
1 and 45 vg/m3.
Concentrations of TRS as high as 30,000 yg/m3 (20 ppm) are not
likely to be realized near existing Kraft pulp mills. For example,
measurements of ambient hydrogen sulfide concentration were made during a
six-month period in 1961 and 1962 in the Lewiston, Idaho area where the
major contributor of gaseous pollutants was a pulp mill which had only
the recovery furnace controlled for TRS emissions. The levels of hydrogen
sulfide were generally less than 15yg/m3. During an air pollution epi-
sode in November 1961, peak 2-hour concentrations of 77 yg/m3 were measured.
These levels are well below the maximum allowable occupational exposure
concentration established by OSHA.
Some common physical complaints include: metallic taste, fatigue,
diarrhea, blurred vision, intense aching of the eyes, insomnia, and
vertigo. Emotional reactions to malodorous compounds such as hydrogen
sulfide have also been noted to produce physical responses: headache,
feelings of nausea, vomiting, decrease in appetite, impairing nutrition
and water intake, hampering proper breathing, offending the senses. Most
of all, malodors can upset good dispositions, provoke emotional disturbances,
mental depression and irritability.
2.3.2.2 Sociological - From a sociological standpoint, foul odors can
ruin personal and community pride, interfere with human relations in
various ways, discourage capital improvements, lower socioeconomic status,
and damage a community's reputation.
Communities are also affected physically. Some compounds, such as
hydrogen sulfide react with paints containing heavy metal salts to darken
or discolor a surface. Likewise, copper and silver tarnish quickly in the
presence of hydrogen sulfide.
2.3.2.3 Vegetation - Hydrogen sulfide emissions can also be harmful to
vegetation. Table 2.7 indicates the time until 50 percent injury to
various vegetation exposed to 1,500,000 yg/m3 of hydrogen sulfide. Though
injury occurs to vegetation at high concentrations, there is little
evidence to support this claim at lower levels. Experimentation revealed
that little or no injury occurred to 29 species of plants when they were
sprayed with less than 60,000 yg/m3 of hydrogen sulfide for five hours.
2-20
-------
After five hours at 600,000 yg/m3, some species were injured, but not
all. Boston fern, apple, cherry, peach and coleus showed appreciable
injury at concentrations of 600,000 vg/m3. At concentrations between
60,000 and 600,000 vg/m3, gladiolus, rose, castor bean, sunflower, and
buckwheat showed moderate injury. Tobacco, cucumber, sal via, and tomato
were slightly more sensitive.
In general, hydrogen sulfide injures the youngest plant leaves rather
than the middle-aged or older ones. Young, rapidly elongating tissues
are the most severely injured. Typical exterior symptoms are wilting
without typical discoloration (which starts at the tip of the leaf). The
scorching of the youngest leaves of the plant occurs first.
TABLE 2.8
TIME IN MINUTES UNTIL 50 PERCENT INJURY TO EXPOSED PLANT
SURFACES AT 1,500,000 vg/m3 HYDROGEN SULFIDE
Plant Surface
Leaves
Stems
Plant
Tomato
Buckwheat
Tobacco
Tomato
Buckwheat
Tobacco
Time in
Minutes
30
60
100
45
120
480
2.3.2.4 Economic - There are also economic repercussions. Malodorous
compounds can stifle growth and the development of a community. Both
industry and workers tend to locate in an area which is desirable to
live, work, recreate and the natural tendency is to avoid cities and
towns with obvious odor problems. Tourists also avoid such areas.
Communities with an odor problem often experience a decline in property
values, tax revenues, payrolls, and sales. This can be an economic
disaster to the community.
2-21
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2.4 LIMITING EMISSIONS
Movement towards doing something about the emission problems from
Kraft pulp mil Is began in the 1960's, when it was realized how harmful
these emissions can be and when it was realized that chemical pulp pro-
duction was going to double between 1970 and 1985, rising by about 35
million to 70 million tons annually. Most of this production is produced
by the Kraft process.
Residents of several communities, Eureka, California, among them,
began to organize to combat the problem. In 1967, at their 29th Annual
Meeting, the American Conference of Governmental Industrial Hygienists
(ACGIH), set the workplace threshold limit for.hydrogen sulfide in air
for an eight-hour-day, 40-hour week at 15,000^1 g/m3. The hydrogen sulfide
ambient air quality standards for various states and governments are shown
in Table 2.9.
TABLE 2.9
HYDROGEN SULFIDE AMBIENT AIR QUALITY STANDARDS
Maximum Single
Country or State Basic Standard Measurement
Avg. Time u9/m3
California
Missouri
Montana
New York
Pennsyl vania
Texas
Czechoslovokia
Canada (Ontario)
Poland
U.S.S.R
Federal Republic
of Germany
150
45
45
150
7.5
120
8
45
20
8
150
1 hr
30 min
30 min
1 hr
24 hr
30 min
24 hr
30 min
24 hr
24 hr
30 min
8
8
In 1970, the Clean Air Act required all states to prepare a
state implementation plan (SIP) that set forth how the State intended to
attain and maintain the National Ambient Air Quality Standards (NAAQS).
Each SIP must contain among other things the necessary legal authority
and emission limitations to ensure attainment and maintenance of the NAAQS.
The Clean Air Act of 1970 and the initial SIPs developed under that
Act placed primary emphasis on initial compliance of sources with a set
of specified emission limitations that reduced emissions sufficiently to
attain the NAAQS. Less attention and consideration were initially given
in the formulation of control strategies that would preserve or maintain
the air quality once attainment was achieved.
In addition, EPA has worked with state governments in establishing
specific TRS compliance deadlines. By June 1982, the digester and evapora-
tion tanks of Kraft pulp mills were controlled within EPA standards.
The established compliance deadlines were April, 1984, for lime kilns
and December, 1984 for recovery boilers.
2-22
-------
Control agencies have long recognized that initial compliance does
not necessarily mean future or continuing compliance. Faced with limited
resources, attainment dates mandated by legislation, emission limits set
by regulations, and already established source compliance dates, the
agencies understandably placed a greater emphasis on promoting initial
source compliance to ensure attainment of NAAQS. Now that most sources
have either demonstrated initial compliance or are in the midst of a
compliance-oriented program, considerable concern has been raised within
the air pollution control community with respect to whether a source is
operating and maintaining its control equipment. Some concern has also
been raised with respect to whether a source is complying with the appli-
cable emission limit on a continuous basis. In many cases, a source can
fine tune its control system and make the necessary adjustments to comply
with an emission limit during a stack test conducted to certify compliance
with the applicable emission limit. Once these tests have been completed,
however, the control system may begin to deteriorate and the source may
no longer be in compliance with the applicable emission limit.
Consequently, in the last few years, continuous emission monitors have
become more prevalent as a means of ensuring continuous compliance with
emission limitations established for stationary sources. Standards of per-
formance established by the EPA for new sources presently require the use of
continuous emission monitors (CEM) on many industrial sources. Other new
industrial sources will be required to install and operate CEMs when per-
formance specifications are promulgated by EPA. The application of
continuous emission monitoring on Kraft pulp mills is just one example
of EPA's efforts to ensure continuous compliance of regulated facilities.
2.5 SUMMARY
In summary, over 80% of wood pulp produced in the United States is
by the Kraft process, the major source of TRS emissions. Characteristic
emissions of the pulp industry coupled with its status as the 10th largest
industry in the U. S. has caused establishment of hydrogen sulfide ambient
air quality standards in many states and emission limitation on NSPS Kraft
pulp mills.
2-23
-------
3.0 REGULATIONS
3.1 THE CLEAN AIR ACT AND ITS AMENDMENTS
Regulatory authority associated with the enforcement of air quality
standards has its basis in the Clean Air Act and its amendments. More
importantly, the Clean Air Act Amendments of 1970 established the Environ-
mental Protection Agency, which was given the mandate to set and enforce
the regulations. It became the responsibility of EPA to "protect and
enhance the quality of the Nation's air resources so as to promote the
public health and welfare and the productive capacity of its population..."
In essence, EPA was mandated to protect the public health and welfare of
its citizens. To accomplish this, EPA established national ambient air
quality standards (NAAQS) for major air pollutants. The 1970 Amendments
established dates for attaining the*ambient standards. Section 110 of
the Act required all states to submit a State Implementation Plan (SIP)
describing the legislative and regulatory process by which the state was
going to attain and maintain NAAQS by the statutory date. The SIP would
be formulated by the state and approved by EPA. This created a cooperative
state - federal partnership as a means of implementing the Act. EPA sets
the standards while the states achieve and maintain those standards. In
contrast to the 1967 legislation, the new Act provided the framework for
enforcing its provisions. The Clean Air Act of 1963 was part of a series
of legislation passed by Congress to protect the environment. Those
major pieces of legislation are:
o 1963 - Clean Air Act (P.L. 88-207)
It was not until 1963 that meaningful legislation in air pollu-
tion occurred. The Clean Air Act of 1963 enabled the federal
government, at the request of the state, to conduct public hear-
ings on industrial polluters within that state and if necessary,
request federal court action.
o 1967 - Air Quality Act (P.L. No. 90-148)
The fundamental basis of the Air Duality Act of 1967, as amended
in 1970 and in 1977, was that major responsibility for control of
air pollution from stationary sources rested with state and local
programs. EPA may get in the picture only in the event that state
or local programs fail to enforce the legislation.
o 1969 - National Environmental Policy Act (P.L. No. 91-190)
The National Environmental Policy Act (NEPA) introduced the con-
cept of preconstruction review in the form of the Environmental
Impact Statement (EIS). The EIS required that the environmental
effects of an industrial project must be examined at the concep-
tion of the project.
3-1
-------
NEPA established a national policy for the environment, and was
followed by an explosion of federal enactments such as the Clean
Air Act Amendments of 1970 and the 1972 Amendments to the Federal
Water Pollution Control Act along with their associated regula-
tions including permit systems and preconstruction (or "new
source") review.
o 1970 - Clean Air Act Amendments (P.L. No. 91-704)
o 1977 - Clean Air Act Amendments (P.L. No. 95-95)
Present day enforcement activities are based on the 1977 Clean Air
Act Amendments. Those sections of the 1977 Act dealing with Federal
Enforcement actions are:
o Section 112: National Emission Standards for Hazardous Air
Pollutants (NESHAPS)
Section 112 of the Act requires the Administrator of EPA to
establish standards for air pollutants to which no ambient air
quality standard is applicable and which in the judgment of the
Administrator may cause, or contribute to "an increase in mor-
tality or an increase in serious irreversible, or incapacitating
reversible, illness." A NESHAP standard applies to any new or
modified source. In addition, existing sources are required to
comply with a NESHAP standard within ninety days after its
effective date.
o Section 113: SIP Violations
This section provides that whenever the EPA Administrator finds
that a violation of a SIP requirement is occurring, he shall noti-
fy the person who is .violating the plan and the state in which
the plan applies. If such violation extends beyond the thirtieth
day after notification, the Administrator may issue an order re-
quiring the violator to comply with the requirements of the SIP
or he may bring civil action in court for appropriate relief, in-
cluding a permanent or temporary injunction, and/or a civil pen-
alty or not more than $25,000 per day of violation.
Under the Clean Air Act of 1970, states were required as part of
their SIP, to establish a permit system for preconstruction review of
stationary sources. Guidelines were broad, with little or no specific
direction. In contrast, the 1977 Amendments set forth detailed review
requirements that must be performed prior to the issuance of the permit.
Basically, the following standards must be met:
o Section 111; New Source Performance Standards (NSPS)
Section 111 of the Act requires the Administrator to publish a
list of categories of stationary sources which may contribute
significantly to air pollution which causes or contributes to the
endangerment of public health or welfare. He must then propose
regulations establishing standards of performance for new sources
within each category. Enforcement of these standards can be
delegated to the states.
3-2
-------
o Section 160-169: Prevention of Significant Deterioration (PSD)
The basic PSD requirement as set out in Section 165 of the Act
provides that no major emitting facility (as defined in the Act)
for which construction is commenced after August 7, 1977, may be
constructed unless:
a. A permit has been issued setting forth emission limitation;
b. An air quality sampling analysis has been conducted;
c. Certain specified increments are not exceeded;
d. Best available control technology (BACT) is applied:
e. The requirements for protection of pristine areas (class 1)
have been met;
f. There has been an analysis of any air quality impacts
projected for the area as a result of growth associated with
the proposed facility; and
g. Monitoring will be conducted to determine the effect of the
facility's emissions on air quality.
The basic concept of PSD was that EPA, with assistance from the
state, should preserve those areas of the country with air quality cleaner
than that prescribed by the NAAQS. A source, if located in one of those
areas, would have to meet the permit review requirements as stated above.
One of the most interesting changes in the concept of PSD is that
it originally applied only in areas that were "cleaner" than the NAAQS.
However, the regulations now extend the PSD preconstruction review to any
"major emitting facility" no matter where that facility will be located.
The rationale behind the expansion is that a source located in a nonattain-
ment area might affect the air quality in a clean area.
o Section 171-178; Nonattainment Areas
The 1970 version of the Act set 1977 as the date by which all
areas had to meet the NAAQS. Many areas of the country, however,
failed to meet that date. Consequently, these nonattainment
areas force states to revise their SIPs to ensure attainment and
maintenance of the standards. EPA developed regulations on
emission "tradeoff" or "offset" as an interim policy. The interim
policy provides that major sources are subject to an air quality
analysis and if the allowable emissions from the proposed source
exceeds the NAAQS, approval may be granted only if the source
achieves lowest achievable emission rate (LAER), or complies with
State SIP or makes reasonable further progress (RFP) toward attain-
ment of the applicable NAAQS.
3.2 CONTINUOUS EMISSION MONITORING BASIS IN THE CLEAN AIR ACT
The Clean Air Act and its amendments is the nation's Federal Law de-
signed to protect the health and welfare of the nation's population. To
protect the health and welfare of the nation's population, the Act pro-
vided three basic programs regulating emissions from stationary sources:
o SIP requirements for new and existing sources as necessary to
attain and maintain the national ambient air quality standards,
including new source permitting requirements;
3-3
-------
Technology-based NSPS requirements for new sources; and
o NESHAPS requirements for new and existing sources of hazardous
air pollutants.
Table 3.1 lists the entities affected by the three different types of
regulatory schemes and the citations wherein the various emission limita-
tions and test procedures are given.
The Clean Air Act Amendments of 1970 and 1977 provide basic authority
for EPA's continuous emission monitoring requirements on affected
facilities. Basic provisions provide:
o Broad authority for developing regulations and carrying out
the provisions of the Act; and
o Require State Implementation Plans, approved by EPA, to include
CEM requirements on monitoring industrial source emissions as
part of their permit approval.
The Act is divided into three titles:
o Title I: Air Pollution Prevention and Control
Part A - Air Quality and Emission limitations;
Part B - Ozone Protection;
Part C - Prevention of Significant Deterioration of Air Quality;
Part D - Plan requirements for nonattainment areas
o Title II: Emission Standards For Moving Sources
Part A - Motor Vehicle Emission And Fuel Standards;
Part B - Aircraft Emission Standards;
o Title III: General
Each title is divided into individual sections. Title I of the Clean
Air Act Amendments of 1977 contains four sections which address applicability
of CEMs to monitor source emissions.
o Section 105 - Grants for support of air pollution planning and
control programs.
Section 105 provides for federal grants to develop and operate State
air pollution control programs. Such grants may be made "upon such terms
and conditions as the Administrator may find necessary to carry out the
purpose of this Section." [If the State did not implement CEMs as part of
its regulatory strategy, then the administrator may make implementation of
a CEM program a condition for receiving a grant.]
o Section 110 (a) (2)(F) - Implementation plans.
Section 110(a)(2)(F) authorizes SIP approval if a SIP provides
"... (ii) requirements for installation of equipment by owners or opera-
tors of stationary sources to monitor emissions from such sources:"
3-4
-------
TABLE 3.1
REGULATIONS UNDER THE CLEAN AIR ACT
Type of emission standard
Affected sources
Source of emission
limitations and
prescribed test
procedures
CO
en
Criteria Pollutant Standards -
Standard set for the pollutant;
applies to all sources of such
pollutant (based on size); standards
for emissions and source testing
vary among the states
New Source Performance Standards -
Standard set for the specific
process (based on size); applies
to all new processes of that type;
nationwide test standards apply;
existing sources are amendable to NSPS
if such sources are substantially
modified or rebuilt.
Hazardous Pollutant Standards -
Standard set for specific pollutant;
applies to all sources of such pollutant;
emission and test standards are nation-
wide in scope; no variation among state
and local jurisdictions.
All facilities which emit particulate
matter, sulfur oxides, nitrogen oxides,
hydrocarbons, carbon monoxide, and lead.
New facilities; fossil-fuel fired steam
generators, incinerators, portland
cement plants, nitric acid plants,
sulfuric acid plants, asphalt concrete
plants, petroleum refineries, storage
vessels for petroleum liquids, secondary
lead smelters, secondary brass and bronze
ingot production plants, iron and steel
plants, sewage treatment plants, primary
aluminum industry, primary copper, zinc,
and lead smelters, phosphate fertilizer
industry operations, coal preparation
plants, kraft pulp mills etc.
Existing facilities:
1) Any of the above which exist prior to
an NSPS but are subsequently modified.
2) Any of the above which emit a pollutant
limited by the NSPS other than particulate,
SOX, NOX, HC, and CO. The particular limi-
tation is set by the state and may be less
stringent than that applicable to new
facilities.
Specified facilities which emit asbestos,
beryllium, mercury, benzene.
State Implementation
Plans and local ordinance
(whichever are more
stringent).
Title 40, Code of Federal
Regulations, Part
60(40 CFR 60)
Title 40, Code of Federal
Regulations, Part 61
(40 CFR 61).
-------
IMPLEMENTATION PLANS
Sec. HO. (a) (l)t "Each State shall, after reasonable notice and
public hearings, adopt and submit to the Administrator, within nine months
after the promulgation of a national primary ambient air quality standard
(or any revision thereof} under section 109 for any air pollutant, a plan
which provides for implementation, maintenance, and enforcement of such
primary standard in each air quality control region (or portion thereof)
within such State. In addition, such State shall adopt and submit to the
Administrator (either as a part of a plan submitted under the preceding
sentence or separately) within nine months after the promulgation of a
national ambient air quality secondary standard (or revision thereof), a
plan which provides for implementation, maintenance, and enforcement of
such secondary standard in each air quality control region (or portion
thereof) within such State. Unless a separate public implementing such
secondary standard at the hearing required by the first sentence of this
paragraph."
"(2) The Administrator shall, within four months after the date
required for submission of a plan under paragraph (1), approve or disapprove
such plan for each portion thereof. The Administrator shall approve such
plan, or any portion thereof, if he determines that it was adopted after
reasonable notice and hearing and that —"
CEM REPORTING REQUIREMENTS
Section 110(a) (2) (F) also conditions SIP approval on inclusion of
provisions for "(iii) for periodic reports on the nature and amounts of
such emissions; (iv) that such reports shall be correlated by the State
Agency with any emission limitations or standards established pursuant to
this Act, which reports shall be available at reasonable times for public
inspection..."
Section 110(a) (2) (F) also provides (i) necessary assurances that
the State will have adequate personnel, funding, and authority to carry
out such implementation plan, (ii) requirements for installation of equip-
ment by owners or operators of stationary sources to monitor emissions from
such sources, (iii) for periodic reports on the nature and amounts of such
emissions/ (iv) that such reports shall be correlated by the State agency
with any emission limitations or standards established pursuant to this
Act, which reports shall be available at reasonable times for public inspec-
tion/ (v) for authority comparable to that in section 303, and adequate
contingency plans to implement such authority/ and (vi) requirements that
the State comply with the requirements respecting State boards under sec-
tion 128 f"
o Section 113 - Federal Enforcement
Section 113(d) (1) (C) provides that delayed compliance orders (DCO)
are to require "the emission monitoring and reporting authorized to be
required under §§ 110 (a) (2) (F) and 114 (a) (1) ..."
3-6
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Section 113(d)(l) also States: " A State (or, after thirty days
notice to the State, the Administrator) may issue to any stationary
source which is unable to comply with any requirement of an applicable
implementation plan an order which specifies a date for final compliance
with such requirement later than the date for attainment of any national
ambient air quality standard specified in such plan ..."
"(C) the order requires compliance with applicable interim requirements
as provided in paragraph (5) (B) (relating to sources converting to coal),
and paragraaphs (6) and (7) (relating to all sources receiving such orders)
and requires the emission monitoring and reporting by the source authorized
to be required under sections 110(a) (2) (F) and 114(a) (1):"
o Section 114 - Inspections, Monitoring and Entry
Section 114 (a) (1) provides that the Administrator may require for
the purpose of developing certain regulations, determining violations, or
"carrying out any provision of this Act," a source to "...(C) install,
use, and maintain such monitoring equipment or methods, (D) sample such
emissions (in accordance with such methods, at such locations, at such
intervals, and in such a manner as the Administrator shall prescribe),
and (E) provide such other information, as he may reasonably require..."
INSPECTION, MONITORING, AND ENTRY
Further, Sec. 114. "(a) For the purpose (i) of developing or assist-
ing in the development of any implementation plan under section 110 or
lll(d), any standard of performance under section 111, or any emission
standard under section 112 (ii) of detarming whether any person is in
violation of any such standard or any requirement of such a plan, or
(Hi) carrying out any provision of this Act (except a provision of title
II with respect to a manufacturer of new motor vehicles or new motor
vehicle engines) —"
(1) the Administrator may require any person who owns or operates
any emission source or who is subject to any requirement of this Act
(other than a manufacturer subject to the provisions of section 206 (c)
or 208 with respect to a provision of Title II to (A) establish and
maintain such records, (B) make such reports, (C) install, use, and
maintain such monitoring equipment or methods, (D) sample such emissions
(in accordance with such methods, at such locations, at such intervals,
and in such manner as the Administrator shall prescribe), and (E) provide
such other information, as he may reasonably require.
3.3 FEDERAL REGISTER AND CODE OF FEDERAL REGULATIONS
The Clean Air Act of 1970 was implemented by Congress to provide a
well-planned manner by which pollutant sources could be regulated.
Basically, two types of sources were addressed: stationary and mobile.
Congress intended to control both new and existing sources. The Clean
Air Act gave broad authority in implementing its provisions. In the
preceding section, we have addressed the authority given to EPA in
association with continuous emission monitoring requirements. The Act
is the foundation for this authority. Regulations passed by Congress are
recorded in two publications:
3-7
-------
o Federal Register, and
o Code of Federal Regulations.
The Federal Register (FR) is published daily by the U.S. Congress.
It provides information associated with the business of the Congress pro-
posed and promulgated regulations, amendments to previously promulgated
regulations, and other announcements associated with all government
agencies.
Those entries into the Federal Register which address continuous
emission monitoring and its application to industrial sources and Kraft
pulp mills in particular are outlined in Table 3.2.
TABLE 3.2
FEDERAL RERISTER ENTRIES APPLICABLE TO
CONTINUOUS EMISSION MONITORING
Dec. 23, 1971 36 FR 24877
March 8, 1974 39 FR 9320
Oct. 6, 1975
40 FR 46240
The U.S. Environmental Protection
Agency published regulations affect-
ing selective facilities requiring per-
formance testing, stack gas monitoring, •
record keeping and reporting requirements.
Those affected facilities were fossil-
fuel fired steam generators, Portland
cement plants, nitric acid plants,
sulfuric acid plants and incinerators.
As part of this regulation, Reference
Methods 1 through 8 were promulgated,
as Appendix A.
Federal Reference Method 11 - Determin-
ation of Hydrogen Sulfide Emissions
from Stationary Sources - was promulgated
as a Reference Method. The method
involves extracting a sample into a
series of impingers containing cadmium
hydroxide (Cd(OH)2). Cadmium sulfide
participates out and is titrated with
iodine to an equivalent end point.
Simultaneous rulemaking addressing
enforceable procedures requiring new
and existing sources to monitor emissions
on a continuous basis.
o Part 51 - Requirements for the
preparation, adoption
and submittal of implemen-
tation plans
o Appendix P - Minimum
emission requirements
3-8
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TABLE 3.2 (contd.)
FEDERAL REGISTER ENTRIES APPLICABLE TO
CONTINUOUS EMISSION MONITORING
Sept. 24, 1976
May 23, 1977
41 FR 42012
42 FR 26205
Aug. 18, 1977 42 FR 41754
Jan. 10, 1978 43 FR 1495
Feb. 23, 1978 43 FR 7568
o Part 60 - Standards of Performance for
New Stationary Sources ...
o Appendix B - Performance
Specification
Proposed standards of performance for new,
modified and reconstructed Kraft pulp mill.
Use of methods other than Reference
Method 9 to he used as a means of
measuring plume opacity.
Published in the Federal Register were
revisions relating to the Reference
Methods. Those of interest are:
RM 1: Sampling and Velocity Traverses for
Stationary Sources;
RM 2: Determination of Stack Gas
Velocity and Volumetric Flow Rate
(Type S Pi tot Tube)
RM 3: Gas analysis for Carbon Dioxide,
Oxygen, Excess Air, and Dry
Molecular Weight;
RM 4: Determination of Moisture Content
in Stack Gases
RM 6: Determination of Sulfur Dioxide
Emissions from Stationary Sources.
On Jan. 10, 1978, revision to Federal
Reference Method 11 were incorporated
into the Federal Register. EPA found
that interferences resulting from the
presence of mercaptans in some refinery
fuel gases could lead to erroneous test
data. The revision involved a new
absorbing solution was incorporated
into the Reference Method.
Standards of Performance for new modified
and reconstructed Kraft pulp mills.
3-9
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TABLE 3.2 (contd.)
FEDERAL REGISTER ENTRIES APPLICABLE TO
CONTINUOUS EMISSION MONITORING
Aug. 7, 1978
43 FR 34784
Jan. 12, 1979 44 FR 1578
Aug.8, 1979
44 FR 46481
Oct. 10, 1979 44 FR 58602
Federal Reference Methods added
o Method 16 - Semi continuous determina-
tion of sulfur emissions from stationary
sources
o Method 17 - Determination of par-
ticulate emissions from stationary
sources (In-stack filtration method)
This action amends the standard of
performance for Kraft pulp mills by adding
a provision of determining compliance
of attended facilities which use a
control system incorporating a process
other than combustion.
o D£ correction to untreated emission
points of total reduce sulfur in
cases of brown stock washers, black
liquor oxidation systems or digestor
systems.
This action amends FRM 16 for determin-
ing total reduced sulfur emissions from
stationary sources. The admendment
corrects several typographical errors
and improves the Reference Method by
requiring the use of a scrubber to
prevent possible interference from high
concentrations of
Advance notice of proposed rulemaking
(ANPR) directing revisions of Part 51
involving state requirements on affected
facilities to monitor emissions on a
continual basis.
Proposed revisions to Performance Speci-
fication Test 1, 2 and 3.
3-10
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TABLE 3.2 (contd.)
FEDERAL REGISTER ENTRIES APPLICABLE TO
CONTINUOUS EMISSION MONITORING
June 18, 1981 46 FR 31904
July 20, 1981 46 FR 37287
March 30, 1983 48 FR 13322
May 25, 1983
48 FR 23608
July 20, 1983 48 FR 32984
Sept. 30, 1983 48 FR 45034
March 14, 1984 49 FR 9676
Aug. 17, 1984 49 FR 32987
Proposed test method for determining
total reduced sulfur (TRS) from Kraft
pulp mills.
o Method 16A: Determination of total
reduced sulfur emissions from
stationary source (Impinger Technique).
Proposed Performance Specification 5
(PS5) for continuous emission monitoring
of total reduced sulfur (TRS) emissions
from Kraft pulp mills.
Promulgation of revisions to Performance
Specification Test 1, specification and
test procedures for opacity continuous
emission monitoring systems in stationary
sources.
Promulgation of revisions to the per-
formance specifications for continuous
emission monitoring systems (CEM's)
for sources subject to Performance
Specification 2 and 3.
Promulgation of Performance Specifica-
tion 5 - Specifications and Test Proced-
ures for TRS Continuous Emission Monitor-
ing Systems in Stationary Sources.
On September 30, 1983, revision to
Federal Reference Method 1 were published
in the Federal Register. The revisions
addressed reduction in number of sampling
points required for sampling and velocity
traverses from stationary sources without
affecting accuracy.
Proposed Appendix F, Procedure 1 adding
quality assurance requirements to gas
continuous emission monitoring systems
(CEMs) when the CEMs are used as the
method for showing compliance with
emission limits on a continuous basis.
The purpose of this action is to propose
amendments to 60.284 of Subpart BB of
40 CFR Part 60 to allow the monitoring
and use of C02 to correct the measured
total reduced sulfur (TRS) concentration
emitted from Kraft pulp mill recovery
furnaces.
3-11
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TABLE 3.2 (contd.)
FEDERAL REGISTER ENTRIES APPLICABLE TO
CONTINUOUS EMISSION MONITORING
Feb. 14, 1985 50 FR 6316 Amendment and Innovative technology
waiver for New Source Performance
Standards for Kraft pulp mills.
March 8, 1985 50 FR 9578 Promulgated Federal Reference Method 16A
as an alternative to Federal Reference
Method 16.
3-12
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3.4 FEDERAL REGISTER, OCTOBER 6, 1975
On October 6, 1975, the U. S. Environmental Protection Agency (EPA)
adopted requirements for the continuous emission monitoring of certain
new and existing sources. The requirements for existing sources were
adopted under 40 CFR Part 51, Requirements for the Preparation, Adoption
and Submittal of Implementation Plans. The requirements for new sources
were adopted under 40 CFR Part 60, Standards of Performance for New
Stationary Sources. These regulations appeared in the Federal Register
as 40 FR 46256, October 6, 1975. The continuous monitoring requirements
adopted by EPA are minimum requirements. State and local agencies may,
at their discretion, adopt more comprehensive or stringent requirements.
Figure 3.1 illustrates the connection between existing sources and
new sources as outlined in 40 FR 46256, October 6, 1975.
40 FR 46240
Oct. 6. 1975
Requirement! for Subraiitml of Implementation
Plans—Standards for New Stationary Sources
JL
Part 51
(page 46240)
for (he Preparation. Adoption
Submittal of Implementation Plant
(Eaumon Monitoring of Stationary Sources)
(Preamble—~
(I
Quarla)
A. Discussion of proposed revisions
B. General discussion of contents to revisions
C. Rationale for emission monitoring
regulations
D. Discussion of major comments
£• Modifications made to the proposed
regulations
F. Summary of revision* mad clarification* to
the proposed
G. Requirements
of States
Procedures
(page 46247)
Appendix P
UDUm ODBBQ
igumxDcnu
(page 46247)
_L
Pan 60
(page 46250)
Standard* of Performance for New Stationary
Sources (Emission Monitoring Requirements and
Revisions to Performance Testing Methods)
(Preamble—John ftuarles)
A. Background
B. Significant comments and changes made to
proposed regulations
(1) on Subpart A—General Provision*
(2) on Subpart D-Fossil-fud-fired Steam
Generators
(3) on Subpart C—Nitric Acid Plants
(4) on Subnan H-Sulfiuk And Plant*
(5) on Appendix B-Performance
Specifications
Subpans
additions)
(page 46254)
Appendix B
Performance
specifications (added)
46289)
Figure 3.1. Federal Register, October 6, 1975
3-13
-------
The date of construction and the date of promulgation of a regulation
will determine whether a Kraft pulp mill is classified as a "new" source
or an "existing" source. Once again, "new" sources are regulated under 40
CFR Part 60, while "existing" sources are regulated under 40 CFR Part 51.
These sources covered under 40 CFR Part 60 and termed NSPS sources, while
those covered under 40 CFR Part 51 are termed SIP sources.
The SIP regulations require that specific categories of industrial
sources shall Install continuous monitoring systems to monitor emissions
of sulfur dioxide, oxides of nitrogen and opacity. In certain cases, it
1s also required to monitor carbon dioxide or oxygen so that the output
from the S02 and NOX monitors can be converted to units of the standard.
The regulations include requirements for design and performance specifi-
cations, procedures for conducting performance evaluations, and require-
ments for record keeping.
Even though the original regulations for SIP sources did not address
Kraft pulp mills, many states, as part of their own SIP program, require
continuous TRS emission monitoring. Regulations under 40 CFR 51 are mini-
mum monitoring requirements. The state requirements can be more strict
than Part 51.
Of the 175 pulp mills located within the United States, as outlined
in Table 2.2, greater than 90% are regulated by Part 51, thus classified
as SIP sources. However, not all states have regulations addressing
Kraft pulp mill emissions. Table 3.3 lists those states with existing
regulations addressing Kraft pulp mill emissions.
3-14
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TABLE 3.3
EXISTING STATE REGULATIONS
ADDRESSING PULP MILLS
State
Alabama
Alaska
Arizona
California
Colorado
Florida
Georgia
Hawaii
Total Reduced Sulfur (TRS) Emissions
General Pulp Mill
20 Ibs/TADP per
24 hours of S02
emissions
Lime Kiln
40 ppm as H2S
on a dry basis
corrected to
10% 02 as a
24-hr avg.
8 ppm as TRS
on a dry basis
corrected to
10% 02 as a
24-hr avg.
40 ppm as TRS
on a dry basis
corrected to
10% 02 as a
24-hr avg.
Recovery Furnace
1.2 Ibs (as hydrogen sulfide)
on a dry basis/ton air dry pulp
(Daily avg/quarter)
20 ppm as H2S on a dry basis
corrected to 8% 02
Straight - 5 ppm by volume on
a dry basis,
corrected to 8% 02
Cross - 25 ppm by volume on
a dry basis, cor-
rected to 8% 02
New Plant - 1 ppm as H2S on a
dry basis
Existing Plant - 17.5 ppm as
H2$ on a dry
basis
Old - 20 ppm of TRS on a dry
basis corrected to 8% 02
(before Sept. 24, 1976) on
24-hr avg.
New - 5 ppm of TRS on a dry
basis corrected to 8% 02
(After Sept. 24, 1976) on
24-hr avg.
Cross - 25 ppm of TRS on a dry
basis corrected to 8% 0?
Smelt Tank
0.0084 g/kg
Black liquor
solids
0.0168 Ibs/ton
Black liquor
solids
Digester
and Stripper
5 ppm by volume
on a dry basis,
corrected to
10% 02
5 ppm by volume on
a dry basis, cor-
rected to 10% 02
CA>
-------
TABLE 3.3 (Continued)
EXISTING STATE REGULATIONS
ADDRESSING PULP MILLS
State
Total Reduced Sulfur (TRS) Emissions
General Pulp Mill
Lime Kiln
Recovery Furnace
Smelt Tank
Digester
and Stripper
Idaho
40 ppm or 0.2
Ibs of sulfur/
ton ADP
^ Kentucky
8 ppm
corrected
to 10% 02
Louisiana
20 ppm cor-
rected to
8% 02
General Provisions
0.5 Ibs of sulfur/ton ADP or
17.5 ppm as H2S on dry basis
for average daily emission.
2.0 Ibs of sulfur/ton ADP or
70 ppm as H2$ on Dry basis
for average daily emission
New Sources
5 ppm as a daily arithmetic
average or 0.12 Ibs of sulfur/
ton ADP on a daily average
40 ppm for any sixty (60)
consecutive minutes
Existing
15 ppm as an arith-
metic average over
any consecutive
24-hr period
40 ppm for more
than 60 total min-
utes in any 24-hr
period
New
0.0084 g/kg
Black liquor
solids
5 ppm corrected
to 8% 02
Straight
5 ppm corrected to
8% 02
Cross
25 ppm corrected to
8% 02
New
Straight-New design 5 ppm
corrected to 8% 02
Straight-Old design 20 ppm
corrected to 8% 02
Cross Recovery
25 pp-"rected to 8% 02
0.0084 g/kg
Black liquor
solids
5 ppm corrected
to 10% 02
-------
TABLE 3.3 (Continued)
EXISTING STATE REGULATIONS
ADDRESSING PULP MILLS
State
Maryland
Montana
New Hampshire
New Mexico
New York
North Carolina
Oregon
South Carolina
Total Reduced Sulfur (TRS) Emissions
General Pulp Mill
0.6 Ibs/ton of
oven-dired un-
bleached Kraft
pulp
0.2 Ibs/ton ADP
Lime Kiln
20 ppm
20 ppm
8.0 ppm cor-
rected to
10% 02
20.0 ppm
corrected to
10% 02
Recovery Furnace
0.087 pounds/1000 pounds
of black liquor or 1.75
ppm as H2$ on a dry basis
2 Ibs/ton ADP
0.1 Ibs of sulfur as
H2S/tons ADP
Old Design - 20 ppm
New Design - 5 ppm
Cross - 25 ppm
Old Design - 20 ppm
New Design - 5 ppm
Cross - 25 ppm
Straight - 5 ppm
corrected to 8% 03
Cross - 25 ppm cor-
rected to 8% 02
Cross - 25 ppm avg. corrected
to 8% 02 over 12 hr
Old Design - 20 ppm
average corrected to
8% 02 over 12 hr
New Design - 5 ppm
average corrected to
8% 02 over 12 hr
Smelt Tank
0.087 lb/1000 Ib
Black liquor
solids
0.0168 Ibs/ton
black liquor
solids
0.0168 Ibs/ton
black liquor
solids
0.0168 Ibs/ton
black liquor
solids
0.0084 g/kg
Black liquor
solids
Digester
and Stripper
5 ppm corrected
to 10% 02
5 ppm corrected
to 10% 02
5.0 ppm by
volume on a dry
basis, corrected
to actual 02
content of
untreated gas
stream
5.0 ppm
CO
-------
TABLE 3.3 (Continued)
EXISTING STATE REGULATIONS
ADDRESSING PULP MILLS
State
Tennessee
Virginia
Washington
Wisconsin
Total Reduced Sulfur (TRS) Emissions
General Pulp Mill
1.2 Ibs of total
reduced sulfur
as H2$/ton air
dryed pulp (daily
average/quarter)
Lime Kiln
40.0 ppm
corrected
to 10% 02
8 ppm as H2$
for more than
2 consecutive
hours /day
50 ppm as TRS
for avg. daily
emission
20 ppm as TRS
for avg. daily
emission cor-
rected to 10%
02 after
Jan. 1, 1985
8 ppm as TRS
by volume on
a dry basis,
corrected to
10% 02
Recovery Furnace
20 ppm by volume, expressed as
H2$ on a dry basis, corrected
to 8% 02 on a 24-hr avg. basis
Old - 17.5 corrected to 8% 02
on a daily average (before
Jan. 1, 1970)
New - 5.0 ppm corrected to 8%
02 on a daily avg. (after Jan. 1
1970)
Straight - 5 ppm by volume on a
dry basis, corrected to 8% 02
Cross - 25 ppm by volume on a
dry basis, corrected to 8% 02
Smelt Tank
0.0084 g/kg
black liquor
solids
0.0084 g/kg
black liquor
solids
Digester
and Stripper
5.0 ppm by volume
on a dry basis,
corrected to
10% 02
5 ppm by volume
on a dry basis,
corrected to
10% 02
00
-------
Table 3.3 demonstrates the wide variation in regulations imposed on
pulp mills regulated under Part 51 of the regulations. Some mills are
subject to emission limits of total reduced sulfur (TRS), while others are
limited as to sulfur dioxide (SOg) emissions. Still others are limited
by ambient air standards around the regulated facility.
Presently, there are twenty-six (26) Kraft pulp mills within the United
States that fall under New Source Performance Standards. This represents
approximately 20% of the Kraft pulp mill population. Table 3.4 lists those
mills currently affected by the NSPS regulations.
TABLE 3.4
KRAFT PULP MILLS
AFFECTED BY NSPS REGULATIONS
Company
Location
Sources Covered
Under NSPS
Stone Container
Buckeye Cellulose
Port Wentworth,
Georgia
Oglethorpe, Georgia
Western Kraft
Stone Container
International Paper
Hawesville, Ky.
Hodge, Louisiana
Mansfield, Louisiana
Boise Cascade
Rumford, Maine
Champion International Missoula, Montana
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Recovery Furnace
Smelt Dissolving Tank
Lime Calciner
Digerster
Multiple-Effect Evaporators
Brown Stock Washer System
Condensate Stripping System
Lime Kiln
Brown Stock Washer System
Multiple-Effect Evaporators
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Digesters
Multiple-Effect Evaporators
Brown Stock Washer System
Recovery Furnace
Smelt Dissolving Tank
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Digester
Multiple-Effect Evaporators
3-19
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TABLE 3.4 (Continued)
KRAFT PULP MILLS
AFFECTED BY NSPS REGULATIONS
Company
Location
Sources Covered
Under NSPS
Federal Paperboard
Boise Cascade
International Paper
Riegelwood,
North Carolina
St. Helens, Oregon
Gardiner, Oregon
International Paper
Tennessee River
Georgetown, S.C.
Counce, Tennessee
Champion International Courtland, Alabama
Container Corporation Brewton, Alabama
Hammer-mi 11 Paper Selma, Alabama
Nekoosa Paper
Ashdown, Arkansas
Digesters
Multiple-Effect Evaporators
Lime Kiln
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Digester
Multiple-Effect Evaporators
Condensate Stripper System
Brown Stock Washer Systems
Lime Kiln
Recovery Furnace
Smelt Dissolving Tank
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Digester
Black Liquor Oxidation System
Multiple-Effect Evaporators
Brown Stock Washer System
Digesters (2)
Digesters
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Multiple-Effect Evaporators
Digesters
Brown Stock Washer System
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Black Liquor Oxidation System
Digesters
Multiple-Effect Evaporators
Brown Stock Washer System
3-20
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TABLE 3.4 (Continued)
KRAFT PULP MILLS
AFFECTED BY NSPS REGULATIONS
Company
Location
Sources Covered
Under NSPS
Georgia-Paci fic
Simpson Paper
Buckeye Cellulose
Container Corporation
Georgia Kraft
Stone Container
Crown Zellerbach
Crossett, ARkansas
Anderson, California
Perry, Florida
Fernandina Beach,
Rome, Georgia
Hopewel 1, Virginia
Camas, Washington
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Multiple-Effect Evaporators
Lime Kiln
Lime Calciner
Cross Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Recovery Furnace
Smelt Dissolving Tank
Lime Kiln
Sources covered under NSPS Regulations, like the SIP regulations,
have specific monitoring and reporting requirements associated with
particulate and total reduced sulfur emissions. A thorough understanding
of both of these regulations is important in any environmental agency.
3.4.1 Existing Source Regulations (40 CFR 51)
The requirements for existing sources to install continuous monitor-
ing systems were designed to partially implement the requirements of
Sections 110 (a) (2) (F) (ii) and (iii) of the Clean Air Act, which
state that implementation plans must provide "requirements for installa-
tion of equipment by owners or operators of stationary sources to monitor
emissions from such sources", and "for periodic reports on the nature and
amounts of such emissions". However, the original implementation plan
requirements did not require SIP's to contain legally enforceable pro-
cedures mandating continuous emission monitoring and recording. At the
time the original requirements were published, EPA had accumulated little
data on the availability and reliability of continuous monitoring
devices. The Agency believed that the state-of-the-art was such that it
was not prudent to require existing sources to install such devices.
3-21
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Since that time, much work has been done by EPA and others to field
test and compare various continuous emission monitors. As a result of
this work, the Agency now believes that for certain sources, performance
specifications for accuracy, reliability and durability can be establish-
ed for continuous emission monitors of oxygen, carbon dioxide, sulfur
dioxide, and oxides of nitrogen and for the continuous measurement of
opacity. Accordingly EPA adopted the requirements now contained at 40
CFR 51.19(e) which requires states to revise their implementation plans
to include legally enforceable procedures to require certain stationary
sources to install, calibrate, maintain, and operate equipment for con-
tinuously monitoring and recording emissions. The specific stationary
sources and pollutants to be monitored are identified in 40 CFR 51,
Appendix P - Minimum Emission Monitoring Requirements. The specific
source categories covered by the requirements are:
1. Fossil Fuel Fired Steam Generators
2. Fluid Bed Catalytic Cracking Unit Catalyst Regenerators
3. Sulfuric Acid Plants
4. Nitric Acid Plants
5. Portland Cement Plants
Appendix P outlines the specifics of the applicability of the contin-
uous monitoring regulations regarding size (throughput) limitations for
the affected facilities, the pollutants that must be monitored, exemptions,
performance specifications and evaluation procedures , data reduction and
maintenance requirements, and special considerations regarding alternative
procedures. As indicated in Table 3.5, many states have expanded the ini-
tial five (5) source categories to include Kraft pulp mills. Consequently,
the following specific regulation will apply to most existing Kraft pulp
mills.
Section 51.19(e) requires that SIPs include "(1) equally enforceable
procedures to require stationary sources subject to emissions standards..
to install, calibrate, maintain and operate equipment for continuously
monitoring and recording emissions...".
3-22
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Section 51.19(e) (3) and (4) require
of files on "emissions measurements..
performance evaluations, calibration
tenance..." and that the information
Appendix P.
that SIPs also require maintenance
.performance testing measurements,
checks, and adjustments and main-
be submitted to EPA as required in
.„— pUn shall provide for moni-
toring the status of compliance with any
rules and regulations which set forth
any portion of the control strategy. Spe-
cifically, each plan shall, as a n**"*"""1".
provide for:
(e) Legally enforceable procedures to
require stationary sources subject to
emission standards as part of an appli-
cable plan to install, calibrate, maintain.
and operate equipment for continuously
monitoring and recording emissions; and
to provide other information as specified
In Appendix P of this part.
(1) Such procedures shall identify the
types of sources, by source category and
capacity, that must install such Instru-
ments, and shall identify for each source
category the pollutants which must be
monitored.
'2) Such, procedures-shall, as a mini-
mum, require the types of sources set
forth in Appendix P-of this part (as such
appendix may be amended trom time to
time) to meet the applicable require-
ments set forth therein.
(3) Such procedures shall contain pro-'
visions which require the owner or oo-
eracor of each source suoject to continu-
ous emission monitoring and recording
requirements to maintain a file of all
pertinent Information. Such information
shall include emission measurements.
continuous monitoring system perform-
ance testing measurements, performance
evaluations, calibration checks, and ad-
justments and maintenance performed
on such monitoring systems and other re-
ports and records required by Appendix
P of this Part for at least two yean fol-
lowing the date of such measurements or .
Installation
<4> Such procedures shall require the
source owner or operator to submit In-
formation relating to emissions and
operation of the emission monitors to the
State to the extent described In Appendix
P as frequently or more frequently as
described therein.
<5> .Such procedures shall provide that
sources subject to the requirements of
!51.19 of this section shall have
Installed all necessary equipment and
shall have begun monitoring and record-
ing within 18 months of (1) the approval
ot a State plan requiring monitoring for
that source or (2) promulgation by the
Agency of monitoring requirements for
that source. However, sources that have
made good faith efforts to purchase, in-
stall. and begin the monitoring and re-
cording of emission data but who have
been unable to complete such Installa-
tion within the time period provided may
be given reasonable extensions of time as
deemed appropriate by the State.
( 6 ) States shall submit revisions to the
applicable plan which implement the
provisions of this section by October 6.
1976.
(40 FR 46240. October 6. 1975 |
Record-
keeping
t Reporting
3-23
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Appendix P of 40 CFR Part 51 sets forth the minimum requirements
for continuous emission monitoring and reporting that each State
Implementation Plans must include. At a minimum, these requirements
include:
o Source categories to be affected - emission monitoring,
recording and reporting requirements;
o Performance Specifications - addressing accuracy, reli-
ability and durability of acceptable continuous emissio
monitoring systems;
on
o Units of the Standard - Techniques to convert emission data
to units of the applicable State Emission Standard.
Section 1.0 of Appendix P of 40 CFR 51 states that CEM data may be used
for: "Such data may be used directly or undirectly for compliance deter-
mination or any other purpose deemed appropriate by the State. Though
the monitoring requirements are specified in detail, States are given
some flexibility to resolve difficulties that may arise during the imple-
mentation of these regulations".
More importantly, Section 3.1 of Appendix P of 40 CFR 51 referenced the
performance specifications test which must be used to determine accept-
ability of the installed continuous emission monitoring equipment as
required on affected facilities outlined in Section 1.1.1.
3.1 Performance specifications. "
The performance specifications MS forth
in Appendix B of Part 60 ±re incorporated
herein by reference, and shall be used by
Sum to determine acceptability of mon-
itoring equipment installed pursuant to
Ibis Appendix except that (1) where refer-
ence is made to the "Administrator* in
Appendix B. Pan 60. the term "State"
•hould be inserted for the purpose of this
Appendix (e.g., in Performance Speofica-
tion 1.1.2."... monitoring systems subject
to approval by the Administrator, "should
be interpreted as,"... monitoring systems
subject to approval by the Stait"). and (2)
where reference is made to the "Reference
Method" in Appendix B. Pan 60, the State
may allow the use of either the State
approved reference method or the Fed*
erally approved reference method as pub*
lished in Pan 60 of this Chapter. "The
Performance Specifications to be used with
each type of monitoring system are listed
below
Performance
Specifications
3.1.1 Continuous monikoniig systems
for measuring opacity shall comply with
Performance Specification 1.
3.1.2 Continuous monitoring systems
for measuring nitrogen oxides shall com-
ply with Performance Specification 1
3.1.3 Continuous monitoring systems
for measuring sulfur dioxide shall comply
with Performance Specification 2.
3.1.4 Continuous monitoring systems
for measuring oxygen shall comply with
Performance Specification 3.
3.1.5 Continuous monitoring systems
for measuring carbon dioxide shall comply
whh Performance Specification 3.
3-24
-------
Finally, within Section 4.0 of Appendix P of 40 CFR 51, minimum data
requirements are established. Addressed in this section are data
acquisiton and storage requirements, reporting requirements of excess
emissions and data reduction procedures.
4 0 Minimum data requirement! "N
The following paragraphs set forth the
minimum data reporting requirements neces-
sary to comply with ISi.l9(ei (3) and (4)
4 1 The State plan shall require owne:
or operators of facilities required to Install
continuous monitoring systems to submit a
written report of excess emissions for each
calendar quarter and the nature and cause of
the excrss rmisxlons If known The averaging
period used for data reporting should be
established bv the State to correspond to the
averaging period specified in the emission
test method used to determine compliance
will) an emission standard for the pollutant
source ratccorv in question The required re-
port shall include as a minimum the data
stipulated m this Appendix
4 2 For opacltv measurements the sum-
marc.Ehall consist of the magnitude In actual
percent opacity of all one-minute (or such
other time period deemed appropriate bv the
State i averages of opacity greater than the
opacity standard In the applicable plan for
each hour of operation of the facility Aver-
age values mav be obtained by Integration
oxer the averaging period or by arithmeti-
cally averaging a minimum of four equallv
spaced Instantaneous opacity measurements
per minute Anv time period exempted shall
be considered before determining the excess
averages of opacttv (e g. whenever a regu-
lation allows two minutes of opacity meas-
urements in excess of the standard, tbe State
shall requite the source to report all opaaitv
averages in any one hour In excess of the
standard minus the two-minute exemp-
tion i If more than one opacity standard
applies excess emissions data must be sub-
mitted In relation to all such standards
4 3 For gaseous measurements the sum-
mary shall consist of emission averages. In
the units of the applicable standard for each
averaging period during which the appli-
cable standard was exceeded
44 The date and time Identifying each
period during which the continuous moni-
toring svstem was Inoperative, except Tor
rero and span checks and the nature of
system repairs or adjustments shall be re-
ported The State may require proof of con-
tinuous monitoring system performance
whenever system repaint or adjustments have
been made.
46 When no excess emissions have oc-
curred and the continuous monitoring eya-
tem have not been inoperative, repaired.
or adjusted, such information snail be In-
cluded in tbe report.
Reporting
Requirements
4.6 The State plan shall require
operators of affected faclUUee to
a nle of all Information reported in tne quar-
terly summaries, and all other data collected
either by the continuous monitoring •Ttteai
or as necessary to convert monitoring data
to the units of the applicable standard lor
a minimum of two years from tbe date at
collection of auch data or submission of
such summaries.
3-25
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The SIP should provide for quarterly reporting by source operators
of excess emissions. The reports must contain data regarding excess emis-
sions and periods when the continuous monitoring equipment was inoperative
(40 CFR 51, Appendix P, Paragraph 4). If neither situation occured during
the quarter, a report documenting the absence of these events must still
be filed.
The reports should identify, where applicable, the cause of excess
emissions, the dates, times, and magnitude of such emissions and the
dates and times when the continuous monitoring system was inoperative
and the nature of repairs and adjustments. Excess emissions for gaseous
pollutants should be reported in units of the standard; the averaging
time should be required to be consistent with the averaging period speci-
fied in the emission test method used to determine compliance with the
applicable SIP emission limitation.
Data reduction procedures are essentially the same as required for
new sources under 40 CFR 60. However, the units of the SIP emission
limitations may he different than those for sources subject to NSPS,
thus requiring some alteration of certain data reduction procedures.
In Appendix P, Paragraph 6.0, EPA has recognized the difficulty in
setting uniform requirements for continuous monitoring systems at existing
facilities and has allowed the SIPs to include flexible requirements that
will not impede the development of new technology and will provide the
minimum installation and operating costs. Alternative monitoring require-
ments may be adopted on a case basis. Specific problems that may be en-
countered at a given facility may include (1) condensed water vapor in the
stack, (ii) infrequent operation of the facility, (iii) extreme economic
burden, and (iv) physical limitations at the facility.
3.4.2 New Source Performance Standard Regulations (40 CFR 60)
Concurrent with the promulgation of Part 51 dealing with existing
sources, EPA promulgated Part 60 - Standards of Performance for New
Stationary Sources. The New Source Performance Standards (NSPS) apply
to new, modified and reconstructed stationary sources of air pollution.
The source categories affected by these standards are those which
have been identified by the EPA as emitting one or more pollutants in
quantities significant enough to endanger the public health or welfare.
Under NSPS these categories must either (1) achieve the degree of emission
limitation or percentage reduction, or (2) apply a design, equipment,
work practice, operational standard, or combination which reflects the
best available technological system of continuous emission reduction
(considering cost and non-air quality impacts). Examples of control
methods currently in use under the New Source Performance Standards are:
o Control equipment (e.g., electrostatic precipitators,
fabric filters, wet scrubbers),
o Fuel selection based on emission characteristics,
o Precombustion cleaning or treatment of fuels,
3-26
-------
o Use of a production process which is inherently low
polluting or nonpolluting, and
o Use of particular work practices and/or operational
standards so as to decrease emissions.
Within Subpart A of 40 CFR 60, General Provisions, are outlined basic
emission monitoring requirements such as: (1) notification and record-
keeping requirements; (2) requirement that the monitoring systems not only
meet, but are demonstrated or certified to meet, certain design and per-
formance specifications; and (3) requirements for proper location of the
monitor in ducts or stacks. Data reduction and calculation procedures are
also specified. All sources affected by NSPS have to comply with these
general provisions of the regulations.
3-27
-------
Requirements for new sources associated with CEM recordkeeping and re-
porting requirements are covered under Section 60.7.
REQUIREMENTS FOR NEW SOURCES
40 C.F.R. Part 60, Subpart A (General Provisions)
CEM RECORDKEEPING AND REPORTING REQUIREMENTS (Section 60.7)
(b) Any owner or operator subject to
the pro\ isions of this part shall main-
tain records 01 the occurrence and du-
ration of anv startup, shutdown, or
malfunction in the operation ot an af-
fected facility: any malfunction of the
air pollution control equipment: or
any periods during which a continuous
monitoring system or monitoring
device is inoperative.
«
(O Each owner or operator required*
to install a continuous monitoring
system shall submit a written report
of excess emissions (as defined in ap-
plicable subparts) to the Administra-
tor for every calendar quarter. All
quarterly reports shall be postmarked
by the 30th day following the end of
each calendar quarter and shall in-
clude the following information:
(1) The magnitude of excess emis-
sions computed m accordance with
i60.13(h). any conversion f actons)
used, and the date and time of com-
mencement and completion of each
time period of excess emissions
(2) Specific identification of each
period of excess emissions that occurs
during startups, shutdowns, and mal-
functions of the affected facility The
nature and cause of any malfunction
(If known), the correctixe action taken
or preventativp measures adopted.
(3) The date and time identifying
each period during which the continu-
ous monitoring system was inoperative
except for zero and span rhecks and
the nature of the system repairs or ad-
justments
(4) When no excess emissions have
occur rod or the continuous monitoring
system(s) have not been moperame.
repaired or adjusted, such informa-
tion shall be stated in the report.
(d) Anv owner or operator subject io-\
the provisions of this part shall main-
tain a file of all measurements, includ-
ing continuous monitoring system.
monitoring device, and performance
lost ing measurements: all continuous
monitoring system performance e\alu-
at ions: all continuous monitoring
system or monitoring device calibra-
tion checks: adjustments and mainte-
nance performed on these systems or
devices: and all other information re-
quired by this part recorded in a per-
manent form suitable for inspection
The file shall be retained for at least
two years following the date of such
measurements, maintenance, reports.]
and records.
3-28
Record-
keeping
Reporting
•Recordkeeping
-------
Section 60.8 addresses performance test requirements of installed
monitors.
9 60.8 Performance tens.
(a) Within 60 days after achieving
the maximum production rate at
which ihe affected facility will be op-
erated, but not later than 180 days
after initial sta.lup of such facility
and at such other tunes as may be re-
quired by the Administrator under sec-
tion 114 of the Act. the owner or oper-
ator of such facility shall conduct per-
formance testts) and furnish the Ad-
ministrator a untien report of the re-
sults of such performance test(s).
(b> Performance tests shall be con-
ducted and data reduced in accordance
with the if si methods and procedures
contained In each applicable subpart
unless the Administrator (1) specifies-
or approves, m specific cases, the use
of a reference method with minor
changes In methodology. (2) approves
the use of an equivalent method. <3>
approves the use of an alternative
method the results of which he has
determined to be adequate for indicat-
ing whether a specific source is in
compliance, or <4> waives the require-
ment for performance tests because
the owner or opt rator of a source has
demonstrated by other means to the
Administrator's satisfaction that the
affected facility is in compliance with
'he standard. Nothing in this para-
graph shall be construed to abrogate
the Administrator's authority to re-
quire testing under section 114 of the
Act.
Tests in
accordance
with
applicable
subparts
0M.1I Compliance with standard* and
mainunane* requirement*.
(a) Compliance with standards in'
this part, other than opacity stand-
ards, shall be determined only by per-
formance testa established by 160.8.
unless otherwise specified in the appli-
cable standard. ,
(b) Compliance with opacity stand-^
ards In this part shall be determined
by conducting observations in accord-
ance with Reference Method 9 in Ap-
pendix A of this part or any alterna-
tive method that is approved by the
Administrator. Opacity readings of
portions of plumes which contain con-
densed, uncombmed water vapor shall
not be used for purposes of determin-
ing compliance with opacity standards.
The results of continuous monitoring
by transmissometer which Indicate
that the opacity at the time visual ob-
servations were made was not in
excess of the standard are probative
but not conclusive evidence of the
actual opacity of an emission, provided
that the source shall meet the burden
of proving that the instrument used
meets (at the time of the alleged viola-
tion) Performance Specification 1 in
Appendix B of this part, has been
properly maintained and (at the time
of the alleged violation) calibrated.
and that the resulting data have not
been tampered with in any way.
(c) The opacity standards set forth
In this pan shall apply at all times
except during penods of startup, shut-
down, malfunction, and as otherwise
provided in the applicable standard.
(d) At ail times, including periods of
startup, shutdown, and malfunction.
owners and operators shall, to the
extent practicable, maintain and oper-
ate any affected facility including as-
sociated air pollution control equip-
ment in a manner consistent with
good air pollution control practice for
minimizing emissions Determination
of whether acceptable operating and
maintenance procedures are being
used will be based on information
available to the Administrator which
may include, but is not limited to.
monitoring results, opacity observa-
tions, review of operating and mainte-
nance procedures, and inspection of
the source.
Compliance
Tests
Use of
Opacity
CEM
Start-up,
Shut-down,
Malfunctions
3-29
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Not all NSPS source categories listed in Table 3.4 are required
to apply continuous emission monitors as part of their performance
standards. Performance standards for new souces are found in the
Subparts of the Code of Federal Regulations. Monitoring require-
ments for each affected facility are found in these Subparts. Monitor-
ing requirements for regulated pollutants are not enforceable until
performance specifications have been promulgated for that pollutant.
Table 3.5 list current continuous emission monitoring requirements
for affected facilities. Those regulated pollutants where performance
specification test have not been promulgated, thus that source not
required to monitor, is indicated by an asterisk.
TABLE 3.5
NSPS SOURCES REQUIRING CONTINUOUS EMISSION MONITORING
Subpart
Facility
Continuous Emission
Monitoring Requirements
Subpart D FFFSG (construction commenced
after August 17, 1971}
Subpart Da Fossil fuel fired electric
utilities (construction
commenced after September
18, 1978)
Subpart G Nitric Acid Plants (construction
commenced after August 17, 1971)
Subpart H Sulfuric Acid Plants (construction
commenced after August 17, 1971)
Subpart J Petroleum Refineries, (FCCU:
construction commenced after
June 11, 1983; Claus sulfur
recovery unit: construction
commenced after October 4, 1976)
Subpart P Primary Copper Smelters
(commenced construction after
October 16, 1974)
Subpart Q Primary Zinc Smelters
(commenced construction after
October 16, 1974)
Subpart R Primary Zinc Smelters
(commenced construction after
October 16, 1974)
Subpart Z Ferroalloy Production
Facilities (commenced construction
after October 21, 1974)
Opacity, SOg ,NOX,
03 or
Opacity, $03, NOX,
02 or C02
NOX
S02
Opacity, CO*,
S02, H2S*
Opacity, S02
Opacity, S02
Opacity, S02
Opacity
Continued.
3-30
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TABLE 3.5 (Continued)
NSPS SOURCES REQUIRING CONTINUOUS EMISSION MONITORING
Subpart
Facility
Continuous Emission
Monitoring Requirements
Subpart AA
Subpart BB
Subpart HH
Subpart NN
Subpart FFF
Electric Arc Furnaces
(commenced construction
after October 21, 1974)
Kraft Pulp Mills
(commenced construction after
September 24, 1976)
Lime Manufacturing Plants
(commenced construction after
May 3, 1977)
Phosphate Rock Plants
(commenced construction
after September 21, 1979)
Flexible Vinyl and Urethane
Coating and Printing
(commenced construction after
January 18. 1983)
Opacity
Opacity, TRS
Opacity
Opacity
VOC*
3.5 STANDARDS OF PERFORMANCE FOR KRAFT PULP MILLS - SUBPART BB
Subpart BB, Standards of Performance for Kraft Pulp Mills, addresses
standards of performance, monitoring of emissions, test methods and pro-
cedures. Figure 3.2 outlines each section of Subpart BB of 40 CFR 60.
FIGURE 3.2
STANDARDS OF PERFORMANCE
KRAFT PULP MILLS
A7568
Standards of Performance for Kraft Pulp Mills
February 23, 1978
Subpart BB
p. 7572
60.280
Applicability and Designation of
Affected Facility
p. 7572
60.281
Definitions |
p. 7573 ~
60.282
Standard for Parti culatre Matter
p.7573 | 60.283 Standard for Total Reduced Sulfure (TRS)
p.7573 | 60.284 Monitoring of Emissions and Operations
p.7574 T60T28T
Test Methods and Procedures
3-31
-------
Within the Subpart of the Regulations, an affected source can deter-
mine which facilities within that source are regulated, the pollutants
that are regulated, emission limits, monitoring requirements and report-
ing requirements. For Subpart BB, Standards of Performance for Kraft
pulp mills, the pollutant regulated, its emission limit and monitoring
requirements are indicated in Table 3.6. Under NSPS for Kraft pulp mills,
total reduced sulfur (TRS) emissions are monitored for operation and
maintenance purposes. Compliance with the emission standard is determined
by Federal Reference Method 16 or 16A.
TABLE 3.6
SUBPART BB. STANDARDS OF PERFORMANCE FOR KRAFT PULP HILLS
POLLUTANT MONITORING REQUIREMENTS
Source Category
Subpart BB - Kraft Pulp Mills
Proposed/effective
9/24/76 (41 FR 42012)
Promulgated
Z/Z3/78 (43 FR 7568)
Revised
8/7/78 (43 FR 34784)
Affected
Facility
Recovery furnace
Smelt dissolving
tank
Lime kiln
Digester, brown stack
washer, evaporator,
oxidation, or strip-
per systems
Pollutant
Participate
Opacity
TRS
(a) straight recovery
(b) cross recovery
Participate
TRS
Partlculate
(a) gaseous fuel
(b) liquid fuel
TRS
TRS
Emission Limit
0.044 gr/dscf
(0.10 g/dscin)
corrected to 8t
oxygen
35S
5 ppm by volume
corrected to 81
oxygen
25 ppm by volume
corrected to 8X
oxygen
0.2 Ib/ton
(0.1 g/kg)BLS
0.0168 Ib/ton
(0.0084 g/kg)BLS
0.067 gr/dscf
(0.15 g/dscm)
corrected to 10X
oxygen
0.13 gr/dscf
(0.30 g/dscm)
corrected to 10X
oxygen
8 ppm by volume
corrected to 102
oxygen
5 ppm by volume
corrected to 102
oxygen
•exceptions; see
standards
Monitoring
Requl rement
No requirement
Continuous
Continuous
No requirement
No requirement
No requirement
No requirement
Continuous
Continuous
Effluent gas Incineration
temperature; scrubber liquid
supply pressure and gas
stream pressure loss
3-32
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Concurrent with the continuous emission monitoring requirement are
parameter monitoring requirements within the Kraft pulp mill facility.
Table 3.7 reflects those affected facilities requiring parameter monitor-
ing.
TABLE 3.7
PARAMETER MONITORING REQUIREMENTS
KRAFT PULP MILLS
Affected
Facility
Parameter
Monitored
Point of incineration of effluent gases
from digester, brown stock washer,
multiple-effect evaporator system, black
liquor oxidation system or condensate
stripper system
Lime kiln or smelt dissolving tank
using a scrubber emission control device
Combustion temperature
Pressure loss of gas
stream through control
equipment
Scrubber liquid supply
pressure to control
equipment
3-33
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3-34
-------
4.0 CONTROL AGENCY CEM INSPECTION PROGRAM
4.1 INTRODUCTION
The Clean Air Act was the Nation's first Federal enforceable law
designed to protect the health and welfare of the population from airborne
pollutants. More importantly, sections within the Clean Air Act provided
the U.S. Environmental Protection Agency authority to (1) implement a re-
search and development program and (2) to provide technical assistance to
State and Local Governments in the execution and implementation of enforc-
ing the provisions of the Act in controlling air pollution from affected
sources. The Act recognizes the primary responsibility in prevention and
control of air pollutant lies with the state. Congress feels that each
state contains a unique inventory of sources and consequently, each state
should have the primary responsibility for designing and operating a con-
trol program to achieve the pollutant reduction necessary to meet the
national ambient standards. The Act recognizes the need for an effective,
cooperative and coordinated effort between the Federal, State and local
agencies to carry out its provisions. It is the ultimate responsibility
of the Federal Government to promote the "public health and welfare and
the productive capacity of its population." This cooperation between
Federal, State and local agencies is structured through the EPA's station-
ary source compliance program. The program was initiated to determine a
source's compliance status with CEM regulations.
The stationary source compliance program addresses pollutants
regulated in three sections of the Clean Air Act.
0 Section 110 - State-adopted, EPA-approved State Implementation
Plan (SIP) requirements to meet the National Ambient Air Quality
Standards for seven criteria pollutants;
o Section 111- Implementation of emission controls to establish
uniform, technology-based national emission standards for cate-
gories of affected new sources. These requirements are known as
New Source Performance Standards (NSPS). These standards are Fed-
erally promulgated and are usually delegated to state authority.
o Section 112 - Hazardous air pollutant standards for certain souce
categories of asbestos, beryllium, mercury, and vinyl chloride. The
National Emission Standards for Hazardous Air Pollutants (NESHAPS)
are also Federally promulgated and are usually delegated to State
authority.
4.2 CONTROL AGENCY COMPLIANCE PROGRAM
Control agency CEM inspection programs have used CEM certification
activities and periodic on-site inspection as a tool to determine a
source's compliance status. The regulatory agency CEM certification activi-
ties involve initial application, agency review and CEM certification of
4-1
-------
installed monitoring systems. The on-site inspection involves records
review, control equipment evaluation, evaluation of installed continuous
emission monitors through selective audits or Performance Specification
Testing (PST). Each of these techniques was designed to provide the inspector
with information so a determination of continued compliance can be made of
the continuous emission monitoring system.
Historically, stack testing has been used as part of a source's ini-
tial compliance determination. As NSPS standards developed, continuous
emission monitors became a part of regulatory agency's compliance program
for those sources required to monitor their emissions on a continuous
basis. .Historically, CEMs have played a limited role in this program.
Even with the 1975 promulgated regulations requiring CEMs as a means of
monitoring a source's "continuous compliance" status, it has taken 10
years to identify CEM data as an enforcement tool and bring it to national
attention. This lack of use may be attributed to early monitor problems
associated with reliability, accuracy and long term performance. However,
many of these earlier problems have been resolved. Consequently, such data
has become a valuable source of information by which regulatory agencies
can base their enforcment decisions. Regulatory agencies have increased
their reliance upon CEM data in its compliance and surveillance programs.
Eventually, CEMs will become part of all NSPS and NESHAPS standards as
they become promulgated or revised, if a compliance method is specified.
Sources subject to the requirements of using CEMs as a compliance de-
termination are generally required to submit to regulatory agencies quarter-
ly excess emission reports (EER's). The EER contains information on
number of excess emission over a standard, time and duration of those
incidences, reason codes for those incidencies and corrective/preventive
action taken to reduce those incidences. As personnel and funding limits
the feasibility of on-site inspections, the EER becomes an important
"feedback" system for both the source and the regulatory agency. The EER
becomes a tracking tool by which agency personnel can evaluate both the
control equipment and CEM performance.
In recent years, the EER report has not only been used to report ex-
cess emissions, but also other information associated with both control
equipment and monitor performance, such as:
o excess drift determinations;
o quarterly audit results;
o relative accuracy tests;
o average control device parameters
(pressure drop, milliamps, flow rates, etc.);
o "out-of-control" situations; and
o control equipment "baseline" information.
With limited control agency resources and manpower, the EER is the
"tracking" mechanism for monitor and control equipment performance during
periods when the agency personnel are unable to perform on-site evaluations,
as part of the "continuous compliance" strategy.
4-2
-------
Knowing that the purpose and scope of agency inspections vary with
manpower, a three phase and four level compliance inspection program has
been developed by the State of Pennsylvania Department of Environmental
Regulations and is presented below as an example of a successful program.
Each inspection phase or level is dependent upon the other for proper
information and determination.
The phase process consists of administrative activities involved
with initial CEM system application, performance testing and final approval.
This enables the state or federal agency agency to approve the monitoring
system through established certification procedures. The type of activities
at each phase are:
Phase I - Initial approval of CEM application as required
through source permit, by the regulatory agency;
Phase II - Observation of performance specification
testing (PST) of the installed CEM system; and
Phase III - Review of the PST report, with final approval
or disapproval.
The level approach begins after completion of the phase evaluation.
The levels of CEM inspection extend from source agency records review
(lowest level) to stack test compliance determination (highest level).
The intensity and thoroughness of the inspection increases numerically.
The primary objective of an agency on-site inspection and excess emission
review is to minimize air pollution through adherence to regulations and
permit stipulations. The inspection provides the determination or con-
firmation of compliance and helps identify causes of excess emissions.
The types of activities at each level of the CEM system inspection are:
Level I - Records review involving excess emission reports,
previous inspection reports, source "working" file review
and permit review;
Level II - On-site inspection involving review of monitor
recordkeeping (maintenance, monitor and control equipment
logs), monitor fault light indicator review, monitor internal
zero/span check, strip chart review and electronic checks;
Level III - Evaluation of installed CEMs through external
audit techniques involving neutral density filters for opacity
monitors and gas cylinders/cells for gas monitors; and
Level IV - Comparative evaluation of installed CEMs through
performance testing utilizing Federal Reference Methods or
portable CEMs.
The purpose of the increasing level of inspections is to concentrate
the resources of the control agency personnel on those facilities that have
the greatest potential to exceed the emission limits.
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The phase and level audit procedures have been designed so that each
activity indicates whether or not the CEM system has achieved the neces-
sary level of compliance before starting the next phase. For example, if
the agency records audit reveals that the PST has not been successfully
completed, the agency may request that this be done before continuing
with the remaining phases. In this case, EERs might otherwise be reviewed
assuming invalid data, precluding any enforcement action based upon
emission rate data contained in the reports. Since the CEM data may be
assumed to be invalid, the source records audit may not be worthwhile.
The phase and level audit procedures are described in greater
detail below and outlined in checklist format, as a Supplement to
this manual entitled: " Technical Assistance Document for Monitoring
Total Reduced Sulfur (TRS) from Kraft Pulp Mills- Evaluation Procedures."
4.3 CONTROL AGENCY ADMINISTRATIVE REVIEW ACTIVITIES - PHASE I, II, III
4.3.1 Phase I - Regulatory Review of Source Application/Permit
Phase I involves the initial application of the source to the regula-
tory agency describing the total CEM program. The application is a response
to permit requirements as regulated by regulatory authorities. The permit
becomes the guideline for implementation of the CEM Program.
in an agency
The permit is part of four major control strategies
enforcement system. These strategies are:
- permit to construct and install operation;
- permit for continuous operation;
- compliance enforcement; and/or
- surveillance and complaint response;
The main objective of the permit regulation is to control emissions
from new or modified sources so those emissions do not:
- violate National Ambient Air Quality Standards (NAAQS);
- cause significant deterioration to prevent attainment
or maintenance of the NAAQS; and
- result in violations of the applicable portions of
existing control strategy.
As required by the Clean Air Act, all states must have an established
permit systems as part of their federally approved State Implementation
Plan. Permits may be administered either by local, state and/or federal
agencies depending upon who maintains regulatory authority over the
industry. Usually all major emitting facilities are included in state
and local permit regulations. Section llOd of the 1970 Clean Air Act
defines a major emitting facility as any stationary facility or source
which directly emits, or has a potential to emit, one hundred tons per
year or more of any regulated pollutant.
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As part of the 1977 CAA Amendments, the federal government was given
the added responsibility of reviewing all permits for major sources con-
structing in Prevention of Significant Deterioration (PSD) and nonattainment
areas. Federal review applied to:
- PSD areas for any source having a potential emission
greater than 250 tons per year or 100 tons per year
for 28 specified sources; and
- nonattainment areas for any source which have a
potential emission greater than 100 tons per year.
The permit, therefore, is an integral part of an agency enforce-
ment program. It provides the vehicle by which agency CEM objectives
become implemented and enforceable. The permit aids both the regulatory
agency and the applicant by:
- providing engineering review prior to construction so
any necessary changes can be made at the lowest cost;
- if proposed facility cannot comply with emission limitations,
then agency can prevent construction;
- agency can require basic quality assurances activities and
proper operative procedures implementations into the permit
to insure continued performance of control and CEM equipment;
- deny operating permit so if source does not meet compliance
limitations, then source cannot operate;
- provides a format for notification of source modification; and
- provides a "document" in which all conditions/specifications to
operate are stated.
The permit also provides guidelines to the source as to control
agency CEM program and objectives. It is within the permit that the
control agency can ensure that an established CEM program exists at the
source that it can meet all regulatory requirements. The permit not only
addresses the operating conditions of the source, but also the total
continuous emission monitoring system.
The permit should include, at a minimum, four major areas of informa-
tion associated with the continuous emission monitoring system. They are:
I. General Information;
II. Management Control System (MCS);
III. Standard Operating Procedure (SOP) Manual; and
IV. Quality Assurance (QA) Program;
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4.3.1.1 General Information -
General information allows the control agency to become familiar with
the process and the monitoring system used to evaluate that process. It
also enables the control agency to evaluate the relationship between the
process and the CEM system. With this information, the control agency can
approve/disapprove the application of the CEM system for that particular
source. Under the General Information section, the permit should require
the following:
- General description of the process and pollution control
equipment. All factors affecting that operation on
maintenance of the maintainable system should be involved;
- Location of monitoring system sample acquisition point(s)
in relationship to:
o Flow disturbance (fans, elbows, inlets, etc);
o Pollution control equipment;
o Emission point of the monitored gases; and
o Flow diagram illustrating location of all sampling points.
- System information, including:
o Operating principle of the pollutant analyzer;
o Equipment manufacturer;
o Manufacturer's literature; and
o Manufacturer's claimed performance specifications.
- Process and pollution control equipment operating parameters which
affect the emission levels of the pollutant(s) being monitored, and
a description of the method to be used to record significant para-
meters.
4.3.1.2 Management Control System (MCS) -
Documentation associated with the Management Control System (MCS) en-
ables the agency to track who is responsible for the CEM system. It assigns
individual management of each subsection. The MCS outlines administrative
procedures applicable to all management systems and assigns responsibility
for all phases of the CEM system operation.
4.3.1.3 Standard Operating Procedure (SOP) Manual -
The SOP manual should be a document defining all activities, responsi-
bilities, communication loops, documentation procedures, flow charts for
data acquisition/data handling, trouble shooting guides and preventive
management task/schedules. Calibration procedures, including acceptance
limit for monitor performance, should be specified. Table 4.1 illustrates
the different sections of a typical SOP manual.
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Section 1.
Section 2.
Section 3.
Section 4.
Section 5.
Section 6.
Section 7.
Section 8.
Section 9.
TABLE 4.1
STANDARD OPERATION PROCEDURE MANUAL
(Typical Outline)
Introduction
1.1 Standard Operational Procedure
Manual Description and Format
1.2 References
Quality Assurance Objectives
2.1 General
2.2 Specific
Organization
3.1 Personnel Assignments and Responsibilities
1
.2
.3
3.1.4
3.1.5
3.1
3.1
3.1
Organization
Program Management
Field Operations
Laboratory Operations
Data Management
3.2 QA Responsibilities
3.2.1 Quality Assurance Coordinator
3.2.2 Field Personnel
System Operation
4.1 Monitoring Site Description
4.2 Start-up Procedures
4.3 System Check-out
4.4 System Operation
4.5 Computer System Troubleshooting
4.6 Software Documentation
4.7 Routine Operating Procedures Checklist
Principles of Operation
5.1 General
5.2 Calibration Modes
5.3 Computer Control Subsystems
5.4 Monitor Subsystems
Quality Assurance
6.2 Performance Audit Procedures and Checklist
6.1 System Audit and Checklists
Documentation
7.1 Monitoring
7.2 Daily Log Book
7.3 Maintenance and Troubleshooting Log Book
Data handling, Validation and Reporting
8.1 Data Logistics
8.2 Data Handling and Statistical Analysis
8.1.1 Quality Control of Data Handling
8.2.2 Calculations
8.2.3 Statistical Evaluation
Control Charts
Data Validation Criteria
Data Reporting
Data Forms
8.3
8.4
8.5
8.6
Maintenance
9.1 General
9.2
Preventive Maintenance
9.3 Corrective Maintenance
9.4 Spare Parts Inventory
9.5 Maintenance Documentation
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4.3.1.4 Quality Assurance Program -
The main objective for requiring a quality assurance (QA) program
for the installed CEM is to insure that all data collected and reported
is meaningful, precise and accurate within a stated acceptance criteria.
The program should be strong enough to insure strict adherence to all es-
tablished procedural requirements, but flexible enough to allow continuing
evaluation of its adequacy and effectiveness. Once a QA plan is written
and implemented, assessment procedures within the plan should point out
any necessary corrective action which, in effect, revises the plan.
The QA program should involve two major divisions:
- Quality Assurance - activities to address the necessary
status and reliability of the installed CEM system; and
- Quality Control - functions initiated when quality assurance
indicates data reliability outside predetermined control limits,
Both of these topics will be discussed further in Chapter 11, Quality
Assurance/Quality Control.
4.3.2 Phase II - Performance Testing of Installed Continuous Emission
Monitoring System
After the approval by the regulatory agency of Phase I, the industry
proceeds with the purchasing, installation and performance testing of the
CEM system. Activities for the regulatory agency during Phase II involve
receiving notification (in 30 days) from the source of pending Performance
Specification Testing of permitted CEM system, observing the testing during
the PST and reviewing results.
4.3.3 Phase III - Regulatory Approval of Installed Continuous Emission
Monitoring System
Phase III, Final Approval, consists of reviewing the Performance
Test report. All information required to be gathered during Phase II
must be reported according to the following specifications:
A. For opacity monitors, 40 CFR 60, Appendix B, Performance
Specification Test 1;
B. For total reduced sulfur (TRS) monitors, 40 CFR 60, Appendix B,
Performance Specifications Test 5; and
C. For oxygen and carbon dioxide monitors, 40 CFR 60, Appendix B,
Performance Specification Test 3.
The reviewer should make a determination of the acceptability of the
test results and procedures. This determination should support a final
approval, or disapproval of the CEM system.
Other activities associated with Phase III involves necessary source
recordkeeping and reporting requirements to the regulatory agency. The
agency specifies what records are to be maintained and what is to be
reported.
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4.4 CONTROL AGENCY CEM INSPECTION REVIEW ACTIVITIES - LEVEL I, II. Ill,
and IV
Level I, II, III, and IV CEM inspection review activities involve re-
cords review, agency records update, source records review and onsite in-
spection. The control agency can make a preliminary determination of the
CEM program compliance status at a given source, without travel or signifi-
cant time expenditure, through a record review. From the EER and PST
reports, compliance status with installation, testing, and notification
requirements can be ascertained. The on-site review involves maintenance
records review and sources process and control system CEM records review.
From this information, the agency can determine the status of the CEM
system and whether it is being maintained. If the source record review
indicates weaknesses, the inspector can proceed to on-site evaluation of
installed continuous emission monitors utilizing external audit techniques.
The purpose of a field inspection is to, therefore, verify first hand
the information already obtained or requested through the records review.
The inspection is especially worthwhile when the source has not demonstrated
compliance with the installation, testing, notification, and recordkeeping
regulations, or when the earlier audit results do not clearly identify
the CEM compliance status. The field inspection may also be used when
conducting a plant inspection or observing an emissions performance test.
Consequently, the on-site inspection involving Levels I, II, III and IV
provides a complete CEM system evaluation, from records review to performance
testing.
4.4.1 Control Agency Records Review - Level I
Level I CEM inspection procedures involves a "thorough" working know-
ledge of the facility from information gathered through file review.
Level I inspection is routine file review and administrative, intended to
identify problem areas without attempting to solve them. The process
involves review of information found in the source's:
- Facility "permanent" file; and
- Facility "working" file.
The facility "permanent" file contains basic information associated
with the application and certification of the continuous emission monitor-
ing system. This would involve:
- Original permit;
- Compliance schedule and variance;
- CEM certification report; and
- Final permit approval documentation.
A review of the available background information on the facility
to be inspected is essential. This review will enable the inspector to
become familiar with the facility's process and emission characteristics.
The following types of information should be reviewed as part
The following types of i
of the "permanent" file:
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4.4.1.1 Basic Facility Information -
- Names, titles, and phone numbers of facility representatives;
- Maps showing facility location and geographic relationship to
residences potentially impacted by source emissions;
- Process and production information; and
- Flowsheets identifying sources, control devices, monitors, and other
points of interest.
4.4.1.2 Pollution Control Equipment and Other Relevant Equipment Data -
- Description and design data for control devices and relevant
process equipment;
- Sources and characterization of emissions;
- Continuous emission monitoring system(s) data; and
- Baseline performance data from both control equipment and
continuous emission monitors taken during certification.
4.4.1.3 Regulations, Reporting Requirements, and Limitations -
- Most recent permits for facility sources;
- Compliance schedule and variances;
- Applicable Federal, State, and local regulations and reporting
requi rements;
- Any required periodic reporting;
- Special exemptions and waivers, if any;
- Acceptable operating conditions for control equipment
and continuous emission monitors; and
- Continuous emission monitor certification reports.
Once the inspector has become familiar with the "permanent"
file, he should then review the source's "working" file.
The "working" file should contain basic information associated
with the facility compliance and enforcement history. In particular,
the review of the source's "working" file should include:
Previous inspection reports;
- Compliance history including reports, follow-up,
findings and remedial action; and
- Quarterly excess emission reports (EERs).
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4.4.1.3.1 Previous Inspection Reports -
Review of previous inspection reports allows the inspector to become
familiar with chronic problems associated with the control equipment or the
continuous emission monitoring system. It allows him to "baseline" both
the pollution control equipment and the continuous emission monitoring
system. The fundamental principle underlying the baseline approach is
that both control equipment and continuous emission monitors are evaluated
by comparison at present conditions with machine/monitor specific baseline
data. Their operating characteristics and performance levels are unique.
By comparing previous inspection reports with initial compliance observation
data, the inspector is able to identify potential source related problems.
4.4.1.3.2 Compliance History -
Compliance history review enables the inspector to identify control
equipment problems and possible continuous emission monitor malfuncitons.
4.4.1.3.3 Excess Emission Reports -
The most important review as part of level 1 "working" file is the
review of the source's excess emission reports.
EPA has promulgated regulations requiring certain NSPS facilities
to install, maintain, and operate continuous emission monitoring systems.
In addition, EPA has required that State Implementation Plans (SIPs) be
revised to require certain existing facilities to install, maintain, and
operate CEM systems. These regulations require "performance testing" and
"periodic reports and recordkeeping of the nature and magnitude of such
emissions." Furthermore, Sections 113 and 114 of the Clean Air Act
(CAA), as amended in 1977, require the use of recordkeeping and reporting
requirements as means of enforcing emission standards.
Historically, the reporting requirements for NSPS sources (40 CFR
Part 60) have involved a written report for any calendar quarter in which
source emissions exceed the value of the standard. The emission value,
as recorded by the CEM system (i.e., % opacity, ppm, Ib/ton, etc.) must
be recorded, as well as the duration (i.e., six minutes, 12 hours, etc.)
of the excess emission. An excess emission is defined as exceedance of
the emission limit values over the time period specified by the subject
standard. Similiarly, 40 CFR Part 51 requires some existing stationary
sources to implement a continuous monitoring program and to provide quar-
terly excess emission reports (EERs). The minimum information required
in the excess emission report is:
- The magnitude, duration and date of excess emissions;
- The identification of each excess attributable to start-
ups, shutdowns, and malfunctions;
- The cause of any malfunction and the corrective action
or preventive measures adopted to the system;
- The date, time, and duration of any monitor outage for
reasons other than zero and span checks;
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- The reason for monitor outage and corrective action taken; and
- Statement of no excess emissions and/or monitor outages, if
applicable.
Excess emission reports are reviewed in three levels. The
three levels are:
- Level 1 - Initial review and summary of the CEM data;
Level 2 - Confirmation of Level 1 results, targeting of
sources for follow-up, and data input to the CEMs subset
of the Compliance Data System (CDS); and
- Level 3 - Follow-up comparison of CEMs data and other
emission data with potential recommendations for
additional testing or compliance/enforcement action.
To assist the inspection in evaluating previous EERs, a standardized
form has been recommended by EPA and is found in Section 10.0 of this manual,
Once the "permanent" and "working" files have been reviewed, the in-
spector should have a good idea of the present operation and maintenance
practices of the control equipment, the continuous emission monitoring
system and the compliance status of the source. He is now ready to pro-
ceed to Level II to verify his findings from the records review (Level
I).
4.4.2 - Source Records and Continuous Emission Monitoring System Review -
Level II
Level II involves a "walk through" inspection of the regulated facility.
The on-site "walk through" inspection is the foundation for a control agency
compliance monitoring strategy and enforcement programs. The on-site in-
spection provides:
- Compliance data to determine or confirm source
compliance with the regulations;
- Information on identification of violations;
- Base for establishing an enforcement action
through documentation;
- promoting agency's continuous compliance strategy; and
- informal consulting to assist facility in identifying
and resolving compliance problems.
A Level II inspection is a detailed evaluation of all aspects of the
continuous emission monitoring system. This involves review of record-
keeping and reporting activities, strip chart/data processor review, CEM
daily zero/span checks, remote display review, and control equipment re-
view. In essence, the control agency inspector is correlating information
from the Level I review and comparing it to the on-site inspection.
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An Inspection of the GEM system includes a general evaluation
of the CEM sample interface and reference method sample locations for gas-
eous systems and evaluation of the representativeness of the optical path-
length of transmissometers. These evaluations can only verify whether or
not the general location criteria are met, and if additional stratification
(gases) or particulate distribution (opacity) evaluations are needed.
This should have been addressed prior to actual installation and testing;
however, the subject of CEM location is often overlooked, especially for
systems installed several years ago.
The field inspection of the CEM installation offers an opportunity
to evaluate environmental aspects such as temperature, vibration, and
other variables which often have a direct bearing on monitor reliability.
When gases are analyzed using extractive monitors located remotely from
the sample interface, the sample and calibration gas transport systems
can be inspected. Heat tracing, insulation, weather protection, transport
line, and connection material should be evaluated. For analyzers measuring
"wet" gas concentrations, gas temperature must be maintained above the
dew point.
Conditioning systems are an integral part of any TRS CEM system. It
is essential for extractive monitors that all moisture and particulate matter
be removed from the sample prior to the analyzer to eliminate interference
and to avoid corrosion in the analyzer. The conditioning system should
be properly designed and maintained, to avoid system malfunctions, which
can cause reduced monitor availability and preclude data validation.
By actually inspecting the analyzer location, the auditor develops
an appreciation of its accessibility for maintenance. Maintenance
accessibility may have been compromised in achieving a representative
location with an environment suitable for operation. When reviewing
future monitor malfunctions in EERs, this information can be pertinent to
the evaluation of malfunction duration.
Calibration gas cylinder location should be reviewed. If the cylin-
ders are exposed to ambient temperatures, some assurance of proper cylinder
material selection to insure thermal stability is recommended. This can
be provided from the gas supplier as part of the purchase agreement, al-
though at some additional cost. The location and pressure of the calibra-
tion gas interface with the sample system should be verified.
The inspector should check the calibration while on-site to document
procedures, calibration reference values, and provide a spontaneous qual-
ity assurance check. Familiarity with the system output during a calibra-
tion will aid in future review of data submitted to the agency in EERs
and any other reports.
Reference material certification documentation such as gas trace-
ability or triplicate analysis should be available in plant records and
verified during the field inspection.
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The analyzer and/or control unit should be inspected to assure that
zero compensation limits have not been exceeded and fault indicators not
illuminated. The control unit and recorder output should be visible to
operators to assure their awareness of malfunctions. An alarm pickup
from the control unit to annunciate excess emissions is an appropriate
means of expediting operator response to reduce emissions, when necessary.
A discussion between the inspector and those operators responsible for
acknowledging excess emissions and monitor malfunctions is recommended to
stress the use of the monitor output to initiate corrective action for
these situations. It is also necessary to inspect the records documenting
these events to ensure that acknowledgement of excess emissions, indicated
by the CEM, and that corrective action by the plant operator has occurred
within a reasonable response time has taken place. Plant O&M records
should be reviewed to insure that both the CEM process and control equip-
ment maintenance is properly documented and corresponds to recorded excess
emissions events and monitor malfunctions.
A similar review of data reduction calculations for conversion to
emission rates to verify conversion factors and formulas is necessary.
When automated computation is utilized, these conversion procedures should
be periodically reviewed to be certain of accuracy. This can be done by
the source and agency when preparing and reviewing quarterly EERs.
To ensure that all information is obtained in order to make a proper
decision, the inspection should be performed in an organized and coherent
fashion. To accomplish this, the counter flow approach is utilized. The
counter flow approach is so named because inspection is accomplished counter
to the flow of information from the continuous emission monitoring system.
Figure 4.1 illustrates the counter flow technique.
CEM
EXTRACTIVE
PROBE
OFFICE
COMPLEX
TRS CEM
ANALYZER
POLLUTION
CONTROL
DEVICE
Figure 4.1 Counter Flow Approach
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The counter flow technique is most applicable for inspecting facilities
where baseline data is available. At each location, the inspector should
compare existing data to baseline data to determine degree of compliance.
4.4.2.1 Office Complex -
The Level II inspection begins at the office complex. All personnel
involved in the inspection should gather in a room for the opening confer-
ence. The purpose of the opening conference is to inform facility offi-
cial^) of the purpose of the inspection, the authority under which it will
be constructed, and the procedure to be followed. The opening conference
also offers the inspector the opportunity to strengthen agency-industry
relations through a positive attitude and provide relevant information
and other assistance. The effective execution of the opening conference
on the inspector's part often "sets the tone" for the remainder of the in-
spection.
During the opening conference, the inspector should cover the following
items:
- Inspection Objectives - An outline of inspection objectives will
inform facility officials of the purpose and scope of the inspec-
tion and may help avoid misunderstandings;
- Inspection Agenda - Discussion of the sequence and content of the
inspection, involving the continuous emission monitoring system
operations and control equipment and its current operating status,
should be discussed. This will help eliminate wasted time by
allowing facility officials time to make any preparations necessary.
The types of measurements to be made and the samples to be collected
(if any) should also be addressed;
- Facility Information Verification - The inspector should verify
or collect the following information:
- Correct name and address of facility;
- Correct names of plant management and officials;
- Principal product(s) and production rates;
- Sources of emissions; and
- Locations of emission points.
- Records Review - A list of records to be inspected should be
presented.TFis will allow company officials time to assemble
needed documentation. Needed records for review are:
- previous quarter excess emission reports (EERs);
- source log books;
o CEM operation log book;
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o Control equipment log book;
o CEM maintenance log book;
- strip charts for previous quarter or computer
print-outs; and
- source permit or variance information.
- Safety Requirements - The inspector should determine what facility
safety regulations including safety equipment requirements will be
involved in the inspection and should be prepared to meet these
requirements. The inspector should also inquire about emergency
warning signals and procedures;
- Inspection Schedule - A timetable associated with the inspection
will allow plant personnel to consider lunch, breaks and quitting
times;
- Inspection - Discuss with plant personnel the techniques of inspec-
tion, the objective of performing the inspection, etc.;
- Closing Conference - A post-inspection meeting should be scheduled
with the appropriate officials to provide a final opportunity to
gather information, answer questions, perform calculations and
make recommendations. At this time the inspector should discuss
any new rules and regulations that might affect the facility and
answer questions pertaining to them. If the inspector is aware
of proposed rules that might affect the facility, he or she may
wish to encourage facility officials to obtain a copy.
Once the opening conference is concluded, the inspector should begin
reviewing source documentation associated with the continuous emission
monitoring system.
The main objectives of document review is to cross-correlate informa-
tion from one source to another. For example, if the strip chart/data log-
ger indicates an excess emission, has it been properly documented in the
excess emission quarterly reports? Likewise, if the strip charts indicate
no emission for a time period, does this correlate with plant log books or
CEM maintenance log books? Strip charts should be reviewed for consistency
of daily zero/span checks, properly noted with date, time, etc., and review-
ed for normal/abnormal emissions. In general, data inspection involves:
- compliance with recordkeeping and reporting requirements of the
permit;
- checking records for data validation and proper data reduction
procedures;
- reviewing strip charts/data logger for consistency with zero/span
values, excess emissions, proper notation, etc.; and
- review of all maintenance logs for proper entries;
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After an extensive review of the records, the inspection proceeds
to the continuous emission monitoring equipment. Historically, the CEM
system involves five major components:
- Data recorder/data processor;
- Analyzer;
- Calibration system;
- Sample conditioning system; and
- Probe/extraction system.
4.4.2.2 Control Room -
4.4.2.2.1 Data Recorder/Data Processor -
There are many kinds of data output and recording devices which can
be attached to the monitoring equipment. Except for checking the zero
and calibration adjustments daily, there is no requirement for any visual
display of the monitor output. Data may be recorded in any manner which
allows the source to reliably and accurately maintain the files required
by the regulations. As a minimum, each analyzer unit in the system must
produce an output signal showing instantaneous pollutant concentration.
When recorded on a strip chart recorder, this signal represents an emission
versus time record which may be manually or mechanically integrated to
provide the various emission averages required by the regulations.
At the source's option, these signals may be wired directly into
various integrating modules, computing devices, or data loggers, which
produce the required averages directly as their output. This information
is then stored on some storage media, or send it to a computer for further
analysis. Regardless of how this is done, these recorded values may be
combined with additional factors (calibration and conversion factors,
zero and span corrections, oxygen correction, etc.) to yield the emission
records required by the regulations.
The inspection of the data processor therefore may involve
certifying that this conversion is performed properly. Additionally,
the data processor may be a source of information concerning routine
maintenance practices and monitor malfunctions. The strip chart or
data logger recorder should be checked to insure that a good record is being
produced from the analyzer output. The total data processing system
should be checked for reliability and accuracy.
4.4.2.2.2 Analyzer -
The analyzer inspection involves noting present operating status of
the analyzer. Various gauges/regulators and valves should be inspected
for proper setting and operation. These settings should be referenced back to
the initial baseline data. Emissions, as displayed by instrument meter,
should be compared to the data processor to insure proper notation. Add-
itionally, any fault light indicators should be noted and recorded on the
field inspection form. At this time, an internal zero/span check should be
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performed. When the checks are made, note the resulting zero and span read-
ings. The values or changes in values from the previous routine check
should be consistent with the changes recorded in the maintenance records.
Finally, the internal zero/ span calibration check should be within the per-
formance specification guidelines.
4.4.2.2.3 Calibration System -
In addition to zero/span verification, the inspector should examine
the calibration system and gases used to generate the zero/span values.
Regulations require that the gases be EPA Protocol 1, or NBS traceable or
analyzed by the Federal Reference methods every six months. The inspector
should verify the procedure of certification and assigned concentration.
The value should be consistent with the value recorded in the data processor
unit or monitor log book. Additionally, the inspector should verify that
the daily zero/span checks evaluate the monitoring system in total. This
includes all components: the conditioning/extraction system, the analyzer
system and the data acquisition system. In some types of monitoring sys-
tems, however, certain instrument components are bypassed during calibra-
tion checks. For instance, in certain types of monitors, calibration is
performed only in the electronics. The inspector should, therefore, at-
tempt to find out how the unit actually performs the calibration. Does
the procedure check the entire system or not? If not, the personnel at
the source should be asked how they check the rest of the monitoring system.
4.4.2.3 Control Device
The purpose of inspecting the control equipment is to determine if
the unit is operating according to manufacturer guidelines and within
limits determined during the Performance Specification Test. In essence,
the inspector is comparing the present operation of the control device to
its individual operating specifications. These specifications values are
"baseline" values by which the inspector can reference to the on-going
inspection. If a particular indicator of the operation of the control
equipment (milliamps, scrubber pH, primary/secondary current) changes from
the baseline value, then this becomes a possible indicator of deteriorating
operation. The inspector is looking for possible deviation from baseline
operating conditions and relating these deviations to operating/maintenance
practices. The malfunction of the control equipment may cause violations
or noncompliance with permit emission limitations.
Consequently, baselining the control equipment is very important in a
control agency continuous emission monitoring program. Baselining the con-
trol equipment helps in the evaluation of the continuous emission monitoring
system on the source. Baselining the control equipment can be performed:
o After initial operation and during normal plant process;
o During stack test to establish representative operating conditions;
o During initial compliance test for NSPS sources;
o During Performance Specification Testing; and
o During each source inspection visit to establish normalized op-
erating parameters.
4-18
-------
Baseline Information also allows the Inspector to note changes from
manufacturer stated values, evaluate the direction and magnitude of those
changes and determine long-term performance of the control equipment. More
Importantly, 1t allows him to re-evaluate his Inspection schedule and up-
date routine Inspections or compliance testing.
4.4.2.4 CEM Interface System -
4.4.2.4.1 Sample Conditioning System -
The sample conditioning system usually Involves removal of interfer-
ing species from the gas stream which would affect the detector system.
This may Involve parti oil ate matter, moisture and S02 removal. Heat
trace lines should be operating to maintain temperature of sample gas
from conditioning system to analyzer. Inspection points are more visual
than action oriented. The Inspector should insure that valves are operat-
ing, the transfer line 1s heating, the moisture removal system working,
etc.
4.4.2.4.2 Probe/Extraction System -
Inspection of the probe/extraction system may be performed by observing
through an additional porthole opposite the system. The inspector should
determine 1f certain problems exist such as: probe plugging, vibratlonal
problems, temperature problems, or moisture problems In the extraction sys-
tem.
Once the inspector has inspected the probe/extraction system, he has
completed the visual inspections of the system. He should then proceed back
to the conference room to compare notes and initiate the closing conference.
4.4.2.5 Closing Conference -
The closing conference enables the Inspector to "close-out" the inspec-
tion Including answering questions from plant personnel. The closing con-
ference enables both the inspector and industry representative to evaluate
the Inspection. For the Inspector, 1t enables him to collect missing data
needed to complete the evaluation. In general, the following should be
covered in the closing conference:
- Review of Inspection Data - All Information gathered during the
Inspection should be reviewed for completeness. Any missing data
or requested data should be exchanged at this time.
- Inspection Discussion - All questions relating to the inspection
should be answered at this time. However, caution should be taken
by the inspector In answering questions relating to, compliance
status or enforcement action as a result of the inspection.
- Recommendations - At this time, the inspector can make recommend-
atlons as to possible solutions to deficiencies noted during the
inspection. The inspector should suggest available technical
publications or documents relating to the continuous emission
monitoring system which would address the noted deficiencies.
4-19
-------
To assist the inspector in performing all functions associated with
Level I and II of the Control Agency Inspection Program, a step-by-step
inspection manual has been developed. The objective of this manual is to
provide documentation and guidance to the inspector so he can determine
if the continuous emission monitoring system is operating according to per-
mit conditions. This document, Field Inspection Notebook for Monitoring
Total Reduced Sulfur (TRS) from Kraft Pulp Mills, is provided as a supple-
ment to this manual.
4.4.3 - Continuous Emission Monitoring System Calibration
Error Determination - Level III
The Level III inspection, for the control agency inspector, is the
most costly and labor intensive. The Level III inspection becomes necessary
only if the Level II inspection indicates deficiencies in the CEM system.
The Level III inspection involves a complete evaluation of the monitoring
system through a dynamic calibration procedure. Multiple concentration
gases are injected, as close to the probe tip as possible, and the monitor
response is compared to the certified gas values. From this evaluation,
a calibration error is determined. If the error falls outside calibration
drift performance specification values, then the monitoring system is
"out-of-control". This would initiate some form of corrective action by
the source or a Level IV evaluation by the regulatory agency.
Chapter 11.0, Quality Assurance/Quality Control, reviews several field
calibration systems which have been used by control agency inspectors as a
Level III audit system. The systems involve both permeation tube and gas
cylinder techniques. These audit devices should be part of a CEM inspection
program.
4.4.4 - Source Continuous Emission Monitoring System Performance Specifica-
tion Re-Evaluation - Level IV
A Level IV evaluation involves a recertification of the installed
CEM system utilizing Performance Specification Test 5 and 3. The role of
the inspector during this Level is to observe the proper extraction and
computation of emissions from the source during testing. At this time,
additional "baselining" of the control equipment and continuous emission
monitoring system can be performed. Inspection procedures, Performance
Specification Test observation forms and report review checklists are
provided in the supplement of the manual titled: "Technical Assistance
Document for Monitoring Total Reduced Sulfur (TRS) from Kraft Pulp Mills-
Inspection Forms."
4-20
-------
5.0 MONITORING SYSTEM INSTRUMENTATION
5.1 INTRODUCTION
The determination of compliance with applicable standards associated
with the Kraft pulp mill industry involves both opacity and gas emission
limitations on a continuous basis. The monitoring system must be able to
differentiate the regulated pollutant from the non-regulated pollutant.
Federal or State regulations will dictate whether an opacity monitor,
gas monitor, or both are required on a given source. Many sources will
be required to monitor opacity only. In such cases, instrument selection
is relatively easy since there is only one measurement principle that
will satisfy the EPA opacity monitor design specifications. Selection of
gas monitors is more difficult since EPA has established no design speci-
fications in this case. All that is necessary for a gaseous emission mon-
itor to be approved is that it perform according to EPA specifications
after it is installed on the source. Any chemical or physical monitoring
method can be used as long as it does the job of accurately monitoring
emissions (accurate, relative to the reference methods for determining
pollutant gas concentration as defined in 40 CFR Part 60 Appendix A).
All categories of sources required to install continuous gaseous
emission monitors are faced with the problem of selecting instruments
that will give data representative of the actual source emissions. The
problems that are encountered in a sulfuric acid plant will be different
than those found at a primary copper smelter or Kraft pulp mill. Even
within a given source category, the plant design will often dictate the
choice of a monitoring system.
There are many instruments marketpd for monitoring emissions from
stationary sources. Opacity monitors may be either single-pass or double-
pass systems. Gas monitoring systems may be either extractive systems,
in-situ systems, or remote monitoring systems. These divisions are shown
in Figure 5.1.
L
SOURCE EMISSION MONITORS
I OPACITY MONITORS
I GASEOUS EMISSION MONITORS |
I
SINGLE-PASS
SYSTEMS
DOUBLE-PASS
SYSTEMS
1
EXTRACTIVE
SYSTEMS
1
IN-SITU
SYSTEMS
REMOTE
SYSTEMS
Figure 5.1. Source Emission Monitoring Systems
5-1
-------
Extractive gas monitors were the first type of instruments to he
incorporated into continuous gas monitoring systems. Many of the first
extractive systems used modified ambient air analyzers or an ambient air
analyzer adapted to source applications with the use of a gas dilution
system. Many problems were found with this type of approach. Systems
were later designed to deal directly with the problems of extracting,
sampling, and analyzing pollutant gases at source level concentrations.
The extraction of a sample gas from a stack or duct presents a
number of problems. To obtain accurate results, the sample must first be
a representative one before entering the monitor itself. The sample must
be processed by removing particulate matter, condensing water vapor, and,
in some cases, removing specific gases that interfere with the analytical
method. In-situ monitors on the other hand, do not require the removal
of particulates or water vapor. The analysis is performed on the gas as
it exists in the stack or duct, (hence, in-situ) generally by some advanced
spectroscopic technique. These analyzers are either installed across a
stack (cross-stack) or employ a probe inserted into the flue gas stream
(in-stack). These two types of in-situ analyzers do not extract or
modify the flue gas.
In-situ monitors do, however, have limitations in their application.
If a stack or duct contains entrained water in the form of liquid droplets,
light scattering problems and absorption of the pollutant gases in the
liquid may cause the instrument values to differ from those obtained by
the EPA reference method. The choice of the type of system (either ex-
tractive or in-situ) to be used in a given application will often depend
upon features of the plant design and state of the art technology. The
choice of a specific instrument will depend upon variables ranging from
practical considerations, such as cost, to purely analytical factors, such
as the scientific principle that will give the most accurate concentration
data for a given pollutant. Presently, because of limitations and monitor-
ing techniques, only extractive systems for monitoring gas emissions of
TRS compounds at Kraft pulp mills are applicable.
The analytical techniques used in continuous source monitors of gaseous
emissions at Kraft pulp mills encompass a wide range of chemical and physi-
cal methods. They vary from chemical methods as basic as coulometric titra-
tion to the measurement of light produced in a chemiluminescent reaction.
A summary of the principles of chemical physics that are used in currently
marketed emission monitoring systems for Kraft pulp mills is given in
Table 5.1.
5-2
-------
TABLE 5.1
PRINCIPLES USED IN TRS CONTINUOUS EMISSION MONITORING SYSTEMS
TRS Monitors
Diluent Monitors
Absorption Spectroscopy Methods
Ultraviolet Differential
Absorption
Luminescence Methods
Flame Photometry
Fluorescence Spectroscopy
Electroanalytical Methods
Electrochemical Transducer
Coulometric Titration
Other
Gas Chromatographic Technique
Lead Acetate Optoelectronic
Electroanalytical Method
Polarographic (Og)
Electrocatalysis (Og)
Paramagnetic (02)
Absorption Spectroscopy
Differential Absorption (C02)
The main objective of the extractive sampling system is to extract
a representative sample from the source and transfer it to the detection
system for analysis without compromising its integrity. If other species
are present in the sample gas which interferes in the detection of the reg-
ulated pollutant, then they must be removed prior to analysis. This may
involve filtering or scrubbing the gas sample before delivering it to the
analyzer compartment. The gas sample is thus conditioned, refined, and
analyzed. Consequently, the extraction of a gas sample from a source
involves four major subsystems: (1) extraction; (2) conditioning;
(3) detection and (4) recorder/data processing systems. The subsystems
which compose an extractive TRS Continuous Emission Monitoring system
are illustrated in Figure 5.2.
5-3
-------
EXTRACTION
SYSTEM
1
DATA
PROCESSOR
SYSTEM
DETECTOR
SYSTEM
CONDITIONING
SYSTEM
Figure 5.2. Subsystems of a TRS Continuous Emission Monitoring System
o Extraction System
The purpose of the extractive system is to extract a rep-
resentative sample from the source, removing particulate
and moisture from the gas stream, if applicable, and
transport the sample to the conditioning system;
o Conditioning System
The conditioning system involves removal of interfering
gases and other species, then oxidizing the sample
(if applicable), and delivering it to the detector system;
o Detection System
The detection system involves the measurement of the gas
stream for TRS or S02; and
5-4
-------
o Recorder/Data Processor System
The Recorder/Data Processor receives the signal from
the detection system and stores/converts this infor-
mation to the appropriate units.
Each system is comprised of individual components, as itemized in
Table 5.2.
TABLE 5.2
SUBSYSTEM COMPONENTS OF A TRS CONTINUOUS EMISSION MONITORING SYSTEM
Extraction
System
Conditioning
System
Analyzer
System
Recorder/
Data
Processor
System
-Probe
-Coarse/Fine
Particulate Filter
-Particulate/
Moisture Removal
-Backpurge
Connection
-Calibration Gas
Connection
-Transfer Line
-S02 Scrubber*
-TRS Oxidizer*
•Transfer
Line
•Fine Particulate Filter
-Detection System
•Calibration Gas System
-Gas Mover
-Flow Measurement Control
Device
-Strip Chart
Recorder
•Data Logger
*If applicable
5.2 CONTINUOUS EMISSION MONITORING SYSTEM
5.2.1 TRS Extractive System Components
5.2.1.1 Particulate Filtration Device -
The main objective of the sampling probe is to extract a representa-
tive sample from the source and transport that sample to other components
of the sampling train. The probe should be of such construction to min-
imize interaction between itself and the gas stream. If needed, the probe
may require additional equipment to aid in parti oil ate removal and moisture
control application.
For particulate control, many designs have been used.
both in-stack and out-of-stack application.
The in-stack filters are divided into two categories:
or internal application.
They involve
external
5-5
-------
The in-stack internal filter, as illustrated in Figure 5.3, normally
consists of a porous cylinder made of various materials, such as: sintered
316 stainless steel, glass, ceramic or quartz. Uith this application, a
baffle plate is usually incorporated with the filter to help deflect larger
particulates from entering the porous filter.
• ' '1
'. •-, "
1
\t\:
•7v V
• , i
••• ••
i * 1 1
•• ••
POROUS
CYLINDER
/
\ ^ ':v'i:.*-:::.":r:iv/.-.'- :'.••:-':-.•'••.'-:•.• ;:-;:X
•: A S^/"' BAFFLE "A.: ;">, /
I'1. STACK GAS :' :. /'"'•':
f; • : //•. • •• • y •' -. /
^^*^ STACK
^* WALL
giHSil
^18
»• s
I]
:*,:„
SAMPLING INTERFACE
Figure 5.3. In-Stack Internal Filter Configuration
Used under this application, a routine back-purge would normally
assist in keeping the thimble clear of particulate.
Figure 5.4 illustrates the in-stack external filter arrangement. This
configuration allows the adaption of a nozzle to the probe, pointing down-
stream of the gas flow, for gas extraction.
NOZZLE
STACK WALL
SAMPLING INTERFACE
Figure 5.4. In-Stack External Filter Configuration
5-6
-------
Since many of the recovery boilers and lime kilns contain a very
large percentage of water, it is very important to keep the filter device
above the water dew point. If not kept above the water dew point, the
filter can become plugged with concentrate, causing a greater pressure
drop across the system and loss of sample.
Filter plugging is the most common problem associated with gas
extraction systems. To help eliminate the filter plugging problem,
techniques such as backpurging periodically with air or steam have
routinely been incorporated into a TRS CEM system. Other techniques
such as Baffle plates and sheaths around the porous filter have also
been utilized. These techniques are illustrated in Figure 5.5 and 5.6
respectively.
r
•
SHEATH
BAFFLE PLATE
( V BAR ) —
Figure 5.5. Use Of A Baffle Plate (V-Bar) And Sheath On A Lime Kiln
Application.
STACK CIS
BAFFLE
PLATE
POROUS
FILTER
Figure 5.6. Recovery Furnace TRS Sampling Probe Utilizing A Porous
Filter and a Baffle Plate.
5-7
-------
Recently, the inertial filter has been used as a secondary filtering
device in conjunction with a primary porous filter. In application,
inertial filter extracts a gas sample from the main gas stream at a 90°
angle. Within the probe, the high speed sample passes through a tubular
(inertial) filter. A small portion of this sample is drawn radially through
the porous filter wall at a velocity so low that the inertia of solid and
liquid particulates will be too high to curve through the wall of the fil-
ter. Figure 5.7 illustrates the use of an inertial filter as part of the
sampling probe assembly.
tM" U. Tub.
V«Ml»ItMk
Figure 5.7. Application Of Inertial Filter As Part Of A Sampling
Probe Assembly.
5.2.1.2. Stack Probe
The sampling probe normally consists of two components: an outer
sheath made of stainless steel and an inner lining made of either glass
or teflon.
5.2.1.3. Sample Line
The main objective of the sample line is to transport the sample gas
from the probe assembly to other components in the sampling train. As
shown in Figure 5.8, the sample line may be grouped with many tubes
providing plumbing and electrical connections to the probe assembly.
PVC
Myl*
COMHIHlMiail W,r» (K QM,,)
Figure 5.8. Umbilical Assembly
5-8
-------
In this configuration, the sample line is part of a total bundle
called the umbilical assembly.
Sampling train configuration will normally dictate important con-
siderations when selecting sampling lines. Such considerations should
include:
o Materials of construction;
o Size and length of sample line;
o Heat trace capability; and
o Cost.
5.2.1.3.1. Materials of Construction -
The choice of proper material of construction is very important,
Acceptable material of construction must meet these important criteria:
o Material must have sufficient chemical resistance to
withstand the corrosive constituents of the sample;
o Material must not exhibit excessive interaction (reaction,
absorption, adsorption) with the sample gases;
o Material used near the stack must be heat resistant; and
o Material must be heated if moisture is not removed prior
to sample transfer.
The corrosive constituency encountered in monitoring emissions
from Kraft pulp mills involves many species. In particular, acid gases
containing sulfuric and nitric gases are typical emissions. The chemical
resistance of various materials to these constituents is summarized in
Table 5.3.
5-9
-------
tn
i
TABLE 5.3
CHEMICAL RESISTANCE OF VARIOUS MATERIALS
Material
304 Stainless
316 Stainless
Carpenter 20
Aluminum
Glass
Teflon
PVC
Tygon
Polyethylene
Polypropylene
Nylon
Viton
Dry
S02
Steel S
(some pitting
observed)
Steel S
SS S
S
S
S
S
S
S
S
S - U
Dry
NOX
S
S
S
_
S
S
S
S
S
S
S
S
Oil.
HN03
S
S
«.051)*
S
S
(.127-. 508)
S
«.127)
S
S
S - Q
S - Q
S
S
S
Oil.
H2S03
Q
S
S
S
(.127-.
_
S
S
S
S
S
U
S
Oil.
H2S04
U
S-Q
(<.508)
S-Q
Q
508) (.508-1
S
(<.127)
S
S - Q
S
S
S
U
S
Cone.
HN03
S
S
«.508)
S
U
.27)01.27)
S
(<.127)
S
U
Q-U
U
U
U
s-u
Cone.
U
U
01.27)
S
U
01.27)
S
0.127)
S
S-Q
S-Q
Q-U
Q-U
U
S-Q
*Quantities in parentheses indicate corrosion rates in mm per year.
S = Satisfactory
Q = Questionable
U = Unsatisfactory
-------
5.2.1.3.2 Heat Resistance
Table 5.4 presents the heat resistance of various plastic materials,
Depending upon the condition and extraction location, all materials are
candidates for transfer material. The less heat resistant plastics
(polypropylene and polyethylene) cannot be used as efficiently in close
proximity to combustion sources. Teflon exhibits the best potential as
a sampling Hne component between the probe and the rest of the system.
TABLE 5.4
MAXIMUM CONTINUOUS OPERATING
TEMPERATURES FOR PLASTICS
Material Maximum Temp. (°C)
Teflon
Vivton
Polyethylene*
Polypropylene
Nylon
CPVC
Tygon*
250
150
80-125.6
110
121.1
110
60-82.2
*Depends on type used.
5.2.1.3.3. Sample Interaction
It is essential that the gas sample be transported from the probe
to the rest of the system with minimum loss and interaction. There are
several mechanisms by which interaction between sample gas and probe
can occur. They are:
- reaction - adsorption
- absorption - dilution
Gas phase reaction in sampling lines can occur by homogeneous gas phase
reaction and by heterogenous catalytic reaction. Materials of construction
such as Teflon®, stainless steel or glass, are generally very poor catalyst
and would not be expected to cause reactions. Absorption and adsorption
by the walls of the transfer line would eventually reach equilibrium;
consequently, would not change the concentration of the constituent stream.
Studies have indicated that absorption and adsorption are negligible, in
association to reduce sulfur compounds, for stainless steel, Teflon®,
polypropylene, polyethylene and Tygon®.
5-11
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5.2.1.3.4. Size and Length of Sample Line
The size of the sample line must be such that it is large enough so a
pump can handle the pressure drop, yet small enough so the response time
is not excessive. Flow rates as a function of pressure drop are shown for
various line sizes in Figure 5.9.
Studies have shown that for a flow rate of two liters per minute,
6.35 mm I.D. tubing will give only a pressure drop of between 1 and 3 mm
Hg per 100 ft. of tubing. This is not an excessive pressure drop for a
sampling system.
The lag time , (t), for a sample line volume, (V), may be calculated as:
t - V
where:
t = Lag time, (sec), V = Sample line volume, (ft3), F = Flow rate, (ft3/sec).
As an example, for a tube with an I.D. of 6.35 mm and 100 ft. from sample
extraction to the analyzer, what is the lag time at a flow rate of 2 1/min?
o 1st - Diameter of tube from mm to ft.
(6.35 mm)(32.808 x 10'4 ft/mm) = 0.0208 ft.
o 2nd - Calculate area of tube
A = Tir2 = Tr/2\2 = irD2 = (0.0208 ft)2 = .0003398 ft.2
W 4 4
o 3rd - Calculate volume of sampling line
V = (A)(L) = (0.0003398 ft2)(100 ft) = 0.03398 ft3
o 4th - Convert flow rate from 1/min to ft3/sec.
(2 1/min)(5.886 x 10'4) = .00117 ft3/sec
o 5th - Calculate lag time using volume and flow rate
t = V. = (0.05598 ft3) = 29.0 sec.
F (0.00117 ft3/sec)
For the above example, the lag time calculation would be 29 seconds.
This lag time is well within EPA guidelines. Table 5.5 displays lag times
for 100 feet of sample line with various inside diameters sample lines
for flow rates of 1 and 2 standard liters per minute.
TABLE 5.5
SAMPLING LINE LAG TIME
Tubing Size (mm)
Lag Time per (30.48 m) length
1 liter per min 2 liter per min
1.651 (3.175 o.d. x .762 wall)
3.175 (3.175 i.d.)
4.318 (6.35 o.d. x 1.016 wall)
4.572 (6.35 o.d. x 0.889 wall)
4.826 (6.35 o.d. x .762 wall)
6.35 (6.35 i.d.)
7.747 (9.525 o.d. x .889 wall)
9.525 (9.525 i.d.)
10.92 (12.70 o.d. x .889 wall)
12.70 (12.70 o.d.)
3.58 sec
13.26 sec
24.54 sec
27.51 sec
30.64 sec
53.06 sec
1.32 min
2.00 min
2.62 min
3.54 min
1.79 sec
6.63 sec
12.27 sec
13.75 sec
15.32 sec
26.53 sec
0.658 min
0.995 min
1.31 min
1.77 min
5-12
-------
0.1
.2261
2.261
Pressure Drop (kN/m2/100 m)
22.61
90.44
Figure 5.9. Flow Rates vs. Pressure Drop For Various Sample Lines Sizes
5-13
-------
5.2.1.3.5. Cost -
Costs are very important when considering putting together a
sampling system. Table 5.6 illustrates the cost of various materials
per 100 feet of line.
TABLE 5.6
COSTS OF VARIOUS SAMPLE LINE MATERIALS
BASED ON 100 FT OF 6.35 mm OD TUBING
Material Wall
Heat Traced Teflon
Heat Traced 316 Stainless Steel
Carpenter 20 Stainless Steel
316 SS
304 SS
Viton
Teflon
Tygon
Aluminum
Glass
Nyl on
Polypropylene
Polyethylene
Thickness
.889
1.016
.889 welded
.889 seamless
.889 welded
.889 seamless
.889 welded
1.575
.787 stiff wall
1.575
1.575
.889
8mm CD x 6mm ID
.762
.787
1.016
List Price per 30.48 m
350.00
325.00
196.00
184.45
80.95
113.07
71.66
145.00
107.00
63.00
15.60
11.00
7.33
4.40
4.31
3.70
5-14
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5.2.2. Conditioning System
5.2.2.1. - Moisture Removal -
Gases sampled from lime kilns and recovery boilers at Kraft pulp
mills usually contain significant quantities of water vapor which, when
cooled to room temperature, will condense out. There are presently very
few analyzers which are insensitive to water vapor. For those analyzers,
the sample gas is maintained above the water dew point by utilizing heat
trace lines, heated filters and pumps and heated analyzer enclosures.
For analyzers which cannot operate with a large quantity of water
vapor present, it is important that before analysis, it be removed as an
interference. This can be accomplished through several techniques. They
are: (1) Condensation; (2) Dessicant Technique; (3) Permeation Dryers; and
(4) Sample Dilution.
5.2.2.1.1. Condensation -
Condensers are the most common form of cooling gas streams to permit
moisture removal. They are generally temperature regulated either by
circulating fluid outside the condensing surfaces or by circulating air.
Figure 5.10 illustrates the use of an air cooled double vortex
condenser in a TRS CEM system.
SAMPLE
INLET
COOLING
AIR
OUTLET
SAMPLE
OUTLET
DRAIN
COOLING
AIR
INLET
LIQUID
RESERVOIR
Figure 5.10. Use Of An Air Cooled Double Vortex Condenser In A TRS
CEM System.
5-15
-------
Because a liquid is condensed from the gas stream, an automatic
drain valve should be incorporated into the system to eliminate gas
absorption in the condensate.
5.2.2.1.2. Permeation Dryer -
In recent years the permeation dryer has become increasingly popular
with extractive CEM systems. Utilizing a non-contact technique, the
permeation dryer is composed of ion-exchange membrane fuses housed in a
hollow stainless steel tube, as illustrated in Figure 5.11. This type of
dryer is termed a tube-and-shell-type.
JL
^-»-
Wet Purge Gas Outlet
— Shell Header-
-=^ ^_ Dry
—- ._
Header L -Permeable Tube Rack
Dry Purge Gas Inlet.
Figure 5.11. Permeation Dryer Technique
In operation, the high pressure wet stack gas enters the dryer through
the tube side. Counter current to this flow is a low pressure dry purge
gas supplied to the shell side of the tube-and-shell. This differential
pressure is sensed along the tubes which are made of ion-exchange membrane.
This unique membrane allows only water vapor molecules to permeate through
its skin, retaining other stack gas constituents. The movement of water
molecules is from the high pressure stack gas stream to the low pressure
purge gas stream through the ion-exchange tube membranes. The now water-
laden purge gas stream is exited out the side of the dryer. The water-
free stack gas stream exits out of the high pressure outlet side of the
condenser.
One can see that it is imperative that the entering water be above
its dew point to allow permeation to occur: liquid water plugs the system,
decreasing its efficiency; likewise, particulate decreases the operation
of the dryer.
Some of the advantages for using a permeation dryer over a
condenser are:
- non-contact technique - less acceptable to corrosion;
- less possibility of sample loss in condensate;
- no condensate trap required; and
- competitively priced.
5-16
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Some of the disadvantages are:
o plugging of the Ion-exchange membrane tubes due to participate; and
o required hardware associated with the Tow pressure dry purge gas
inlet.
5.2.2.2. SO? Separation Devices -
For these systems that measure reduced sulfur compounds as SOg,
the stack gas S02 must be removed prior to sample analysis to prevent a
positive bias. Early TRS CEM systems employed wet chemical scrubbers to
remove the interfering SOg pollutant, while allowing the reduced sulfur
compounds to pass. Recently, dry bed scrubbers have been employed equally
well. Using either system, the user must be aware of potential drawbacks.
They are:
o Solubility/Reactivity with scrubber media by reduced
sulfur compounds;
o SOg breakthrough potential;
o Maintenance/Upkeep of scrubber media;
o Monitor response to scrubber deterioration;
o Residence time; and
o Variable S02 concentrations.
5.2.2.2.1. Viet SO? Scrubbers -
A wet SOg scrubber is selected on the basis of S02 solubility in the
scrubber (buffer) solution. A buffered solution of potassium citrate (pH
5.5-5.6) has been found to be optimum for retarding SOg while allowing
reduced sulfur compounds to pass through. The scrubber system can either
be "batch" or "continuous" removal technique.
A batch scrubber is normally a solution of potassium citrate-citric
acid in a series of glass or Teflon® impingers. In operation, the gas is
pulled through the impingers, allowing the S02 to be absorbed while
passing the reduced sulfur compounds. Periodically, the scrubber solution
is changed as it becomes "exhausted."
Continuous SO? scrubber systems are different from batch scrubber sys-
tems in the fact that a fresh buffer solution is constantly fed into the
container while the expended solution is removed. Continuous S(>2 scrubbers
require more maintenance, but better response time is provided than with
the batch scrubber.
5-17
-------
Figure 5.12 illustrates the "batch" S02 scrubber while Figure 5.13
illustrates the two-stage "continuous" S02 scrubber.
Figure 5.12. "Batch" S02 Scrubber
GAS SAMPLE
IN
SCRUBBING
SOLUTION
OVERFLOW
GAS SAMPLE
TO ANALYZER
Figure 5.13.
S02SCRUBBING
SOLUTION
2 STAGE
CONTINUOUS S02
SCRUBBER
"Continuous" S02 Scrubber
5.2.2.2.2. Dry Bed Scrubber -
In recent years, dry bed scrubbers for S02 removal have been replac-
ing wet scrubbers. Dry bed scrubbers normally employ resin beads impreg-
nated with a solution which has a high absorbability for S02 while reject-
ing reduced sulfur compounds. The gas sample is once again pulled through
the cartridge, allowing the gas stream to contact the impregnated resin
beads. The 562 is retained on the beads while the reduced sulfur compounds
pass unaffected. The dry bed scrubber requires less maintenance than the
wet scrubber. However, breakthrough is possible after exhausting all
active sites on the resin.
5.2.2.3. TRS Oxidizer -
For those detection principles which detect the presence of sulfur
dioxide (S02) rather than total reduced sulfur (TRS), the stack gas TRS
components must be oxidized to S02. Studies have indicated the best avail-
able and most cost effective technique is a heated quartz tube, as illus-
trated in Figure 5.14.
5-18
-------
1500- 1750 °F
Quartz Tube
Figure 5.14. Heated Quartz Tube TRS Oxidizer
The main objective of the oxidation furnace is to oxidize the major
reduced sulfur compounds to S02. However, it is desirable not to oxidize
carbonyl sulfide (COS) or $03 to $03. This would, in effect, bias all
measured results.
Three important factors which govern what is oxidized in the furnace
are:
o Oxygen concentration in the sample;
o Furnace temperature; and
o Sample residence time in the furnace.
5.2.2.3.1. Oxygen Concentration in Gas Sample -
Because of the nature of the process at Kraft pulp mills, it is
believed that a sufficient amount of sample oxygen (^ 5%) is available to
allow complete combustion of major reduced sulfur compounds in the sample
gas. However, it is advisable to verify this periodically by injecting a
known concentration of certified H£S gas at the inlet of the probe along
with the stack gas sample. If the monitor responds properly (+_ 5% of
certified value), then the system is operating properly.
5.2.2.3.2 Furnace Time and Temperature -
Field experience has indicated that the furnace temperature should
be maintained between 1500-1750°F for effective combustion of reduced sul-
fur compounds. Studies have indicated that maintaining this temperature
insures 100% conversion efficiency for hydrogen sulfide, methyl mercap-
tan, dimethyl sulfide and dimethyl disulfide, while only 25% of the carbonyl
sulfide (COS) present is oxidized to S02- However, the presence of COS
in recovery furnace flue gas has been found to be less than 5% of the
total reduced sulfur compounds at a level of 10 ppm. This concentration
would be fairly insignificant compared to the final TRS value. Tempera-
tures greater than 2000°F are required to oxidize SOg to $03 without an
active catalyst. Field experience has demonstrated a residence time of 2.5
to 5 seconds in the combustion tube is sufficient for oxidation.
In summary, a thermal oxidation furnace should be constructed of
quartz tube heated to 1500-1750°F with a sample residence time of 2.5
to 5 seconds.
5-19
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5.2.2.4
The main purpose of a pump in a sampling system is to transfer the
gas stream from one location to another. This may be done either by po-
sitioning the pump upstream of the collection service (positive pressure)
or downstream of the collection device (negative pressure). The pump
location will determine the characteristics of that pump.
Pumps can be divided up into three broad categories:
(a) positive displacement pumps,
(b) centrifugal pumps, and
(c) eductor.
5.2.2.4.1 Positive Displacement Pumps -
Positive displacement pumps can be characterized by a linear relation-
ship between the change in capacity (AQ) of the pump and the pressure drop
( A P) across the pump. In essence, as the volumetric How rate changes,
there is a concurrent and direct change in pressure drop across the pump.
This becomes a constant. Figure 5.15 represents this characteristic of
the positive displacement pump.
Positive
displacement
w
2L
Pressure (p)
Figure 5.15. Positive Displacement Pump Characteristics
The name positive displacement pump arises from the fact that air is dis-
placed by the movement of the inner components of the pump. The mechanism
by which the moving part displaces the air determines the principle of opera-
tion. For example, pumps containing fixed casings with movable pistons are
called reciprocating pumps, part of the positive displacement classification.
Those pumps which utilize a gear or lobe to move air are called rotary pumps.
Table 5.7 illustrates the two subdivisions of the positive displacement pumps.
TABLE 5.7
SUBDIVISIONS OF POSITIVE DISPLACEMENT PUMPS
Principle of Operation
Reciprocating
Rotary (not discussed
in this manual)
Type of Pump
piston
plunger
diaphragm
gear
lobe
vane
screw
rotary plunger
5-20
-------
The piston pump is characterized by the movement of a piston into
and outside of a fixed volume. The piston displaces the air occupying
the same space on the discharge side. Likewise, the air displaces the
piston on the suction side. Figure 5.16 demonstrates the action of the
piston (reciprocating) pump.
I/////////////////
Suction
valve
Discharge
valve
Chamber
Figure 5.16. Reciprocation Pump
The reciprocating pump is by far the most common pump used in sampling
trains. The operation is very similar to the piston pump. Once again,
air is displaced by movement of a diaphragm, the outer edges of which are
bolted to a flange on the pump casing. The diaphragm may be made of metal,
Teflon®, or neospore. The most important characteristic of the diaphragm
material is its flexibility and resistance to reaction with the air being
moved. As the diaphragm moves up, air flows into the pump via a suction
valve. As the diaphragm moves down, air is funneled through a discharge
valve. Consequently, the gas moves into and out of the pump.
Figure 5.17 illustrates the operation of a typical diaphragm pump.
Diaphragm
Piston
Discharge valve
, Diaphragm
•exj-
Suction valve
Figure 5.17. Diaphragm Pump
5-21
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5.2.?..4.2. Centrifugal Pump -
Different from the positive displacement pumps, centrifugal pumps
employ centrifugal force to move air. The movement of an impeller rotating
in a volute ("snail's shell") casing causes a differential pressure, thus
pulling air into the center of the shaft. The air is then picked up by the
rotating vanes and accelerated. It is then discharged by way of the dis-
charge nozzle. Figure 5.18 illustrates the operation of the centrifugal
pump.
Suction
Discharge
nozzle
Impeller
Volute
Impeller
eye
Figure 5.18. Centrifugal Pump
5.2.2.4.3 Air Driven Eductor -
Air driven eductors are becoming more prevalant as the pump in a TRS
CEM sampling train configuration. Present application of the eductor has
been both as the primary or secondary air mover. In the primary configura-
tion, the eductor acts according to the jet principle, as depicted in
Figure 5.19.
At the nozzle, the high pressure driving force is converted into a
high velocity stream. The passage of the high velocity stream through
the suction chamber creates a decreased pressure (vacuum), thus drawing
air into the chamber. The incoming air is mixed with the high velocity
gas mixture and is ejected against a moderate pressure through a diffuser.
In this configuration, the high pressure gas stream pulls the stack gas
into the eductor area. A second pump, located downstream of the condition-
ing system, pulls the needed gas sample off of the air inlet position
before the eductor or nozzle.
5-22
-------
Nozzle
Suction
chamber
Diffuser
Air in
High
velocity
driving
force
Figure 5.19. Air Driven Eductor
It is evident from the above discussion that there are many choices
available in selecting a pump. A comparison of some of the advantages
and disadvantages of certain pumps is given in Table 5.8.
TABLE 5.8
ADVANTAGES/DISADVANTAGES OF AIR MOVING SYSTEMS
Pump type
Piston pump
(reciprocating)
Diaphragm pump
(reciprocating)
Advantages
1. Can operate at high
suction pressure
2. Can be metered
1. Wide range of
capacities
2. No seal required
3. Good in continuous
operation
Disadvantages
1. Small capacity
2. Seal required
between piston
and piston chamber
3. Working parts such as
check valves and
piston rings may cause
difficulties
4. Pulsating flow
5. Moderate maintenance
1. Limited materials
of construction
2. Operation at limited
suction pressures
3. Pulsating flow
4. Periodic diaphragm
replacement
5. Moderate maintenance
5-23
-------
TABLE 5.8 (Continued)
ADVANTAGES/DISADVANTAGES OF AIR MOVING SYSTEMS
Pump type
Advantages
Disadvantages
Centrifugal pump
1. Large Range of
capacities
2. No close clearance
3. Can obtain high
suction heads by
multistages
4. Light maintenance
1. No smal1 capacities
2. Turbulence
3. Operational noise
Eductors
1. No moving parts
2. Limited hardware
in contact with
gas stream
1. Requires unrestricted
flow
2. Plugging in exit
port of eductor
3. May require steam
to help dislodge
particles
5.2.3 DETECTOR SYSTEM
As indicated earlier, many analytical techniques are available for
monitoring TRS emissions from Kraft pulp mills. The techniques either
employ some form of direct measurement of the TRS components (gas chro-
matographic) or remove S02 from the gas stream, then oxidize the remaining
TRS to SOg with detection as S02. The following section discusses the most
common detection principles utilized in continuous emission monitoring
for TRS.
5-24
-------
5.2.3.1 Electrochemical Transducers -
One of the most popular methods of detecting S0£ in a gas stream is
the electrochemical transducer. The electrochemical transducer consists
of a sensing membrane, electrolytic reservoir and a counter electrode, all
in a self-contained cell, as illustrated in Figure 5.20.
Sample In
Semi-permeable
~1membrone
Thin Film
""[Electrolyte/'
Sensing Electrodes
Bulk Electrolyte
Reference
""lEIectrode
^/>^//y/y/%r/////
Sample Out
rr
S Output
Figure 5.20. Electrochemical Transducer
The transducer is generally a self-contained electrochemical cell
in which a chemical reaction takes place involving the pollutant molecule.
Two basic techniques are used in the transducer: (a) the utilization of a
selective semi permeable membrane that allows the pollutant molecule to
diffuse to an electrolytic solution, and (b) the measurement of the current
change produced at an electrode by the oxidation or reduction of the
dissolved gas at the electrode.
In operation, the flue gas is drawn into the electrochemical
transducer, where the selective semi-permeable membrane allows only
the S02 pollutant gas to diffuse. The S02 undergoes electro-oxidation,
releasing electrons. The net reaction is a release of electrons to the
counter-electrode by means of the electrolyte reservoir, as illustrated
in the following equation:
SO,
If the flow of electrons is diffusion controlled, the current will
be directly proportional to the concentration of reactants. This is
known as Fick's Law of Diffusion. Mathematically, this can be stated
by the following equation:
1 = nFADc = kc
nl-APc
5-25
-------
where:
i = current in amps;
n = number of exchanged electrons per mole of pollutant;
F = Faraday constant (96,500 coulombs);
D = diffusion coefficient of the gas in the membrane and film;
c = concentration of the gas dissolved in the electrolyte layer
A = thickness of the diffusion layer, in cm.
The selectivity of one pollutant diffusing through the membrane over
another is affected by two important design features. First, the membrane
is specifically selected for the pollutant of interest. Second, a re-
tarding potential is maintained across the electrodes of the system to
prevent the diffusion/oxidation of other pollutant species that are not
as easily oxidized. The oxidation-reduction reaction occurs at the
sensing electrode because the counterelectrode material has a higher
oxidation potential than that of the species being reacted. In the cell,
the sensing electrode has a potential equal to that of the counterelectrode
minus the voltage drop across a register. The sensing electrode is electro-
catalytic in nature, and being at a high oxidation potential, will cause
the oxidation of the pollutant and a consequent release of electrons.
Other pollutant molecules, having higher or lower oxidizing potential,
therefore, cannot participate in the cell reaction. The system there-
fore, becomes selective by design. The flow of electrons consequently
becomes directly proportional to the initial $03 concentration which re-
flects the initial TRS concentration in the gas stream.
5.2.3.2 Fluorescence Detection -
Another popular technique for monitoring S02 in a gas stream is
fluorescence spectroscopy. Fluorescence spectroscopy is a photolumi-
nescent process in which the S02 molecule absorbs light of a given wave-
length and re-emits this light at a different wavelength. This release of
energy is directly proportional to the original concentration of S02 present.
As illustrated in Figure 5.21, the conditioned gas sample is brought into the
measurement chamber for excitation.
Sample out
210nm Bandpass
filter
Xe
UV lamp
350ran Bandpass filter
Electronics Border
Photooultiplier
tube
Figure 5.21. Fluorescence Spectroscopy
5-26
-------
An ultraviolet (UV) lamp provides the needed energy to excite the S02
molecule to a higher energy state. The UV energy (hi-) can be a constant
or pulsed source. As the S02 molecule absorbs this energy, it becomes
an electronically excited molecule, as illustrated in the following
equation:
S02 + hv —^ SOp* Absorption
ground
state
excited
state
In this process the excited molecule will remain excited for about
IQ-4 to 10-3 seconds. During this period of time, the molecule will
dissipate some of this energy in the form of vibrational and rotational
motion. However, most of the energy will be re-emitted as light energy
(hv) at a longer wavelength. Figure 5.22 demonstrates the difference
between the absorption and fluorescence spectrum for the S0j> molecule.
0.3r
0.2
E
•S O.I
o>
0.0
S02 ABSORPTION SPECTRUM
[Bandpass
Filter Fluorescence
I I Emission
I \
*
I
.Absorption
\Filter
200
250 300
WAVELENGTH
(nanometers)
350
400
Figure 5.22. Absorption/Fluorescence Spectrum for the S02 Molecule
5-27
-------
The re-emittance of light can be illustrated in the following
equation:
S02 * —* Sf>2 + hv Fluorescent
excited
state
ground
state
A photomultiplier tube is used to change the emitted light energy into
an electronic signal. A bandpass filter in front of the photomultiplier
tube allows only the energy of interest to strike the tube.
Because of interference from water and hydrocarbons, those pollutants
must be removed before sample analysis. In addition, calibration of the
instrument must be performed with S02 in nitrogen or S02 in air, but
not interchangeably. If one calibrates the instrument in 863 in nitrogen,
then the source should have the same level of nitrogen as the span gases.
Fluorescence detection, outside of this quenching problem, has no other
significant interference problems.
5.2.3.3 Flame Photometric Detection -
Flame photometric detection is based upon the principle of a
chemiluminescence reaction of sulfur molecules in a hydrogen-rich
or reducing flame. The sample gas containing the sulfur specie is
introduced into the hydrogen-rich flame, as illustrated in Figure 5.23.
Air pump
Optical window
Light filter
Secondary flame
Primary flame
Amplifier and
read-out
Sample gas
Figure 5.23. Flame Photometric Spectroscopy
5-28
-------
Within the primary flame, the sulfur reacts to provide a Sj>
species. As the $2 specie migrates from the primary flame to the
outer cooler gases, an excited $2* molecule is formed by the following
equation:
•H + 'H + S2-*H2 + S2*
or
•H + -OH + S2 -*S2* + H20
This sulfur specie ($2*) is in a very excited state. Conse-
quently, it remains in that state momentarily, then converts to a
lower energy state. It is this transformation from a high energy
state to a lower energy state that the molecule releases energy as
a strong luminescent emission (hv), as illustrated in the following
equation:
S2* •* S2 - hv
The observed luminescent emission (hv) is monitored by a
photomultiplier tube and is directly related to the concentration
of the sulfur pollutant present by the following equation:
1S2 = I0[S]n
Where:
IS2 = observed intensity of the molecular emission due
to the $2 species
[S] = concentration of sulfur atoms
I0 = constant under given experimental conditions
n = constant (usually assumed to be 2) under given
experimental conditions
The original concentration of sulfur molecules present in the
gas stream becomes directly proportional to the amount of light emitted.
Due to the non-linearity of observed light intensity to the concen-
tration of sulfur pollutant present, most instruments use a linear-
izing electronic circuitry to yield a linear output voltage.
Since all sulfur species burn in the flame differently, it is
imperative that the instrument be calibrated with a particular pollutant
gas of interest. Likewise, since the detection principle cannot
distinguish between different sulfur compounds, added instrumentation
must be used to selectively remove unwanted sulfur species. This can
be accomplished by dry bed scrubbers, liquid scrubbers or gas
chromatography techniques.
5-29
-------
5.2.3.4 Coulometric Detection -
Coulometric detection of SO? in a gas stream has been widely used in
ambient monitoring. The technique utilizes the electrical charge generated
by either the oxidation or reduction of a pollutant gas in the electrolytic
cell as a direct correlation to measuring pollutant gas concentration.
One of the common configurations of this detection principle consists of
four electrodes in a reactor cell as illustrated in Figure 5.24.
Air
Indicator
Reference
'rrf
Generator
Auxiliary
Basic amplifier
Titration amplifier Current amplifier
Figure 5.24. Coulometric Technique
It is within this "titration" cell that the S02 in the gas stream
reacts with the bromine to produce a flow of electrons.
Typically, bromine concentration is maintained at a constant level
by a set of indicator-reference electrodes and the electronic circuits.
As sulfur dioxide is introduced into the detector cells, the bromine
(Br?) concentration is reduced by the reaction.
S0
Br
2H2S04
2 Br~
This reaction disturbs the Brp/Br" ratio, and this change is sensed by
a basic amplifier. The current required to regenerate the bromine (Br2)
through the generator-auxiliary electrodes is proportional to the sulfur
dioxide concentration. The gas sample passes continually through the
titration cell at a constant flow rate. When there is no Sfy ^n ^ne 9as
stream, a constant level of bromine is maintained in the cell by the
platinum wire generating electrode located at the end of the gas cell
inlet. If $03 is present in the gas stream, then the constant concentra-
tion of bromine in the "titration" cell is interrupted. This causes the
sensing electrode to vary the current supplied to the platinum wire, thus
generating more bromine to bring the system back into equilibrium.
5-30
-------
At the anode, the following reaction occurs:
28 r — 2e~^Br2
and at the cathode, the reverse reaction occurs:
When excess bromine is generated, a depolarization current flows and
is proportional to the bromine concentration. The concentration can be
determined by Faraday's Law, which states that one gram equivalent of a
material is oxidized or reduced by one Faraday of electricity. By measuring
the current across the cell, the concentration of the sample may ibe de-
termined since the quantity of electricity (0, coulombs) is given as the
integral of current (i, amperes) over the time interval (t, seconds):
"(i)dt = 0 =
M
Where: m = mass in grams of the species consumed or produced during
electrolysis
M = gram molecular weight
z = number of Faradays (equivalents) of electricity required
per gram mole (i.e., the number of electrons appearing
in the equation for the net reaction of interest)
F = proportionality constant: 96,487 coulombs/mole
This type of coulometric technique measures the amount (i.e.,
coulombs) of electricity directly produced as the result of a
reaction of a pollutant at the electrode.
In current instrumentation, however, pollutant concentration
is determined indirectly by measuring the current required to main-
tain a constant bromine (Rr2) concentration. The sample gas passes
through an electrolysis cell and oxidizes the halogen to halide
(for example, Br2 + pol lutant -*Br~), thereby reducing the halogen
concentration. The current required to maintain the electrochemical
balance is directly proportional to the pollutant concentration.
5-31
-------
5.2.3.5 Gas Chromatography Detection -
Gas Chromatography is a process by which a mixture is separated into
its constituents by a moving phase passing over a sorbent. The technique
is similar to the widely practiced liquid-liquid partition column chroma-
tography except that the mobile liquid phase is replaced by a moving gas
phase.
The basis of the method lies within the separation column. In gas
solid Chromatography, this consists of a solid, porous absorbent packed
in a small thin tube. The packed column is normally 4 mm (i.d.) tubing
of stainless steel, copper, or glass, either bent into a u-shape or
coiled. Lengths vary anywhere from 120 mm to 150 mm. It is the ability
of the column to separate a gas stream into its constituents which enables
the GC to efficiently operate as a TRS monitor.
Basically, gas Chromatography consists of five basic parts: (1)
pressure regulator and flow meter for carrier gas; (2) sample injection
system; (3) separation column; (4) detector, and (5) strip chart recorder,
as displayed in Figure 5.25.
GAS CHROAAATOGRAPHIC SYSTEM
Recorder
Figure 5.25. Typical GC System
5.2.3.5.1. Carrier Gas -
A high pressure gas cylinder serves as the source of the carrier
gas. Commonly used gases are hydrogen, helium and nitrogen. The carrier
gas should be:
o inert to avoid interaction with the sample or solvent,
o able to minimize gaseous diffusion,
o readily available and pure,
o inexpensive, and
o suitable for detector use.
The basic function of the carrier gas is to transport the sample from
the injection port through the column to the detector without interfering
with the analytical technique.
5-32
-------
5.2.3.5.2. Injection Port -
The injection port must be able to allow the introduction of the
sample into the system without fractional on, condensation or adsorption
in other components of the system. Typically, injection ports are heated
to insure that the integrity of the sample does not change.
Historically, gas samples were injected into the GC through a
self-sealing silicon rubber septum by a gas-tight syringe. Technique
has to be quite good in order to inject the same amount of gas into the
system each time. Consequently, gas-sampling valves were introduced to
insure precision injections. In their simplest forms, they include a
system of stopcocks or valves operated by compressed air. Between the
valves is a sample loop of known volume. Gas from this sample loop 1s
introduced into the GC by rotating a valve to connect the loop with the
carrier gas.
5.2.3.5.3 Chromatographic Column -
Once the gas is introduced into the carrier gas stream, it is moved
to the Chromatographic column where separation occurs. As illustrated 1n
Figure 5.17, the column is composed of a liquid phase on a solid adsorbent
packed in a tube. The selection of the liquid depends upon the pollutant
to be separated. For sulfur compounds, the recommended column 1s Teflon
tubing packed with 30/60 mesh Teflon coated with 10% Triton X-305 solution.
Column
Figure 5.26. Chromatographic Column
As the sample gas passes through the column, different species of
sulfur compounds will be retained on the column.
The retention of the pollutant on the column depends upon its inter-
action with the solid support and liquid phase of the packing. As the
carrier gas moves the pollutant through the column, the more easily ad-
sorbed sulfur compounds will be retained first while others flush through.
This separation depends upon:
o solvent properties of the liquid support,
o column temperature,
o solute-solvent interaction, and
o other factors.
5-33
-------
As the separated pollutants exit the column, they are sensed by
the detector, as illustrated in Figure 5.27, and recorded by a data
processor.
I 4 x 10-8 A 1 1 1 1 1 1 T
- 0.10 ppm
H2S
0.18 ppm
C2H5SH
2 x 10-9 A
0.24 ppm
C3HJSH -
TIME
Figure 5.27. GC Chromatogram
5.2.4 Data Handling System
The data handling system is the last component of the TRS continuous
emission monitoring system. Data handling systems can perform many tasks.
Basically, the system receives the input signal from the TRS and diluent
monitor and converts that signal to units of the standard. The data
handling system can also provide
o instantaneous/averaged printout of pollutant concentration,
o perform daily zero/span checks with appropriate adjustments,
o perform quality control check,
o signal warning/alert for high or out-of-control situations, and
o provide maintenance and input notation.
All of the above functions are important tools in a source quality
assurance program.
The most important functions of the data handling system are
o emissions corrected to a percent oxygen, and
o moisture correction.
5.2.4.1 Emissions Corrected to A Percent Oxygen -
Subpart BB specifies that the TRS concentrations for a 12-hour average
must be corrected to 10 percent oxygen for lime kilns incinerators or
other devices and 8 percent oxygen for recovery furnaces. This can be
expressed by the following equation:
5-34
-------
^corr = Cmeas
where:
ccorr = the concentration corrected for oxygen.
cmeas = tne concentration unconnected for oxygen.
X = the volumetric oxygen concentration in
percentage to be corrected to (8 percent
for recovery furnaces and 10 percent for
lime kiln, incinerators, or other devices).
Y = the measured 12-hour average volumetric
oxygen concentration in percent.
5.2.4.2. Moisture Correction -
If both the stack gas and calibration gas are analyzed on the same
basis (dry or wet) then no further correction is needed. However, if one
is on a dry basis and the other is on a wet basis, then the following
correction applies:
Monitor span = (calibration gas, ppm) (1 - Bws) x 100
(monitor response to calibration gas, ppm)
in which Bws = moisture content of the stack gas
Source TRScorr dry = (% response) (monitor span)
' (1-Bws)
When 02 is measured on a wet basis, then
TRScorr, dry = (* response) (monitor span)
(1-BWS, source gas)
When Og is measured on a dry basis, then
TRScorr, dry ~ TRSdry
20.9 - % 0? Specified
20.9 - % 0? measured
? mi
When dry calibration gas is used to calibrate a TRS monitor and the
gases pass through a wet S02 scrubber, the reported data is on a dry
basis and does not need to be corrected for the moisture content of the
gases leaving the scrubber.
5-35
-------
5.3 COMMERCIALLY AVAILABLE TOTAL REDUCED SULFUR CONTINUOUS EMISSION
MONITORS
As discussed In the previous section, the continuous monitoring of
total reduced sulfur from Kraft pulp mills involves different methods of
extraction and analysis. Some systems require moisture removal while
others don't. Some systems convert the TRS to S02 and then analyze the
resultant S02 as TRS, while others measure the TRS directly after column
separation.
Table 5.9 lists the manufacturers who provide TRS systems to the
pulp and paper industry. However, not all systems listed in Table 5.9
have been used in the field or are commercially available as a package
system. Table 5.10 summarizes those systems with reference to experi-
ence categories, while Table 5.11 discusses the operation and maintenance
of those systems with field experience.
Following Table 5.11 are descriptions of the operating principle of
all, commercially available TRS CEM systems.
5-36
-------
TAflLE 5.4
CONKRCIAILY AVAILABLE TOTAL REDUCED SULFUR OMTIRUOUS EMISSION MONITORS
Conpaw *M>
Address and Phone
AnMOn
P.O. Bo> 416
South Bedford Street
Burllnfton. M*. 01M3
Applied Automation, Inc.
Panhuska Road
Bartlcsdlle. W MOO*
(918)676-6141
uendli Corporation (MM
coebuslon engineering)
Environmental 1 Process
Instruments Bullion
P.O. Ormr 831
lenlsburg. N« 24901
(104)647-4358
tandel Industries lldted
986S Host Ssnlch Hud
P. 0. Bo> HBO
Sidney. 8. C. Cmtdi
«8L-4C1
(604)6S6-0156
fharlton Technology. Inc.
P. 0. Bon 26818
S«i Olego. CA Wl»
(61»)S;S-SO*0
Comundi N>«urad
SOj. MjJ. KO,
CO. CO;. H2S.
TR5
TftS. BZ
TBS. S02> '?. u.
«>•
TRS. S02. 0?. CO.
w«
TRS. S02. 02. W,.
CO. Cl. H;S.
Cortuitlbln
TftS. [ilio Ut,
».. Oj. Uz. int
iQrdroctrtMMi )
Nithodi of
NtMUKMAt
Infrared
RadUtlon
Bat ChroHtooraph
fiai chroutogrtpn
nun rim pnoto-
Mtrlc detection
Traniducer
(contlnuoui)
TrtnOnt.tr
(one to tin
•aoplei at a tl«)
Trimducer
(elect rocheolcal
reaction detec-
tion)
FRIAIuoreicent
Monitor
Sjritn
Idintiri cation
Anacon Monitor 206
OptfchrooP 2100
Bendln TS5 Enhiloni
Monitoring Syitec
Eitrackor Model
EP-JOOO
Eitractor Series
EC1000 Source
Saoplen
Oynaljpier Series
3000 (Portable)
Model CM-MOO and
DRISTMt Conditioner
(Models SC-IO.
S01016. 16)
Probe
Ten
stack
Steel
Hetted
Stack
Filter
Inert lal
Filter
Inertlal
F< Iter
Coalescing
Stalnloti
Steel
8»-pa»i
*«*>
StffiB
Eductor
Iductor
Eductor
Air
Eductor
Conditioning S.tte.
Condenter
Do
Air
Cooled
4-5'/£
No
Viporlier
No
Tes
Voi
No
No
"n^
Pew-
pure
Orjrer
Perw-
pure
Dryer
Perae-
pure
Oryer
•era-
pure
Oryer
Transfer
tlnefer
Heated
Not
Heated
Heated
Rot
Heated
so*
Hater cooled
Barton Filter
None
None
Dry SO; Scrubber
Vet Scrubber
CoriMitlon
Furnace
Quorti chips
None
None
Qutrti Tube
QuartiTube
Puoo
Heated
Healed
Heated
Enclo-
sure
Heated
Enclo-
sure
Hooted
Enclo-
sure
Pollutant
Anal«or
UV Differential
Absorption
Gas ChroHtOBriplqr
fiat CnroMtographjr
Tltratlon
Elect roeke.U (hide
Technique
oo
-------
TARLE 5.9 (Continued)
COMMERCIALLY AVAILABLE TOTAL REDUCED SULFUR CONTINUOUS EMISSION MONITORS
Caipany Naeej
Colu4li Scientific
Imkiitrlci Corporation
t. 0. Boil 9908
Austin. T« 787M
(800)531-5003
(5I2I257-51A1 (In TM»)
thVnio Electron Corp. '
10B South Street
Hopktnton. Hill. fll?4fl
(6I7I43S-S32I
ITT Barton Instructs
900 S. Turnout 1 Cinjron Rd.
P. 0. hoi 1MB
Clt> of Industry. M 91749
Lear Slegler. Inc.
74 Inverness Drl>e East
Englemd. CO 801 10
Soling Technology. Inc.
P. 0. toi B
Haldron. All 7295B
Thete Sensors. Inc.
17635-A msland St.
City of Industry. CA 91748
(213)965-1539
Tricor Atlii. Inc.
9441 Baytnorne Or.
Houston. TI 77041
(7I3M62-MIK
Veilern Reieirch
1313-44 Amnue north Cut
Calgary, Alberta
Canada T2E6LS
TRS. SO?. NO,
COz, hydrocarbon
TltS SO;. HOT CO,
TRS. BZ. Op.cH,
TBS '
TIB
TRS. SOj,. Oj
H2S
HjS
TR
Methods of
F1*M PhotoMtrlc
(SOj)
Dtlutlon
Probe Kith Flue
Photontrlc
Detector
Coulowtrlc
tltratlon
Dlfferentli!
Ahiorptlon
Theml (hldetlon
Iff Fluorescent
Tramducer
(elect ruchoriul)
reectlon
detection)
Lead Acetate Tape
optoelectnnlc
detection
(Us throMtmraph
Noeltor
SjPltCM
SA28SE
Model Hit
Syita TRS Monitor
ITT Barton Model
411 TBS Monitor
(Kraft Mill CEN)
TRS Monitor
Model IM TR! Syjte.
Model »M Autoutlc
TRS Analyier
722R HjS Analyier
Model 8?W
-ffideTBRITRS
Analjfier
-£&-
Stack
Stack
Stick
st.a
Stack
Siack
Stack
.Kg! .
Hone
In-Stacl
flul-of-
Stack
Inerllal
Filter
Inertlal
Filter
In-stack
In-itack
fav
Ejector
rwp
Mr
Eeucto
Sieaa
Eductoi
*lr
Eductoi
Conditioning Sjrstea
Hlutlon Principle
Dilution Principle
Refrigeration
Air
Cooled
Dilution
Principle
Air
Cooled
pure
Pern-
pure
Transfer
Llnefer
Rot
heated
Hot
heated
Rot
Heated
Heated
Heated
Not
Heated
Not
Heated
Heated
SOj
Re«,.l
Dry Scrubber
Dry Scrubber
Vet Scrubber
None
irith mlsture
o Dry scrubber
o Liquid scrubber
Liquid Scrubber
Gas ChroMtography
Coftuitlon
Furnace
Horn
Ouarti Tube
Duartt Tube
Dilution Kith
quart! tube
Dilution ulth
overti tube
None
to
Heated
Enclo-
sure
Heated
Heated
Enclo-
sure
Enclo-
sure
Enclo-
sure
Heated
Heated
Aspirator
Pollutant
Analner
Flaie Pbotoectrlc
Fine Photometric
Couloietrlc
Tltratlon
Differential
Absorption
Spectracopy
Transducer
optoelectronic
photowtrlc
Diluent
Analyzer
Ilrconliai Oilde
Cell
Fuel Cell
Tramducer
in
IA>
00
-------
TABLE 5.10
TRS CEM EXPERIENCE CATEGORIES
I. Available TRS Systems with Field Experience
Sampling Technology Inc.
ITT Barton Instruments
Bendix Corporation
Western Research Corporation
Charlton Technology Inc.
II. Available TRS Systems Without Field Experience
Applied Automation Inc.
Candel Industries Limited
Lear Siegler Inc.
III. Systems Not Commercially Available As A Package System
Anacon
Columbia Scientific Inc.
Thermo Electron Corporation
Theta Sensors, Inc.
Tracer Atlas, Inc.
5-39
-------
TABLE 5.11
OPERATION/MAINTENANCE EXPERIENCE OF FIELD INSTALLED TRS MONITORING SYSTEMS
Company Name
Address and Phone
ITT Barton Instruments
900 S. Turnbull Canyon Rd.
P. 0. box 1R82
City of Industry. CA 91749
Sampling Technology, Inc .
P. 0. Box B
Maldron. AR 72958
Traeor Atlas, Inc.
9441 Baythorne Or.
Houston, TX 77041
(713)462-6116
Western Research
1313-44 Avenue North East
Calgary, Alberta
Canada T2E6L5
(403)276-8806
Bendix Corporation (new
cornbusfon engineering)
Environmental i Process
Instruments Division
P.O. Drawer 831
Lewisburg, WV 24901
(304)647-4358
Candel Industries Limited
9865 West Sanich Road
P. 0. Box 2580
Sidney, B. C. Canada
V8L-4C1
(604)656-0156
Charlton Technology, Inc.
P. 0. Box 2BB1H
San Diego, CA 92126
(619)57fl-5040
Compounds Measured
TRS, 02. Opacity
TRS
H2S
H2S
TRS
TBS. Oj,
TRS, S02, nz. CO,
NO,
TRS, S02, Of, CO.
NO,
TRS. S02. 02. NOX.
CO, Cl. H2S,
Combustibles
YDS. (also S02.
NO,, Oj, CO?, and
Hydrocarbons)
Methods of
Measurement
Coulometnc
titration
Thermal Oxidation
IIV Fluorescent
Lead Acetate Tape
optoelectronic
detection
Gas Chromatograph
fias chroma tograph
with flame photo-
metric detection
Transducer
(continuous)
Transducer
(one to six
samples at a time)
Transducer
(electrochemical
reaction detec-
tion)
WMuorescent
Monitor
System
Identification
ITT Barton Model
411 TRS Monitor
(Kraft Mill CEM)
Hade) 100 TRS System
722R H2S Analyzer
Model 82 5R
Model BOO TRS
Analyzer
Bendix TRS Emissions
Monitoring System
Extractor Model
EP-3000
Extractor Series
EC 1000 Source
Samplers
Oynalyzer Series
3000 (Portable)
Model CM-finon and
IWYSTAK Conditioner
(Models SC-in.
SOlOlfi. ]fi)
Operation and Maintenance Problems
o Maintaining constant flow o Cell Replacement o Negative Response to
TRS concentrations o Corrosion o Carbon Intense o Detector cell sensitive
to temperature and pressure variations o Pump o Electrical failure
o Cell and scrubber solutions o Excess drift after changing cell
o Condenser problems o Probe plugging o Leaks in Teflon ferrules
o Dry SOj scrubber and flow control o Eductor problems o Value ticking
o Permeation system o Large dry air requirement
o Refilling of acetic acid bubbler o Replacement of sensitized tape and
»2 tank biweekly o Unit is flow sensitive o Upstream/downstream pressure
sensitive
o Complex o Software problems
o Eductor problems o Perma pure dryer failures o Stainless steel
inertial filter element replacement due to corrosion from lime kiln
o Corrosion o Software problems o Higher degree of technical experience
required o Auto valving failure o Moisture
o Limited Field Experience
o Hydrocarbon cutter replacement
Installations
None
X
0-10
7
X
X
X
11-25
>25
X
X
Hanhours
Per Month
40
45
1 50
N/A
7>
-------
5.3.1 Candel Industries Limited
Candel Industries Limited (CIL) has developed a highly specialized
system for monitoring TRS compounds in the presence of SC^. In essence,
a source sample is extracted from the source, conditioned and analyzed
for S02 by an electrochemical transducer. As illustrated in Figure 5.28,
the basic components of the system are:
o Probe/conditioning system;
o S02 scrubber and TRS converter system; and
o Electrochemical sensor.
V
ANALYZER- — — — — —|
NEMA 4 ENCLOSURE
Figure 5.28. Candel Industries TRS System.
-------
5.3.1.1 Probe/Conditioning Sustem -
The probe/conditioning system consists of a titanium probe, an air
cooled condenser with condensate trap, and an eductor for sample gas
extraction. As illustrated in Figure 5.29, the sample gas is extracted,
by the eductor (E), through the probe to the air cooled condenser (CC).
There, the gas stream is cooled between 0-5°C. Condensibles are condensed
and collected in the condensate trap (Co). By way of a second pump
located in the instrument module, a sample portion of the sample gas (S)
is extracted from the larger gas stream for subsequent analysis.
0
orobe
IT
Figure 5.2°>. Probe/Conditioning System.
5.3.1.2 SO? Scrubber and TRS Converter -
The particulate and moisture free gas stream is transported to the
analyzer enclosure by way of an unheated umbilical cord. Once at the en-
closure, the gas enters a dry bed scrubber where S(l2 is selectively re-
moved from the gas stream without interfering with the TRS components. The
scrubber element also removes any entrained particulates and moisture from
the sample gas. The moisture absorbed from the sample gas also aids the
S02 scrubber action. Once S02 is removed from the gas stream, the stack
gas then passes through an oxidizer which converts the TRS components to
S02- The sample gas is then pumped, by a continuous duty corrosion re-
sistant pump, to the analyzer.
5.3.1.3 Electrochemical Sensor -
As illustrated in Figure 5.30, the CIL TRS analyzer utilizes the
polarographic principle of detection for measuring S02 (TRS converted) in
the gas stream.
b-42
-------
Sample
gas flow
Membrane
Sensing
electrode
Counterelectrode
-------
Figure 5.31. Charlton Technology Model CM-6000 TRS System.
5.3.2.1 Probe/Sample Conditioning Assembly -
The probe assembly is typically a 3/4" corrosion-resistant alloy
unit about 3 feet long. The probe is mounted on the source with a mount-
ing hub. A locknut on the mounting hub permits the operator to slide the
probe body into the stack to any desired depth. The probe is designed
for a single point extraction. Because the probe is attached to the
sample conditioner with a heat trace line, it can be removed easily for
periodic service or inspection.
The gas sample is extracted from the stack by means of a venturi-
type air eductor. The sample is brought into the heated fiberglass sample
conditioner enclosure and maintained at a temperature above sample dew point.
A side-stream withdraws a small portion of the gas by a diaphragm pump
through a sintered stainless steel bypass filter (to remove particulate
down to 1 micron or less). This technique is termed inertial filtration.
The clean, filtered sample is then introduced to a permeation dryer,
externally mounted on the side of the module, where moisture is removed to
achieve a dew point below ambient temperature. This eliminates the require-
ment for a heat-traced sample line between the sample conditioner and the
analyzer in the control room. Figure 5.32 displays the components of the
probe/sample conditioner system.
5-44
-------
PROBE FILTER
316 STAINLESS STEEL
SINTERED ELEMENT. 40 MICRON
PROBE
/
FLVASH DWERTOR
EOUCTORVENT
OPTIONAL RETURN TO STACK
OVEN 50* C-100* C
CALIBRATION
VALVE
AIR EDUCTOR
BYPASS FILTER
318 STAINLESS STEEL
SINTERED ELEMENT. 5 MICRON
BLOWBACK VALVE
n
CALIBRATION INLET
EOUCTOR AIR
WET VENT
PERMEATION
DRTER
MT PURGE AMI
•9
SAMPLE OUT
Figure 5.32. Probe/Conditioning System.
5.3.2.2 Sample Transport Line -
From the conditioning system, the moisture and particulate free gas
stream is transported, by positive pressure from the diaphragm pump, to
the sample control module by a 7-bundle sample transport line. The 7
bundle transport line involves:
Tube #
1
2
3
4
5
6
7
5.3.2.3 Instrumentation Module -
Function
AC Power to Sample
AC Switching
Calibration Gas.
Sample Line
Purge Air
Eductor Air
Spare
Conditioner
The instrumentation module contains the diluter module, the dry-bed
S02 scrubber, the TRS to SOg converter, the CSI fluorescence S02 analyzer,
the Thermox oxygen analyzer and recorder/data processor. As shown in
Figure 5.32, the undiluted sample gas flows from the sample conditioner to
the analyzer where it is divided into two streams. The major portion of
the sample (dry and undiluted) flows to the oxygen analyzer for analysis
while the smaller flow enters the sample diluter where a precision dilution
is made with zero air. From the diluter, the sample passes through a dry-
bed S02 scrubber, then to a TRS oxidizer to convert TRS to SC»2 then finally
to the fluorescence 502 analyzer for analysis. Figure 5.33 displays the
instrument rack containing all monitoring systems associated with the TRS
system. The amount of SC<2 present, as indicated by the fluorescent S02
analyzer, is directly proportional to the original concentration of TRS
present in the stack gas.
5-45
-------
Figure 5.33. Charlton Technology TRS Instrument Rack.
5.3.3 Columbia Scientific Industries
The Columbia Scientific Industries (CSI) dilution probe operates on
the principle of extracting a gas sample from the source, diluting that
sample with clean, dry instrument air and analyzing the gas components
with EPA certified ambient air monitors. The CSI stack gas analyzer
comprises two parts:
o The in-situ sample conditioning/dilution probe; and
o Meloy Labs flame photometric or fluorescence S02 analyzer.
5-4fi
-------
5.3.3.1 Conditioning/Dilution Probe
The main objective of the conditioning/dilution probe is to extract
a precise sample volume from the source, remove particulate and dilute
the source sample to ambient concentration, all at stack conditions.
Figure 5.34 illustrates the major components of the conditioning/
dilution probe.
I M IISI /1KOC, \i
CJiiulii)
I OAHif FILIH
Figure 5.34. CSI Dilution Probe.
In operation, stack gas is first drawn through a fine filter and
metered by a critical orifice, as shown in Figure 5.35.
CALIBRATION LINE
CRITICAL ORIFICE
COARSE FILTER
STACK GAS
NE FILTER
STACK GAS
Figure 5.35. Fine Filter/critical Orifice of CSI Dilution Probe.
A vacuum is drawn on the stack continuously, through the filter and
critical orifice, by a small eductor pump mounted behind these components
(Figure 5.36). Pressurized dilution air creates a vacuum in the space
between the primary and secondary nozzle causing the movement of the
stack gas through the system.
5-47
-------
CAL. LINE / ZERO GAS
DILUTED SAMPLE
• MOUNTING FLANGE
DILUTION AIR / HEAT EXCHANGER
PRIMARY NOZZLE
BORE HOLE
SECONDARY NOZZLE
TO VACUUM GAUGE
DILUTION AIR
Figure 5.36. Secondary Nozzle of CSI Dilution Probe.
The sample is then diluted in the ejector pump in the stack probe to
a known proportion with dry air.
The diluted gas stream, 100:1 ratio, is then fed through unheated
sample lines to a dry S02 scrubber and then to the ambient continuous
emission monitors, located off the stack, for subsequent analysis by
flame photometry.
When utilizing the dilution probe technique, the measured pollutant
concentration is on a wet basis.
5-48
-------
5.3.3.2 CSI Analyzer
In flame photometry, the sample is excited to luminescence by intro-
duction into a flame. A hydrogen flame is used in the flame photometric
method to excite the sulfur atom. The excited atom will, in turn, emit
light in a band of wavelengths centered at about 394 nm, which is then
detected by a photomultiplier tube, as shown in Figure 5.28.
EXHAUST
FILTER
PHOTOMULTIPLIER
TUBE
SAMPLE
Figure 5.37. CSI Flame Photometric Detector.
A disadvantage of flame photometric analyzers is the required hydrogen
for the flame. Facilities that have strict regulations concerning the
use of hydrogen and hydrogen cylinders may find it inconvenient to utilize
this method. For this reason, fluorescence spectroscopy has been used for
the detection of SOg in the gas stream more often than flame photometry.
5-49
-------
5.3.4 Tracer Atlas, Inc. Total Reduced Sulfur Continuous Measurement
System
The Tracer Atlas Total Reduced Sulfur measurement system is based on
the chemical reaction between lead acetate and hydrogen sulfide to produce
black lead sulfide. The total reduced sulfur measurement system is divided
into two subsystems: (1) sample acquisition and conditioning, and (2)
sample measurement.
5.3.4.1 Sample Acquisition and Conditioning System -
The two constituents of the stack atmosphere that can interfere with
TRS measurements are particulates and water vapor. The Tracer Atlas TRS
sample acquisition and conditioning system is designed to eliminate
particulates and to lower the water vapor concentration in the sample gas
so that its dew point will be under reasonable ambient temperatures.
The sample acquisition/conditioning system begins with a probe
containing a stainless steel fritted filter. The fritted filter is
periodically cleaned by back flushing with dry dilution gas. The back
flushing procedure takes place each tape update of the analyzer or every
3 minutes. The back flushing pulse will last only 1/4 of the tape movement
time to allow normal forward flow to be re-established before tape movement
stops and the next reading begins.
Under normal sampling the gas is extracted from the stack by a pump
placing a vacuum on the probe. At the back of the probe is a tee. A dry
gas is injected into the sample stream in sufficient quantity to drop the
dew point of the sample diluent mixture below the ambient temperature
range. The flow rate of the sample from the stack is essentially the
flow rate of the pump minus the flow rate of the diluent gas. The flow
rate of the pump is kept higher than the diluent flow rate to maintain a
net sample flow from the probe. The ratio of flows is not critical as
long as the dew point of the mixture is below reasonable ambient condition
and the flows remain constant.
5.3.4.2 Sample Measurement System -
The conditioned stack gas sample is then introduced into a barium
acetate S02 scrubber where SOg is removed while allowing all other sulfur
species to remain in the sample gas. The gas exiting from the scrubber is
mixed with hydrogen and introduced into a tube furnace where all remaining
sulfur species are hydrogenated to
The reacted gas then exits the furnace and enters the H2S analyzer
where the H2S concentration of the gas is determined. The ^S concentration
is directly proportional to the amount of total reduced sulfur in the stack
gas sample.
5-50
-------
The H2S analyzer is based on the lead acetate detection principle.
The analyzer has no known interferences. Very high sensitivity is achieved
by using a stopped-tape method, detecting the darkening of the tape opto-
electronically, and then differentiating the signal with respect to time.
The output of the analyzer is the rate of change of darkness of the tape
which is directly proportional to the HgS concentration for a given set
sample flow rate. The method is capable of measuring ^S in samples in
the low parts per billion range.
The H2S sample flows into the reaction window (Sample Chamber) where
it passes over an exposed surface of lead acetate impregnated paper, as
shown in Figure 5.38.
TUNGSTEN
LAMP
PRIMARY
FOCUSING
LENS
MIRROR
PHOTOCELL
FINE FOCUS
BALANCING
LENS
REFERENCE
PHOTOCELL
MEASURING
PHOTOCELL
RATE-OF-
CHANGE
INDICATOR
REACTION WINDOW
SAMPLE CHAMBER
EXPOSED SENSING TAPE'
Figure 5.38. Sample Measurement System; Impregnated Lead Acetate Paper.
The lead acetate paper darkens due to the presence of ^S, as lead
sulfide is formed. The rate of darkening of the exposed tape is proportion-
al to the HgS concentration in the stack gas. The amount of darkening of
the tape is monitored by a patented optical system.
5-51
-------
As illustrated in Figure 5.29, light from a 14 volt DC tungsten lamp
is focused into the viewing area by a primary lens. The light then strikes
the sensing tape and is reflected to the measuring photocell. Simultaneous-
ly, the light from the same 14 volt DC tungsten lamp is reflected from a
mirror and focused to produce a reference beam for the reference photocell.
Signals from the measuring and reference photocells are sent to the rate
reading electronics to produce a meter deflection. The difference between
these two signals is directly proportional to the TRS originally present
in the stack gas stream.
5.3.5 Lear Siegler Continuous TRS Monitoring System
For continuous monitoring of TRS, Lear Siegler utilizes an extractive
measurement system whereby a representative sample of stack gas is contin-
uously extracted from a sample point. The reduced sulfur compounds (hy-
drogen sulfide, methyl mercaptan, dimethyl sulfide and dimethyl disulfide)
are thermally oxidized and analyzed as S02 utilizing Lear Siegler's dif-
ferential SOg analyzer. The dual beam differential SO2 analyzer produces
an output reading of equivalent part per million TRS independent of the
coexisting SOg concentration. The differential signal is processed by a
data acquisition system to produce an oxygen-corrected TRS concentration.
Figure 5.39 illustrates the basic components of the Lear Siegler TRS system.
Figure 5.39. Lear Siegler TRS CEM System.
5-52
-------
5.3.5.1 Probe and Primary Filter Assembly -
Unique In Its design, the probe assembly Includes an electrically
heated filter chamber, located outside the mounting flange. This allows
the filter to be maintained without removing the probe from the gas
stream. The filter location also eliminates pluggage of the filter by
direct impact of particulates or water droplets on the filter. For ease
of maintenance, separate gas connections for sample extraction, backpurge,
and calibration gas injections are incorporated in the filter chamber
design.
The probe is mounted sloping downward into the stack. The open end
of the probe is cut at an angle to create an opening away from the gas
flow. This eliminates direct impingement of particulates, enabling the
filter backpurge system to maintain a clear sample tube in most cases.
The straight-through design of the sample tube allows blockage to be
cleared with a ramrod without removing the probe from the gas stream.
For TRS monitoring applications, the probe includes a Teflon lining
and a non-reactive, sintered glass heated filter to remove particulates
without loss of TRS components. Check valve inlets are provided for both
calibration gas and high pressure backpurge air, both automatically se-
quenced from the analyzer cabinet. Manual valves are provided for periodic
backflush of probe with either water or air.
5.3.5.2 Sample Transport Line -
The Lear Siegler system includes heat-traced teflon®-lined sample
transport lines from the probe location to the analysis cabinet. Self-
limiting, heattraced lines operate without any external temperature con-
trol or voltage limiting devices. The sample gas stream temperature is
maintained above the dew point throughout its run, thereby preventing
condensation and resultant loss of TRS in transport.
5.3.5.3 Sample Drier -
The sample is dried to a dew point corresponding to the coolest am-
bient temperature in the gas transport system by means of a simple air
to air cooling system. For maximum cooling efficiency, the gas flows
through multiple teflon tubes which are in direct contact with the ambient
air. The condensate exits the bottom of the heat exchanger to an automatic
liquid drain, while the dried sample is drawn out for final filtration
and analysis. For lime kiln applications, a sample drier may be located
in a heated enclosure at the probe to remove moisture before entering
the heated sample line.
5.3.5.4 Thermal Oxidation Furnace -
An electrically heated quartz tube thermal oxidation furnace is
provided to oxidize the sample stream reduced sulfur compounds to S02
prior to analysis. Sample temperature in this oxidizer is approximately
750°C and residence time is maintained so that further oxidation to $03
does not occur. Due to the relatively small amount of TRS and the
typically high content of Og, the TRS compounds are completely oxidized
b-b3
-------
without substantially altering the f»2 content of the sample gas stream. A
coiled tube heat exchanger following the oxidizer is provided to cool the
sample gas prior to analysis.
5.3.5.5 Gas Prime Movers -
Low flow rate air eductors operated by compressed air draw the
sample from the stack and transport the sample stream to the analyzer
cabinet. A teflon lined diaphragm pump moves the gas sample through the
thermal oxidation furnace, secondary filters and to the analyzers. A
back pressure regulator and calibrated rotameter are provided for flow
control to the analyzers. As a result, the analyzers are operated at
near atmospheric pressure.
5.3.5.6 Dual Beam Differential SO? Analyzer -
The S02 analyzer provides dual beam differential measurement of $03,
which produces an output reading of equivalent parts per million of TRS
independent of the coexisting S02 concentration. tAn ultra-violet light
source is directed through the measurement cell, which is divided into
measurement and reference sections. The light beam passing through the
cell is gated alternately through the measurement and reference sections
by a continuously rotating chopper. The light reaching the detector at the
opposite end of the cell is attenuated by the S02 present in each section
of the cell. The gas stream extracted from the process is flowed continu-
ously through the reference section of the cell, providing a reference S02
level equal to the process S02 concentration. At the same time, the ex-
tracted gas stream is oxidized by the thermal oxidation furnace where the
TRS is oxidized to S02 and the original S02 In the extracted gas stream re-
mains. This gas stream continuously flows through the measurement section
of the analyzer. The detector, therefore, measures a varying light inten-
sity as the light beam is alternated between the measurement and reference
sections, and the difference in the two measurements is proportional to the
S02 produced by oxidizing the TRS compounds. Rotating at 1600 revolutions
per minute, the chopper generates two test periods in each rotation and
gates the light beam through the reference and measurement sections of the
cell. During each test period, zero and gain of the instrument are auto-
matically adjusted to compensate for the effects of line voltage variation,
lamp and detector aging, and varying concentrations of background S02-
5.3.5.7 Microprocessor Controller -
The microprocessor controller accumulates continuous concentration
data and provides both one and twelve-hour averages. Diluent (02) correc-
tion is also provided and required violation summaries are generated. Re-
corders and/or printers can be located remotely for operator convenience.
Automatically sequenced calibration is initiated by the microprocessor
controller and accomplished at the probe location through the introduction
of known concentrations of h^S and 62 span gases. Calibration gas is de-
livered to the probe via a separate Teflon line thus allowing the sample
line to be used only for transport of the sample gas. This assures fast
5-54
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response time to changes in sample TRS concentration. Further, the mea-
surement of calibration gas injected at the probe ensures a valid evalua-
tion of the entire measurement system including the normal sample line.
All components function under normal operating conditions during the cali-
bration check thereby verifying normal operation. The automatic calibration
cycle normally occurs once every twenty-four hours.
5.3.6 Theta Sensors, Inc. Model 7600 TRS Monitor
The Model 7600 consists of several individual components designed
for and integrated into the overall system. The main components of the
system are the sample probe, pump, sample line, sulfur dioxide scrubber,
TRS oxidizer, oxygen and sulfur dioxide analyzers, and the data logger.
The heart of the monitor is an electrochemical transducer which
selectively measures $03.
Source monitoring requires the sample to be acquired from the source
and conditioned so as to be compatible with the requirements of the
monitor. These tasks must be accomplished without degrading the sample's
integrity. The complexity of the sampling system, therefore, depends
primarily on the monitor requirements. TSI instruments require a clean
gas, free of particulates, and a dry gas free of entrained water with a
dew point less than the monitor's ambient temperature.
5.3.6.1 Sample Probe -
The analysis begins with the extraction of the sample from the source
by a probe/conditioner system. Within the probe, the high speed sample
passes through a tubular (inertial) filter. A small portion of this sam-
ple is drawn radially through the porous filter wall at a velocity so low
that the inertia of solid and liquid particulates will be too high to curve
through the wall of the filter. The resulting sample is free of interfering
particulates, but will be saturated with water vapor. To prevent water from
condensing in the lines the sample is immediately dried using a permeation
dryer. The cool, clean, and dry sample is transported to the rest of
the system.
5.3.6.2 Sample Pump -
Since the sample now has a very low water content, it is pumped with-
out further condensation. A stainless steel and inert plastic diaphragm
pump provides a sample flow of approximately two liters per minute. The
pump is located at the probe so that the balance of the system will be
under pressure to eliminate small leaks in the sample line.
5.3.6.3 Sample Line -
Because the sample has very low moisture content, the sample lines are
not heated. Almost any line material can be used which will not degrade
the sample. TFE or FEP may be used as well as polypropylene or 316
stainless steel.
5-55
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5.3.6.4 Sulfur Dioxide Scrubber -
Theta sensors utilize several methods for removal of S02, including
both solid and liquid techniques. Although the solid scrubbers are attrac-
tive because of their apparent ease of use, they have limited capacity,
and must be replaced or serviced frequently. Theta sensors use a number
of liquid scrubbers, including saturated sodium bicarbonate and citric
acid/sodium citrate. Both of these liquid scrubber solutions are non-
toxic and non-corrosive. From the S02 scrubber, the sample goes to the
TRS oxidizer.
5.3.fi.5 TRS Oxidizer -
Before entering the oxidizer, the stack sample is diluted to ensure
enough oxygen present for oxidation.
The diluted sample is heated to 100°C in a quartz reaction tube. The
result is a complete conversion of the reduced sulfur compounds to SOg.
5.3.6.6 Detector
The Theta Sensors transducer utilizes the chemical reaction occurring
between a gas and a charged electrode to produce a current flow which is
measured in an electronic circuit. The transducer is often referred to
as an electrochemical transducer.
The transducer is divided into two major sections. The upper section
provides a flow path for the sample gas while the lower section is the
reaction chamber. The two sections are separated by a permselective membrane
and sealed by the compression of an "0" ring and gasket. A snap ring
fastens the assembly together.
The permselective membrane accomplishes three important tasks. First,
the proper choice of membrane allows the gas specie under investigation to
diffuse through it more rapidly while inhibiting the passage of interfering
gases, thus providing a degree of specificity. Second, the membrane reduces
the amount of reactive gas reaching the sensing electrode, thereby increasing
the life of the transducer. Third, the membrane seals the electrolyte in
the body allowing the transducer to be operated in any position.
As the sample gas diffuses through the membrane, the gas specie under
investigation is either oxidized or reduced by the sensing electrode which
is maintained at a fixed potential in relation to the counter-electrode.
This potential is unique to each gas specie.
The oxidation or reduction of the gas specie, i.e., the gain or loss
of electrons, causes a flow of electrons between the two electrodes. This
current is measured in the external electronic circuitry. The current
produced is directly proportional to the concentration of the specie in
the sample gas, thereby assuring linearity over the entire dynamic range.
Accordingly, a direct relationship exists between reduced sulfur compounds
in the gas stream and current produced at the detector.
5-56
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b.3.6.7 Oxyen and Sulfur Dioxide Analysis -
The oxygen 1s measured In the sample stream just prior to the addition
of the diluent air. The measurement is made with an electrochemical sensor.
5.3.6.8 Data Logging
The computer provides for all self-testing and data logging needs
of the system. The TRS measurements and any corrections for oxygen
concentration are based on a dry sample, and need not be corrected for
the moisture content of the stack. Consequently, the data logger produces
all concentrations in units of the standard.
5.3.7 ITT - Barton Titrator
The ITT-Barton Model 411 recording sulfur analyzer consists of three
distinct components: (1) probe module; (2) sample module and (3) titration
module. A stack gas is extracted from the source, conditioned and analyzed
coulometrically through an oxidation-reduction reaction. The measurement
is performed by adding a known amount of reagent to a sample until the
reactive components are exhausted. By measuring the current required to
maintain a constant concentration of reagent, a concentration of pollutant
entering the module can be calculated.
Coulometric analysis uses the electrical change generated by the re-
duction of bromine in a titration cell to measure the S02 gas concentration
in the measurement stream. The titration cell consists of three electrodes
arranged to form two functional pairs. One pair acts as the bromine gener-
ating electrode and the other pair serves as a sensing and control electrode,
The anode is common to both pairs of electrodes. Figure 5.40 demonstrates
the arrangement of these electrodes.
Detector I
cell* I
Platinum anode
Reference electrode
Constant
current
source
"TpiS
Ic
tinum
cathode
Recorder
*Gas phase sample is continuously introduced
into detector cell
Figure 5.40. ITT Barton Titrator.
5-57
-------
The operation of the cell involves maintaining a constant concentra-
tion of bromine in the electrolytic solution. As SOg is introduced into
the cell, the bromine concentration is reduced by the following reaction:
S02 + Br2 + 2H20 —> H2S04 + 2Br~ + 2H+
The equilibrium of the electrolytic solution (Br2/Br~) is disturbed
and this change is sensed by the basic amplifier. Changes in the concen-
tration of bromine in the cell electrolyte cause the sensing electrode
to vary the current supplied to the input of the electrical circuit. This
current provided by the control module causes the production of bromine
at the sensing electrode to return the cell to its original equilibrium
or end-point condition. The amount of current required to maintain this
equilibrium (end-point) is proportional to the concentration of S02 (and
consequently TRS) in the sample gas. The following reactions occur at the
individual electrodes:
2 Br - 2e~ --> Br2 (anode)
Br2 + 2e~ --> 2 Br (cathode)
By measuring the current across the cell from these combined reac-
tions, the concentration of SOg in the sample gas can be determined
through Faraday's Law. Faraday's Law states that one gram-equivalent of
material is reduced by one Faraday of electricity according to the follow-
ing reaction:
(I) dt = Q = nwF
m
Where:
I = current (amperes);
dt = time interval (seconds);
Q = quantity of electricity (coulomb);
n = number of Faradays (equivalent) of
electricity required per gram mole;
w = weight of species consumed or produced
during electrolysis;
F = proportionality constant (96,487 coulombs/mole)
M = molecular weight of pollutant (grams)
5.3.7.1 Probe Module -
The probe module consists of the extraction probe, a calibration gas
injection port and a refrigerated condensate trap, as shown in Figure 5.41,
The gas sample is extracted K 1 CFM) through the probe by a pump located
5-58
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in the sampling module, and transported to the condensation trap in the
refrigerated lower section of the module. The refrigeration is supplied
by a vortex tube cooler controlled by a thermostat-solenoid valve combina-
tion. As water is removed from the gas stream, it collects in the conden-
sate reservoir which empties once per day. The moisture-free gas stream
exits the probe module and moves through heat traced tubing to the sampl-
ing module.
5.3.7.2 Sampling Module -
The sampling module contains the high volume sample pump, back-purge
equipment and the heat controller for the heat trace line. Back-purge is
controlled by a timer which actuates a solenoid valve. The valve allows
instrument air (regulated to 10 psi) to purge the heat-traced sample
line, the probe and the condensate reservoir. While the sampling assembly
is being back-purged, the sample pump draws ambient air and routes it to
the analyzer for instrument zero. Figure 5.42 displays the physical
arrangements of these components in the sampling module.
5.3.7.3 Titration Module -
The titration module contains the Sfy filters, thermal oxidizer, ti-
tration cell and aspirator. Only a small fraction ( 250 cc/min) of the
total sample from the sample module is analyzed. As demonstrated in Fig-
ure 5.43, the aspirator pulls the sample from the sampling module and into
the SOg scrubber. The scrubber is a solution of potassium citrate/citric
acid in water. Next, the S02-free gas stream passes through a thermal oxi-
dation device which oxidizes all remaining sulfur compounds to S02. From
the oxidizer unit, the gas stream enters the titration cell where S02 reacts
with the bromine solution to produce a current. The amount of current gen-
erated is directly proportional to the SOg concentration (thus TRS) in the
gas stream.
5-59
-------
CAL GAS
Figure 5.41. ITT Barton Probe/Extractive System.
5-60
-------
HEAT TRACED
SAMPLE LINE
SAMPLING MODULE
> VENT
SAMPLE
250 CC/MIN
J
AMBIENT
AIR
Figure 5.42. ITT Barton Sampling Module.
5-61
-------
SAMPLE
ZBO CC/MIN
CAL. «A$
VENT
CONTROL
MODULE
TITRATION MODULE
I
Figure 5.43. ITT Barton Titration Module.
5-62
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5.3.8 Western Research TRS CEM
The Western Research Model 800 Series Total Reduced Sulfur (TRS)
analyzer consists of these basic modules:
o Probe/Conditioning System;
o Analyzer; and
o Remote Output.
The system is based upon gas chromatographic analysis for hydrogen
sufide, carbonyl sulfide, dimethyl disulfide, methyl mercaptan and dimethyl
sulfide. Western Research employs gas chromatography as its analytical
technique because: (1) other analytical methods cannot distinguish between
the different molecular forms of reduced sulfur in the gas sample; and
(2) there is no alternative methodology which equally responds to all
reduced sulfur compounds, thus limiting established calibration techniques.
Western Research developed a process chromatographic technique to dis-
tinquish between all sulfur compounds. Since the presence of SOg and H20 in
the stack gas interferes with the detection of the reduced sulfur compounds
they had to be either removed or separated. Consequently, Western Research
developed a process TRS gas chromatography analyzer. Figure 5.44 illus-
trates the basic components of the Western Research Model 800 Series
Total Reduced Sulfur Analyzer.
STACK
=| PROBE
t
CONDITIONING
SYSTEM
DETECTOR
SYSTEM
DATA
PROCESSOR
SYSTEM
Figure 5.44. Western Research TRS CEM System.
5-63
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5.3.8.1 Probe/Condi'tiom'ng System -
The probe/conditioning system consists of a straight-in sampling
probe and a Balston filter for particulate control, all enclosed in a
heated weatherproof unit. As illustrated in Figure 5.45, the system
allows for back-purge and injection of span gas as close to the probe
tip as design specifications allow.
^STRtAH SfLCCr
X
\
BALSTON 33 S FILTER
CHECK
VALVE
TJ
MOUNTING
fLANGl
2 MY SOLENOID
SPAN GAS
ELECTRICALLY HEATED
TFE StMPLZ LINE.
SPAN GAS LINE
f IHTE&RAL V/rW,
SAMPLE LINE I
TO AHALfZEA
BACK - PURGE
IN5TRVM£.NrAtR
Figure 5.45. Western Research Probe/Conditioning System.
The sample is extracted from the source by an air driven teflon
aspirator located downstream in the main analyzer enclosure. The sample
then passes through the particulate control device and moves through heat
trace teflon line to the main analyzer enclosure. Since water is not
removed in the sample/conditioning system, the sample line is maintained
at 120°C.
5.3.8.2 Analyzer -
Once the heated sample reaches the analyzer, it is separated and
analyzed by gas chromatography. In gas chromatography, an aliquot of
the stack sample is physically separated into its components by passing
it through a packed column with an appropiate carrier gas. The migration
rate of each component through the column is governed by its absorption
affinity relative to the material of the absorber. Column materials,
lengths and operating conditions are selected so that each specie of
interest is separated from its neighbors and quantified by an appropriate
5-64
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downstream detector. As Illustrated in Figure 5.46, the stack gas enters
the analyzer, passes through a line filter and then into the heated
sample loop where an aliquot is retained for analysis. At a select time,
carrier gas is injected into the sample loop and fences the pollutants
downstream through the chromatographic column to the detector.
CARRIER GAS
fEMP PROGRAMMED
OVEN
I CHROMATOGRAPH
VENT TO
ATMOSPHERE
t
SAMPLE
INJECT
WLVE ACTUATOR
J
1
- 1
FPD
DCTC.C*
•TOK
«„ da
MAIN OVEN
I"
LOOP
TEMP
AIK
—o
SAMPLE
LOOP r-
PZE5S
L
FILTER
FROM
SAMPLE
CONDITIONING
SYSTEM
INSTR AIK TO
ASPIRATOR
wive
CALIBRATION GAS
I
INS1RUMNT AIK
Figure 5.46. Western Research Analyzer System.
5-65
-------
By virtue of the column material , temperature and physical con-
figuration, the separation of reduced sulfur compounds in the presence
of carbonyl sulfide (COS), sulfur dioxide (SOg) and water vapor (^0)
is accomplished. Figure 5.47 displays a typical chromatogram from a
Western Research TRS CEM system.
HP 3338R
DLV OFF
MV/M 38
STOP
RTTN
OFF
123
REJECT 188
5-s5 JEST 1-18(H*S)
1.
1.
4
6
'STOP
RT
13
64
33
43
RRER
TVPE
M
9. 31
RRER
549468
583233
293716
533918
152572
25. 57
27. 59
14. 13
25. 49
7. 213
Figure 5.47. Typical Chromatogram from Western Research TRS CEM System.
R-66
-------
Once separation is accomplished by the chromatographic column, a
dual flame photometric detector (FPD) quantitatively detects molecular
sulfur in the presence of other components. The output response of the
FPD is independent of the molecular form of the sulfur and is proportional
to the square root of the sulfur mass entering the detector. The concent-
ration of each sulfur species present in the sample is measured on a hot
and wet (i.e., "as is") basis and printed out. The TRS emission is
calculated as the sum of the concentrations of the reduced sulfur compounds.
COS and S02, if present, are not included in the calculated and reported TRS
emission. The system automatically checks and adjusts its calibration by
means of span gas injected at the sample conditioning unit every 8 hours.
Changes in calibration are printed on the hard copy output.
5.3.8.3 Remote Output -
The Remote Output processes the signal from the detector and displays
final concentrations of individual TRS components of the gas stream. A
typical printout of the system is displayed in Figure 5.48.
81/H/OI
PRECIP 0/L
TIhE P T »?
16:00 646 374 01
H2S
28
AUTO CALIBRATION CHANGE = 1.11
GC CALIB GAS
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
PRECIP 0/L
16:13 611 374
16:25 643 373
16:36 646 371
16:47 645 372
16:57 646 372 01
17:08 645 372 01
17:19 648 371 01
17:29 647 371
17:44 649 374 01
17:54 648 371 01
18:05 648 372
18:15 647 371
18:26 648 372 01
18:36 647 372 01
18:47 648 371 01
18:58 648 371 01
19:08 648 371 01
19:19 646 371 02
4.7
24
30
42
22
26
21
20
34
30
31
19
42
30
39
45
51
50
COS
34
25
29
33
32
36
40
32
27
34
32
33
33
42
37
42
44
42
37
502
RSH
4.7
3.1
5.0
3.5
4.6
4.1
3.7
2.8
4.5
5.1
2.3
4.1
4.5
6.0
4.2
5.4
R2S
0.8
1.5
R2S2
0.8
1.6
1.6
1.2
1.0
0.9
1.1
1.4
0.6
1.3
1.1
1.1
TRS
34
4.7
28
35
47.
27
31
25
25
41
37
33
21
49
36
48
53
SB
53
Figure 5.48. Western Research TRS CEM System Remote Output Display,
5-67
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5.3.9 Sampling Technology Incorporated TRS CEM System
The Sampling Technology Inc. (STI) Model 100 Total Reduced Sulfur
(TRS) monitoring system is designed to measure and report TRS data from
lime kilns, recovery boilers, smelt tank vents and other TRS sources
within the Kraft pulp mill. Like other extractive systems, it is able to
monitor several sources simultaneously. The system is based on Proposed
Federal Reference Method 16A where a sample is extracted, conditioned,
(particulate, water and S02 removed), oxidized and then analyzed.
Unlike proposed Federal Reference Method 16A, the STI system can incorpor-
ate either UV fluorescence or coulometric titration analysis in place of
16A wet chemical analysis.
The system consists of six functional components
o probe/conditioning system - the objective of the probe/
conditioning system is to extract a sample from the
source, remove moisture and transport the sample to the
dilution system,
o dilution control system - the dilution control system
properly dilutes the stack gas to ambient concentra-
tion,
o sulfur dioxide scrubber - similar to proposed Federal
Reference Method 16A, sulfur dioxide must be removed
from the gas stream prior to analysis. Consequently,
a dry bed S02 scrubber is used,
o thermal oxidizer - the thermal oxidizer converts the
remaining reduced sulfur compounds to S02,
o SO? detector - the S02 detector generates an electrical
signal proportional to the generated S02 concentration
in the gas stream, and
o data system - the electronic signal from the detector
is received and converted to units of the standard by
the data system.
5.3.9.1 Probe/Conditioning System -
The purpose of the probe/conditioning system is to supply to the
analyzer a parti culate, moisture and acid free sample gas for subsequent
TRS and 02 analysis. The probe is made of a porous ceramic tube which is
resistant to physical abrasion, corrosion and thermal shock (Figure 5-49).
The probe configuration utilizes the principle of inertial filtration to
remove large particulate matter from the sample gas. The inertial filter
depends on the acceleration of the stack gas to critical velocity through
the center of a porous ceramic tube. The gas is accelerated by a vacuum
flow transducer (eductor) connected to the exhaust end of the porous
filter tube. At the critical velocity of 88 ft./sec the vacuum on the
' 5-68
-------
outer surface of the filter tube removes a portion (1/20) of the gas
phase from within the porous tube. Only sample gas and slight amounts of
entrained mists will penetrate the filter wall. Particle build-up on the
inner surface of the filter tube is inhibited by the scrubbing effect of
large particles as they accelerate through the ceramic tube.
Calibration/Purge
Inlet
Eduetor
Blowback
Salve
Extension—Inertia 1
Tube Filter
Steam-
Inlet
Figure 5.49. STI Probe Configuration.
As illustrated in Figure 5.50, the gas conditioning system receives a
paniculate free gas stream at a constant temperature from the ceramic probe.
Figure 5.50. STI TRS Conditional System.
5-69,
-------
The sample gas is heated and maintained at constant temperature
by the steam used to drive the ceramic filter's eductor. The high-
boiling condensibles are removed by condensation and wall absorption
on the helical coil condenser tube within the Pyrex heat exchanger.
Figure 5.51 illustrates the double vortex coils used in the STI system.
OUfllT
Figure 5.51. STI Heat Exchanger/Condenser Assembly.
5-70
-------
During the condensation of the high boiling condensibles, water is
also condensed and is collected in the head space trap at the bottom of
the condenser tube. Since the pressure in the condenser tube is lower
than that of the process gas stream, the water and high boiling conden-
sibles can be removed by the head space trap and automated drain. This
method does not alter the TRS or 02 concentration of the sample gas.
From the condenser, the gas enters a filter body (vaporizer filter). The
purpose of the vaporizer filter is to raise the gas temperature well
above the water dew point and to act as a safety filter from the dryer
and analyzer downstream. From there, the sample gas is dried in a per-
meation dryer (Perma Pure Products) comprising 100 selective membranes.
The membranes are arranged in a tube-and-shell configuration with the
sample gas in the tubes and a countercurrent flow of instrument air from
the dry air assembly on the shell side. At the outlet of the dryer, the
sample gas is free of acids, corrosives, and particles larger than 0.6
microns. The sample gas at this point has a dew point of approximately
-40°F.
The probe/conditioning system employs steam injection for probe
cleaning and incorporates a port for injection of calibration gases.
The probe controller controls those functions as well as
o blowback time,
o air pressure,
o vaporizer temperature,
o enclosure temperature, and
o probe alarm closure.
From the probe/conditioning system the sample gas moves to the
dilution module through unheated teflon lines.
5.3.9.2 Dilution Control Assembly -
The dilution control assembly dilutes the sample and calibration
gases. The purpose of diluting the sample gas is to reduce the TRS
and background S0£ to ambient levels. At ambient levels, the S02 can
be removed by the dry-base S02 scrubber. After oxidation the TRS com-
pounds can be measured on an EPA (ambient air) reference method S02
detector. Sample dilution also ensures that adequate oxygen is
available for the quantitative oxidization of the four TRS compounds
(hydrogen sulfide, methyl mercaptan, dimethyl sulfide, dimethyl
disulfide) to sulfur dioxide.
The dilution control system incorporates precision orifice flow
controllers and mass flow controllers for sample and calibration gas.
The flow controller outputs are independent of down stream pressure.
They require only one atmosphere (approx. 15 psig) of pressure drop
across the controllers to maintain stable flow. The precision orifice
controllers utilize multistage jets to accomplish the flow rate stability.
The mass flow controllers operate on a variable orifice which compensates
for fluctuations in mass flow rate with variations in downstream pressure.
The dilution system is also the inlet for the calibration gas supplied to
5-71
-------
the probe/conditioning system during calibration.
After the pollutants in the gas stream have been diluted to ambient
concentrations, S02 is removed by a dry bed scrubber.
5.3.9.3 Sulfur Dioxide Scrubber -
The sulfur dioxide (S02) scrubber is a molecular sieve based absorber.
The sample gas passes directly through a canister filled with the coated
sieves which selectively remove S02 from the gas stream. From the S02
scrubber the sample gas containing the TRS passes directly into the thermal
oxidizer.
5.3.9.4 Thermal Oxidizer -
The thermal oxidizer (quartz furnace) is a quartz tube controlled
to a temperature sufficient to convert hydrogen sulfide, methyl mer-
caption, dimethyl sulfide, and dimethyl disulfide to S02 by thermal
oxidation. The oxidation occurs in the quartz tube as the sample gas
(oxygen must be present) passes through. The temperature is controlled
by a resistance heating coil around the quartz tube. The temperature
of the coil is controlled by a variac voltage controller and displayed on
a front panel mounted pyrometer. The output gas is routed to the ambient
specific analyzer for S02 analysis, from which TRS is reported as sulfur.
5.3.9.5 Analyzer
The STI analyzer utilizes the well established principle of fluores-
cence spectroscopy to measure S02 in a gas stream.
In fluorescence spectroscopy, a pulsating ultraviolet light is focused
through a narrow bandpass filter into a fluorescent chamber. The TRS as
S02, if present, is excited to a higher energy level. However, in a very
short time (10~9 to 10~8 second), the S02 excited molecule returns to its
original state, giving off characteristic decay radiation. A second filter
in front of a photomultiplier tube allows only this energy to reach the tube.
The energy detected by the photomultiplier tube is directly proportional
to the concentration of S02 in the sample stream.
Because the regulations require reporting TRS corrected to a percent
oxygen, STI utilizes the Teledyne Oxygen Analyzer to monitor the oxygen
content of the gas stream prior to dilution. The percent oxygen is detected
by a micro fuel cell detector. The fuel cell is specific to oxygen and has
a micro fuel cell detector. The fuel cell is specific to oxygen and has a
linear response from 0-100%.
The oxygen and S02 analyzers, along with the dilution, scrubber and
oxidation systems are all housed in an analyzer rack, as illustrated in
Figure 5.52.
5-72
-------
Figure 5.52. STI Analyzer Rack.
5.3.9.6 Data System -
The STI Data System functions are to log data and generate output
reports. The data system incorporates the following components:
o Computer - 128 K bytes of RAM Memory (basic programming);
o Disc Drive - 5 one-fourth disc, capable of 512 K bytes
of data storage;
o CRT Display;
o Battery back-up on full data system;
o Micro-Mac 4000 Input/Output system; and
o Printer - 10 inch, impact dot matrix.
All operator interface with the Data System is accomplished through
special function keys on the computer keyboard.
A manual switch panel is provided to control all stream and cali-
bration solenoid valves. These switches are normally operated in the
AUTO position. This allows the data system to control the valves. The
manual valve switches are required for system start up and trouble-
shooting.
5-73
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5.3.10 Bendix Total Reduced Sulfur Analyzer
The Bendix Total Reduced Sulfur Analyzer Is based upon Federal
Reference Method 16- Semi continuous Determination of Sulfur Emissions
from Stationary Sources. The analytical principle is gas chroma-
tography (GC), with flame photometric detection (FPD) of hydrogen sulfide
(H2S), methyl mercaptan (CHsSH), dimethyl sulfide, (C^JgS and dimethyl
disulfide (CH3)2S2- The typical analyzer system consists of five sub-
systems
o probe/conditioning assembly - conditions stack sample emissions and
provides a particulate-free dry gas sample to the analyzer system,
o support assembly - provides pneumatic and electrical control for
probe/conditioning assembly operation. The umbilical assembly
transports gases and electrical signals between the probe/condi-
tioning and support assemblies,
o sample transport system - provides analytical flow control and
includes a pump as a prime sample mover. This system extracts the
sample from the stack through the sample conditioning system and
supplies the specified sample flow rate to the analyzer system,
o analyzer system - the analyzer is the sensor portion of the system
enabling the analysis of stack emissions, and
o system control - specific functions of this system includes control
of electromechanical devices (i.e. solenoids and sliding plate
valves) located in the analyzer and sample conditioning system, data
collection, computation, recording, and/or reporting.
Figure 5.53 illustrates the major components of the Bendix Total Reduced
Sulfur Analyzer System.
5-74
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Probe/Conditioning Assembly
Electrical Control
Umbilical Assembly (Plumbing and Electrical Interface)
Analyzer
Support Assembly
Sample Transport
01 y
System Control
Figure 5.53. Bendix Total Reduced Sulfur Analyzer System.
5-75
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5.3.10.1 Probe/Conditioning System -
The probe/conditioning assembly conditions the sample stack
emissions and provides a particulate-free dry gas sample to the analyzer
sub-system.
The probe assembly (Figure 5.54) removes a representative gas sample
from the stack and filters particulates that would clog the analytical
system downstream. The probe uses two types of filtration to provide a
particle free gas stream for analysis
o stainless steel screen, and
o inertial filter system.
Eductor
Sample Line
Inertial Filter
500 Micron Filter
7T
Back Purge Supply Line (1-inch)
Figure 5.54. Bendix Probe/Conditioning Assembly.
R-76
-------
The stainless steel screen filter located at the sample inlet
prevents large particles (>500 micron) from entering the probe and
secondary filtering mechanism.
The sample gas passing through the screen is drawn into the probe
to the secondary inertial filtration system within the stack by an air
driven eductor located on the probe. As illustrated in Figure 5.55, the
inertial filter is constructed of a concentric tube of sintered stainless
steel and an outer tube of stainless steel pipe.
Eductor
Inertial Filter
1/4" &&. Tub.
Vent In Stack
SMI
Sample
Sample Out
Figure 5.55. Bendix Inertial Filter Assembly.
The sintered stainless steel has an effective pore size of 5 microns.
In operation, stack gas is extracted through the inner tube by the educ-
tor at a flow rate of 56 liters/minute. Downstream of the probe/con-
ditioning assembly is a second pump which extracts gas from the porous
sintered tube at a rate of 3 liters/minute. This action actually
5-77
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causes gas to diffuse through the inner tube to the outer tube by the
downstream sampling pump. As illustrated in Figure 5.55, particulates
flowing through the inner sintered tube travel at such high velocity
that they are unable to make the 90° turn into the secondary gas stream.
The low sampling volume to internal flow volume ratio aids in this process,
Consequently, the sample gas is free of particles down to 5 microns due
to the initial screen and the inertial filter mechanism.
From the sample extraction system, the stack gas sample is dried in
the conditioning system, as illustrated in Figure 5-5fi.
Stack Environment
Probe
Conditioner
Trap i
Screen Filter
V
0
Flue Gas
Inertial
vL
Eductor '
Support
Assembly
Calibration Gas
Blowback Tank
Figure 5.56. Bendix Sample/Extraction System.
b-78
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The conditioning assembly removes entrained liquids and water
vapor from the sample. The sample is extracted through the inertial
filter, entering the conditioning system before it is pulled through
a teflon tubing air heat exchanger. The teflon tube heat exchanger
utilizes air from the air supply as the cooling medium. Cooling air
flow is counter to the sample flow. Any condensibles or entrained liquids
are collected in a liquid trap. The stack sample is pulled from the head
space of the trap (reservoir) and transported into a vaporizer located in
a temperature controlled block. The vaporizer is heated to approximately
120°C. An emergency filter located within the vaporizer protects the
permeation dryer from particulates during upset conditions. The vaporizer
aids the permeation dryer, vaporizing any entrained liquids. The sample
is then pulled through a 200 tube permeation dryer. The first 10 inches
of the dryer are located in a heated enclosure for increased dryer effic-
iency. Water is removed from the sample gas by a unique ion transfer
mechanism within the Perma Pure dryer. Purging the outer shell of the
dryer with dry air transfers water vapor contained in the sample to the
purge gas. This drives sample gas to a dew point of less than 11°C.
Clean, dry sample gas then exits the conditioning assembly.
Figure 5.57 displays the major components of the conditioning system.
Perma Pure Dryer
Simple Lin*
Blowback Tank
Blowback Solenoid
Master Calibration Solenoid Vaporizer/Filter
Figure 5.57. Bendix Conditioning System.
5-79
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Two additional functions of the probe/conditioning system are
backpurge and span gas injection. At predetermined time intervals a
back purge of the 500 micron screen is accomplished with high pressure air
via a pressurized air tank. Any particles embedded in the screen are
blown back into the stack. This cleaning action renews the filter.
After the blowback mode, the air tank is recharged for approximately 15
seconds. Then the bypass purge and drain solenoid valves are actuated for
approximately 10 seconds. During this time high pressure air purges the
inertial filter shell space.
During the calibration mode, calibration gas flows into the
inertial filter shell space. Simultaneously the air supply to the
eductor is stopped, preventing contamination of calibration gas with
stack gas. Introduction of excess calibration gas to the inertial
filter causes the filter to act as a manifold for referencing cali-
bration gas to the same pressure as in the normal sampling mode.
The calibration gas is then extracted by the secondary pump located
downstream of the probe/conditioning system.
5.3.10.2 Support Assembly -
The support assmebly contains three flow channels which provide flow
control for probe/conditioning assembly support gases.
The zero/span flow control channel provides flow control of zero
and span gas input to the calibration solenoid valve. The plant air
flow control channel provides flow control of plant air for the blow-
back, bypass purge and drain solenoid mode operation. The sweep air
flow channel provides flow control of sweep air for the permeation dryer
operation.
5.3.10.3 Sample Transport System -
The sample transport assembly extracts the sample from the stack
through the sample conditionng assembly and supplies sample at the desired
flow rate to the analyzers. The sample transport assembly houses the analy-
tical flow and electromechanical components. These controls set and indi-
cate sample input pressure and flow rate to the analyzers through pressure
regulators, gauges, needle valves, flow indicators, solenoid valves and
pumps.
5.3.10.4 Analyzer System -
The analysis system consists of a GC analyzer that measures TRS
components and a fuel cell-type oxygen analyzer that measures the per-
centage of oxygen in stack emissions. The oxygen analyzer requires no
support gases, while the analyzer requires hydrogen and carrier air.
The analyzer individually separates the four TRS gases (hydrogen
sulfide, methyl mercaptan, dimethyl sulfide and dimethyl disulfide) from
COS, CO and C02. To accomplish this, the analyzer incorporates two 10
port sample back flush valves and two chromatographic columns (a PPE column
and a Chromapak). Sample is injected into the columns at different times
in the analysis cycle. Sample valves are programmed by a control valve to
5-80
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route column output to the FPD when TRS component of interest is eluting.
Figure 5.58 displays the analyzer rack assembly for these various compo-
nents of the GC system.
Figure 5.58. Bendix Analyzer Rack Assembly.
5-81
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Reduced sulfur compounds are analyzed by the following mechanism.
Sample gas enters the SAMPLE IN connector of the analyzer via the sample
transport assembly. The sample then enters the sample loop. Carrier gas
enters the instrument via the CARRIER inlet fitting and then enters the
detection cell through a pressure regulator at the detector cell.
Hydrogen enters the unit from an external cylinder via the rear
panel bulkhead connection. The hydrogen then flows through a series of
regulators to the detector cell to sustain the flame.
Through the use of two sample loops and four columns, each venting
or forcing the TRS containing gas through selected columns, the analysis
of the reduced sulfur as the different species elute at different times
is accomplished.
Column selection is based on sample concentration and volume, which
determines the physical characteristics of the column (material of con-
struction, column length, and diameter). Columns are coiled tubes packed
with inert solid material that supports a thin film of nonvolatile liquid
phase. The solid support, type and amount of liquid phase, physical
characteristics of the column, and temperature are critical factors for
obtaining the desired separation. All other analytical considerations
such as valve selection, timing, etc., are based on the specific column
selection. The columns allow for the needed separation for analytical
detection of reduced
ntaining a teflon lined burner chamber. The burner
chamber is optically coupled (via an optical filter) to a nitrogen
sealed photomultiplier assembly. The burner chamber consists of a hydro-
gen well, burner, and ignitor. As a sample flows into the cell, it
mixes with hydrogen at the burner tip and is burned.
The photomultiplier assembly consists of a photomultiplier tube,
printed circuit board, and thermoelectric coolers. The coolers maintain
the photomultiplier tube at 25°C, preventing thermal noise (background
signal related to non-signal light caused by heat or dark current).
When the sulfur sample is burned, light (luminescence) is emitted.
The luminescence passes through an optical filter which blocks light not
of the characteristic wavelength (394 nanometers) of sulfur. The optical
filter eliminates interference from non-sulfur components (i.e. hydrocar-
bons). The light is sensed by a photomultiplier tube which outputs current
proportional to the square of sulfur concentration. The combination of
gas chromatography with flame ionization detection is very sensitive to
sulfur bearing species. Figure 5.59 illustrates the eluting pattern with
subsequent detection by the photomultiplier tube of the reduced sulfur
components of the gas stream.
5-82
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Figure 5.59. Bendix TRS Chromatogram.
5.3.10.5 System Control -
The system control contains the software packaged for generating
all data to meet EPA reporting requirements. It performs all control,
logic and data handling functions of the TRS system. The TRS software
package supports the front panel keyboard/display, and a remote tele-
printer.
Coupled with the TRS system is an oxygen analyzer for continuous
measurement of oxygen. The system control receives the oxygen concen-
tration and applies that value to the TRS measurement to develop a
TRS corrected concentration.
5-83
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5.4 COMMERCIALLY AVAILABLE OXYGEN CONTINUOUS EMISSION MONITORS
5.4.1 Introduction
Performance Specification 5 (PS5) - Specifications and Test Procedures
for TRS Continuous Emission Monitoring Systems in Stationary Sources - was
promulgated on July 20, 1983 in the Federal Register by the Environmental
Protection Agency. As a result, Kraft pulp mills subject to New Source
Performance Standards (NSPS), 40 CFR Part 60, Subpart BB, were required to
install, test, operate and maintain TRS continuous monitoring systems
(CEMS) in affected facilities. The main objective was to require affected
facilities to continuously monitor their TRS emissions to monitor operation
and maintenance.
As part of the reporting requirements of Subpart BB - Standards of
Performance for Kraft Pulp Mills, all reported excess emissions are to be
corrected to a percent oxygen, depending upon the affected facility.
Table 5.12 illustrates those affected facilities within the Kraft pulp
mill required to report oxygen-corrected TRS excess emissions.
Consequently, Kraft pulp mills were not only required to monitor TRS
emissions on a continuous basis, but also oxygen on a continuous basis so
emissions data could be corrected. Several continuous emission monitoring
techinques have been demonstrated in the field to be excellent methods
for monitoring oxygen from stationary sources. This section will cover
three basic methods:
- Electrochemical Transducer;
- Electrocatalytic; and
- Paramagnetic.
5-84
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TABLE 5.12
STANDARDS OF PERFORMANCE FOR KRAFT PULP MILLS
REGULATED EMISSIONS CORRECTED TO PERCENT OXYGEN
Source Category
Subpart BB - Kraft Pulp Mills
Proposed/effective
9/24/76 (41 FR 42012)
Promulgated
2/23/78 (43 FR 7568)
Revised
S7777B~(43 FR 34784)
Affected
Facility
Recovery furnace
Smelt dissolving
tank
Lime kiln
Digester, brown stack
washer, evaporator.
oxidation, or strip-
per systems
Pollutant
Partlculate
Opacity
TRS
(a) straight recovery
(b) cross recovery
Partlculate
TRS
Partlculate
(a) gaseous fuel
(b) liquid fuel
TRS
TRS
Emission Limit
0.044 gr/dscf
(0.10 g/dscm)
corrected to 8X
oxygen
35X
5 ppm by volume
corrected to 8X
oxygen
25 pan by volume
corrected to 8X
oxygen
0.2 Ib/ton
(0.1 g/kg)BLS
0.0168 Ib/ton
(0.0084 g/kg)BLS
0.067 gr/dscf
(0.15 g/dscm)
corrected to 10X
oxygen
0.13 gr/dscf
(0.30 g/dscm)
corrected to 10X
oxygen
8 ppm by volume
corrected to 10X
oxygen
5 ppm by volume
corrected to 10
oxygen
^exceptions; see
standards
Monitoring
Reojil rement
No requirement
Continuous
Continuous
No requirement
No requirement
No requirement
No requirement
Continuous
Continuous
Effluent gas Incineration
temperature; scrubber liquid
supply pressure and gas
stream pressure loss
5-R5
-------
5.4.2 Oxygen Analytical Techniques
5.4.2.1 Electrochemical Transducer -
The most common method of detecting 02 in a gas stream is the elec-
trochemical transducer. The electrochemical transducer consists of a sens-
ing membrane, electrolytic reservoir and a counter electrode all in a self
contained cell. In operation, the flue gas is drawn into the electrochemi-
cal transducer, where the selective semi-permeable membrane allows only
the pollutant gas to diffuse. The pollutant undergoes electrooxidation,
releasing electrons. The net reaction is a release of electrons to the
counter-electrode by means of the electrolytic reservoir. Figure 5.60
illustrates this movement of electrons throughout the electrochemical
transducer. If the electron flow is diffusion controlled, the current
will be directly proportional to the concentration of reactants. This is
known as Pick's Law of Diffusion.
Sample In
Semi-permeable
Sample Out
[membrane
Thin Film
Sensing Electrode
Bulk Electrolyte
Reference
HEIectrode
Output
+
Figure 5.60 Electrochemical Transducer
Consequently, two basic techniques are used in the electrochemical
transducer:
(1) utilization of a selective semipermeable membrane that allows the
pollutant molecule to diffuse to an electrolytic solution; and
-------
(2) measurement of the current change produced at an electrode by
the oxidation/reduction of the dissolved gas at the electrode.
The selectivity of one pollutant diffusing through the membrane is
affected by two important design features. First, the membrane is specif-
ically selected for that pollutant of interest. Second, a retarding
potential is maintained across the electrodes of the system to prevent the
diffusion/oxidation of other pollutant species that are not as easily
oxidized. The oxidation-reduction reaction occurs at the sensing electrode
because the counterelectrode material has a higher oxidation potential than
that of the species being reacted. In the cell, the sensing electrode has
a potential equal to that of the counterelectrode minus the iR drop across
the resister. The sensing electrode is electrocatalytic in nature and,
being at a high oxidation potential, will cause the oxidation of the
pollutant and a consequent release of electrons. Other pollutant molecules,
having higher or lower oxidizing potential, therefore cannot participate in
the cell reaction. The system therefore becomes selective by design.
Overall, the detection of the pollutant gas is achieved by the
following mechanism: (a) the diffusion of the pollutant gas through the
semi-permeable membrane; (b) the dissolving of the gas molecules in the
thin liquid film; (c) the diffusion of the gas through the thin liquid
film to the sensing electrode; (d) oxidation-reduction at the electrode;
(e) transfer of the charge to the counterelectrode; and (f) reaction at
the counterelectrode. The electron current through the resistor can then
be picked off as a voltage and suitably monitored.
The electrochemical transducer comes in a number of configurations,
depending upon the manufacturer: Various claims have been made about the
response and selectivity of the instrument related to the cell design.
The advantages of these systems are in their small size and portability.
Compared to practically all other source monitoring instruments, they are
the least expensive. These two factors make them ideal for spot checks
during a source inspection or as warning detectors. Each sensor is a
sealed unit. The sensor operating life may vary from 3 to 12 months,
depending upon the condition of the sample entering the cell. Particu-
late and high temperature shorten the life of the detector cell. Removal
of particulate and lowering sample temperature will lengthen the life of
the cell.
In operation, a gas sample is extracted through a filtered probe to
a condenser by way of a pump. After particulate and moisture removal, the
sample is "pushed" through the analyzer at a flow rate of 0.5 to 2.0 scfh.
The instrument reading is relatively independent of flow rate. However,
the sensor is designed for operation at atmospheric pressure. It can be
operated at pressures slightly above or below atmospheric, but any pressure
changes should occur slowly in order to prevent damage to the sensor.
The instrument operates best under positive pressure since the zero/span
gases are supplied under pressure.
5-87
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5.4.2.2 Electrocatalytic Technique -
In recent years, a new method of monitoring oxygen in a sample gas
stream has developed from the fuel cell technology. Similar to the electro-
chemical transducer, the fuel cell replaces the bulky liquid electrolyte
with a special solid catalytic electrolyte. Based on electrochemical
principles, the detection of oxygen involves the movement of reference
oxygen through a temperature-controlled solid porous electrolyte to the
sample oxygen, based upon differential partial pressures. The closed end
tube sensor, which is responsive to these changes in partial pressure, is
coated on the inside and outside with platinum and maintained at a tempera-
ture of 1550°F. At this temperature, vacancies in the lattice structure
exist. These vacancies provide a path for the oxygen ion to migrate from
one side of the electrolyte to the other due to existence of the differen-
tial pressure on either side of the electrolyte. The migration of oxygen
from the reference side to the sample side produces a current through a
basic oxidation/reduction reaction. A schematic of a typical electrocat-
alytic sensing system is shown in Figure 5.61.
POROUS
ELECTRODE,
Zr 02 POROUS ELECTROUTE^
Figure 5.61 Electrocatalytic Technique
In sampling combustion gases, the partial pressure of the oxygen in
the sample side will be lower than the partial pressure of oxygen in the
reference side. This imbalance of pressures causes the oxygen on the
reference side (high partial pressure) to pass through the heated porous
electrolyte to the sample side (low partial pressure) in an attempt to
equilibrate the two sides. At the cathode, the reference gas , which is
generally ambient air (20.9% O?), is electrochemically reduced by the
following equation:
o2 +
[The electrons (e~) are supplied to the cathode by a load in the circuit.]
The oxygen ion, 0=, becoming part of the 1550°F zirconium electrolyte, mi-
grates to the anode and reacts with hydrogen by the following equation:
20= + 2H,
5-88
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The water produced is carried away by the sample gas. The released
electrons flow through the load and back to the cathode. The electro-
motive force (EMF) produced from the electrochemical reactions at the
cathode and anode Is directly proportional to the differential partial
pressures existing between the reference side and sample side of the
electrolyte. This process can be represented by the Nernst equation.
RJ_ P ref (0? )
EMF = 4F In p sample (02 ) + c
where:
EMF = Electromotive force, volts;
R = Ideal gas constant;
T = Temperature of cell;
F = Faraday's constant;
P ref (03)= Partial pressure of oxygen in
reference gas;
P sample (02)= Partial pressure of oxygen in
sample gas; and
C = The cell constant.
If the cell temperature can be stabilized (1550°F) and the partial
pressure in the reference gas is known, then the partial pressure in the
sample gas can be calculated by the above equation.
A number of manufacturers are presently marketing oxygen analyzers.
Both extractive and in-situ-type systems have been developed, providing
the source operator with versatility in application. It should be noted
that a constant supply of clean dry air for the reference side of the
cell is required. Calibration gases can be injected into the measuring
cavity contained within the ceramic thimble to check the instrument
operation.
5.4.2.3 Paramagnetic Technique
One of the earlier principles of monitoring oxygen was the para-
magnetic analyzer, based upon the natural paramagnetic behavior of
oxygen molecules. Molecules react differently to magnetic field. Those
that are repelled are termed "diamagnetic" molecule while those that are
attracted by a magnetic field are termed "paramagnetic". Diamagnetic
molecules have paired electrons: the same number of electrons spinning
counterclockwise as spinning clockwise. Oxygen, however, has two "un-
paired" electrons that spin in the same direction. These two electrons
give the oxygen molecule a permanent magnetic moment. When an oxygen
molecule is placed near a magnetic field, the molecule is drawn to
the field and the magnetic moments of the electrons become aligned with
it. This striking phenomenon was first discovered by Faraday and forms
5-89
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the basis of the paramagnetic method for measuring oxygen concentrations,
There are two techniques presently marketed utilizing the paramagnetic
properties of oxygen:
o Magneto-Dynamic Techniques; and
o Magnetic Wind Technique.
5.4.?.3.1 Magneto - Dynamic Technique -
The magneto -dynamic technique utilizes the paramagnetic nature
of oxygen in suspending a specially construction torsion balance, as
shown in Figure 5.62.
LED
TWIN
PHOTOCELLS
o o
RECORDER
Figure 5.62. Magneto - Dynamic Technique
In operation, a diamagnetic quartz "dumb-bell" is suspended in a
symmetrical, nonuniform magnetic field within the instrument. A mirror
is attached to this quartz "dumb-bell" with the entire apparatus fixed
upon a torsion spring. The magnetic field acts upon the diamagnetic
quartz "dumb-bell" to force it to a position away from the most intense
part of the field. At zero position a light source is reflected by the
mirror from the suspended quartz spheres to a photocell which generates a
signal used to keep a known torque applied to the torsion spring. The
presence of oxygen in the sample cell changes the shape of the magnetic
field causing the quartz "dumb-bell" to be further deflected. The photo-
cell signal is used to apply a restoring torque to the spring and return
the quartz spheres to the original position. The torque applied to
restore the quartz to a "null balance" is proportional to the oxygen
concentration present.
5-90
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5.4.2.3.2 Magnetic Wind Technique -
The magnetic wind instruments are based on the fact that the
paramagnetic attraction of the oxygen molecule decreases as the tem-
perature increases. A typical analyzer utilizes a cross-tube wound
with filament wire heated to 200°C, as shown in Figure 5.63.
MAGNETIC FIELD
L
Figure 5.63. Magnetic Wind Technique
A strong magnetic field covers one half of the coil. Oxygen
contained in the sample gas will be attracted to the applied field and
enter the cross-tube. The oxygen then heats up and its paramagnetic
susceptibility is reduced. This heated oxygen will then be pushed out by
the colder gas just entering the cross-tube. A "wind" or flow of gas will
therefore continuously pass through the cross-tube. This gas will,
however, effectively cool the heated filament coil and change its resistance.
The change in resistance detected in the Wheatstone bridge circuit can be
related to the oxygen concentration.
5-91
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5-92
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6.0 GENERATION OF STANDARD TEST ATMOSPHERES
6.1 INTRODUCTION
As we develop new and improved techniques to monitor total reduced
sulfur species from Kraft pulp mills, it has become imperative for the
analytical systems to be calibrated so their results can be used as part
of an agency's enforcement options. Consequently, in recent years more
emphasis is being placed on the calibration of air pollution monitors.
This ensures that the data generated actually represents the pollutant
concentration being monitored.
Sampling systems may be designed to operate within a specific range
of conditions, but due to deterioration, electrical or mechanical, the data
generated by the monitor may differ from the true concentration of pollu-
tant in the stack gas. In order to continually evaluate the performance
of the sampling equipment, a known concentration of the pollutant should
be challenged to the monitor. The response of the monitor to the known
is compared to determine accuracy of the system. A relationship is de-
veloped between the known vs. monitor response. From this relationship,
the data generated can be corrected, accounting for monitor deterioration,
etc.
The methods available for generating known concentrations of reduced
sulfur compounds are divided into two broad categories:
o dynamic calibration systems; and
o static systems.
In discussing these two techniques for generating known concentrations
of test atmospheres, we will have to keep in mind that we are interested
in part per million concentration ranges for the monitored pollutants. At-
tempts to prepare static standards in fixed volume containers and in bags
may be impossible. Such features as adsorption, absorption, stability and
other concerns must be considered. Dynamic calibrations overcome many of
the inherent problems of static systems. But dynamic calibrations are not
without their drawbacks. Traceability, stability, availability of standards,
etc. are just some of the limitations associated with dynamic calibrations.
The purpose of this section is to discuss the methods available for generat-
ing known standards of reduced sulfur compounds for both static and dynamic
systems.
6.2 DYNAMIC CALIBRATION SYSTEMS
6.2.1 Permeation Tubes
In 1966, O'Keefe and Ortman, of the U.S. Environmental Protection
Agency, discovered that a gas confined above its liquified form will per-
meate through a permeable material at a constant rate if held at a constant
6-1
-------
temperature. This discovery satisfied the primary objective of a calibra-
tion system: to generate a known concentration over a period of time. With
this in mind, O'Keefe and Ortman discovered that Teflon® or other plastic
materials allowed the permeation of gas through their surfaces enabling
them to generate test atmospheres. By placing the liquified pollutant in
a tube of Teflon® or other plastic material, sealing both ends and putting
it in a water bath at a constant temperature, they discovered that they
could generate known test atmospheres. This discovery led to the develop-
ment of two major permeation devices:
o Permeation tubes or diffusion tubes; and
o Permeation vials.
6.2.1.1 Permeation Tube Construction -
The performance of a permeation device depends on the type of polymer
film used in its construction and the pollutant. Major factors to consider
in the use of a permeation device are:
o temperature;
o humidity;
o gas stability; and
o equilibrium time.
Table 6.1 lists some of the materials used to construct permeation
devices and Table 6.2 lists permeation rates for a number of compounds
through Teflon® film.
TABLE 6.1
PERMEATION TUBE CONSTRUCTION
Material
Trade Name
Thickness (in.)
Fluorinated ethylene propylene resin
Fluorinated ethylene propylene resin
Fluorinated ethylene propylene resin
Polyethylene
Polyethylene
Polyethylene
Polyvinyl acetate
Polyvinylidene chloride
Polyamide
Polyester
Polyethylene terephthalate
Polyethene
FEP Teflon®
FEP Teflon®
FEP Teflon®
Alathon
Saran Wrap
Nylon 6
Mylar
Mylar
Diothene
0.030
0.12
0.001
0.027 to 0.526
0.025
0.001 to 0.037
0.135 to 1.332
0.025
0.113
0.031
0.00031 to 0.006
0.0635 to 0.0254
6-2
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TABLE 6.2
PERMEATION RATE FOR SELECTED COMPOUNDS
THROUGH TEFLON FILM
Compound
S02
S02
N02
Propane
Butane
CHF2C1
CF3CHClBr
CH3CHCH3
n-C5H12
C6H5CH3
H2S
CH3SH
(CH3)2SH
(CH3)2S2
Film
Thickness
(in.)
0.012
0.030
0.012
0.120
0.012
0.012
0.012
0.012
0.012
0.012
0.012
0.012
0.016
0.030
0.016
0.030
0.012
0.012
0.012
0.012
Temgerature
( C)
20 + 0.5
20 + 0.5
20.1
29.1
13.8
21.1
29.1
21.1
29.1
15.5
29.1
20
93
31
93
20
35
35
35
35
Permeation Rate
(ng/ cm/mi n)
213
138
203
396
605
1110
2290
53
119
6.4
22.3
2.8
1.3
0.29
0.065
0.00006
816
541
120
12.7
The permeation tube is made by sealing a liquid chemical in a tube
made of some permeable material. It is essential that the chemical be in
the liquid state for the permeation tube to operate properly. In many
cases the chemical is a gas at atmospheric pressure, but is maintained in
the liquid state under its own saturation vapor pressure in the permeation
tube. The tube is sealed at both ends with a non-permeable plug, as illus-
trated in Figure 6.1.
T
5 mm
JL
IL
Teflon tube
LiquifiedHgS gas
iimiiiiiimiiiiui
\
X
Retaining collar
Retaining collar
(indicating tube
I.D.r'33-64")
Figure 6.1. Construction of a Typical Permeation Tube
6-3
-------
Permeation of the pollutant vapor within the tube occurs through the
exposed sidewalls because of the concentration gradient that exists between
the inner and outer tube walls. By passing different flows of diluent gas
over the tube, gases of varying concentration can be generated. If the tube
is held at a constant temperature, the permeation rate will remain constant.
By measuring the weight loss at this constant temperature over a given
period of time, the permeation rate may be determined. The output rate of
the tube will remain essentially constant until nearly all of the liquid in
the tube has permeated through the walls. In general, permeation tubes can
be used to generate known pollutant concentration between 0.1 and 10 ppm.
6.2.1.1.1 FEP Teflon® Permeation Tubes -
FEP tubes were the first tubes developed and proved to be most practi-
cal in terms of obtaining low permeation rates. One major drawback, how-
ever, is their sensitivity to fluctuations in temperature, thus changing
their permeation rate. An error of approximately 10% per °C change has
been documented. Consequently, the correct temperature must be maintained
when using FEP Teflon® permeation tubes.
6.2.1.1.2 TFE Teflon* Permeation Tubes -
TFE Teflon® Permeation tubes were developed and studied in recent
years to provide a device with a considerably higher permeation rate.
TFE permeation rates are typically 3 to 5 times higher than FEP permea-
tion rates. Because of the higher rates available with TFE, standards
can be made with materials which would normally have vapor pressures too
low for the FEP devices. Similar to the FEP permeation devices, TFE
Teflon® permeation tubes are also sensitive to temperature variation
(_+ 10% per °C change).
Table 6.3 demonstrates the difference in permeation rates for both FEP
and TFE Teflon® permeation tubes and permeation vials for selected chemicals,
TABLE 6.3
PERMEATION RATES FOR FEP AND TFE TEFLON® PERMEATION TUBES
Chemical
S02
H2S
Dimethyl Disulfide
Dimethyl Sulfide
Methyl Mercaptan
Bath
Temperature,
°C
30
30
35
30
30
30
30
35
70
70
30
30
30
Permeation Rate
(ng/min/cm)
Vial1
50 (FEP)
300 (FEP)
1300 (FEP)
Tube Wall Thickness
0.030 in.
-
730 (FEP)
-
-
-
-
-
-
130 (TFE)
300 (FEP)
70 (TFE)
65 (FEP)
270 (TFE_L
0.062 in.
265 (FEP)
-
420 (FEP)
-
-
-
240 (FEP)
330 (FEP)
-
-
-
-
Life,
Months
7.9
6.6
5.0
480
89
20
6
4.4
28
9.5
41
46.7
11.2
thickness of the vial cap.
6-4
-------
6.2.1.2 Permeation Tube Rate -
Before a permeation device can he used in the laboratory or in
the field, its permeation rate must be determined. The permeation
rate, R, is determined gravimetrically. In essence, the tube is weighed,
then placed in a temperature bath (+1°C) for a period of time. The tube
is removed and reweighed. This process is repeated over several days to
calculate a permeation rate at that specific temperature. The difference
between initial and recorded weight (ng), divided by time (min.) determines
the permeation rate.
R-
where:
R = permeation rate, ng/min
W = weight change, ng
T = time, minutes
The permeation rate can be calculated either manually, as shown in
the above equation, or recorded automatically. Figure 6.2 illustrates the
apparatus used to determine the permeation rate of a permeation device
automatically. Figure 6.3 displays the stripchart read-out of the
automated system.
Weighing unit
Purge air
Constant
temperature
bath±0.1C
Figure 6.2. Automated Weighing Unit to Determine Weight Loss of a
Permeation Tube
6-5
-------
-0800
-0700
-0600
240
f-0500
H0400
0300 1
mm
1
20 30 40
50
70 80 90 100
12/3/70 H2p#24 temp. 25°C, range 0-1 Mg f.S.
Figure 6.3. Stripchart Readout of Automated Weighing Unit for
Permeation Rates
Once the permeation rate of the diffusion device is determined, it
is used to calculate the concentration of pollutant test atmosphere
generated, using that permeation device, by the following equation:
c =
/24.46/tf/At-mo/g\/ T°K \/760 mm Hg\
\ (M) Mg//t-mo/e/\^980A.y\P mm Hg /
(PR)\(M)
P/min
Where: c = concentration, fif/( or ppm by volume
T = temperature of the system, °K
P= pressure of the system, mm Hg
PR — permeation rate, ftg/min
Q= total flow rate, liters/nun
M = molecular weight of the permeating gas, (ig/p-mole
24.46= molar volume (V) of any gas at 25 °C 9 760 mm Hg,
An example of a typical permeation calibration system used in
generating a known concentration of pollutant is shown in Figure 6.4.
(Several tubes can be placed in temperature controlled containers to
generate different pollutants at one time.)
6-6
-------
F
(
•«H
r
low mete
>r dry test
meter
n r-
O
r
i
——Q^— Clean dry air
Needle valve
Permeation tube J^
Y
3 Mixing
bulb
^Sampli
^ systen
r
Thermometer
Purified air
or cylinder 1 r W \
ng nitrogen Drier Z*3C3
1 ^@
3s
^XS
V.
\
M
Flow meter
— 1 A/ °r
&J* critical orifice
1
r
.. ^T~1 i Wnrrr
-»_' ^-^-*_~-^-^^J 1 pump
.A-< AAS^^S^>J C
.^^ A-S^-A-^^sxl^Is.
A-*_^-^-A-*_*_A_»_^^.
Vent
Figure 6.4. Typical Permeation Calibration System
6.2.1.3 Permeation Tube Availability
6.2.1.3.1 National Bureau of Standards - Standard Reference Materials
(NBS-SRHs)
The National Bureau of Standards presently provides three Standard
Reference Materials involving permeation tubes for sulfur dioxide. The
tubes are available in three lengths - 2, 5 and 10 centimeters. The per-
meation rates are certified over the temperature range of 20 to 30°C.
Table 6.4 provides a guide to the availability of NBS-SRM permeation
tubes for sulfur dioxide.
TABLE 6.4
AVAILABILITY OF NBS-SRM's for S02
SRM
#
1625
1626
1627
Type
Sulfur Dioxide
Permeation Tube
Sulfur Dioxide
Permeation Tube
Sulfur Dioxide
Permeation Tube
Tube Length,
Cm
10
5
2
Permeation*
Rate C^g/min)
2.8
1.4
0.56
Typical Concentrations for
Various Flow Rates
(ppm)
1 1/min
1.07
0.535
0.214
5 1/min
0.214
0.107
0.0428
10 1/min
0.107
0.0535
0.0214
*Permeation Temperature = 25°C
6-7
-------
6.2.1.3.2 Commercial Tubes Availability
Commercially available permeation tubes, vials and wafers are
available from a number of manufacturers. Typically, the manufacturer
will provide, with each tube, information associated with:
o Permeation rate at designated temperature;
o Tube dimensions;
o Tube construction; and
o Certification level
Figure 6.5 displays a typical information sheet provided by major
manufacturers.
CHEMICAL
C
B
CS
FEP
TFE
NYL
062
030
V
2-10 cm
0,1-5 cm
(V)
30-70°C
ng/mm
EXAMPLES
Ammonia
Chlorine
Acrolem
CS
CS
B
Methyl Hydrazine C
FEP
FEP
TFE
TFE
062
V
030
030
5
0
10
6
30
10
30
70
1100
320
1640
1190
•C = Certified Permeation Tube
B = Batch Permeation Tube
CS = Certified Stock Permeation Devices
Figure 6.5. Permeation Tube Information
6-8
-------
The selection of the proper permeation tube from a manufacturer
can be performed In four steps.
Step 1 : Identify gas of interest
Step 2: Select the gas concentration (in parts per million by
volume) you need. Designate this concentration C.
Step 3: Determine minimum flow rate (in cubic centimeters/minute)
needed to support the TRS continuous emission monitor.
Designate this flow rate E.
Step 4; Calculate the needed permeation rate (in nanograms/min)
using the following formula:
P= f£
K,
Where:
m
P = permeation rate, ng/min;
F = flow rate, cc/min;
C = concentration, ppm by volume; and
Km= the molar constant;
= 24.46
MW
Where: 24.46 = molar volume in liters
at 25°C and 760mm Hg; and
MW - molecular weight of pollutant,
Step 5; Check the manufacturer literature to obtain closest
permeation rate.
There are several manufacturers which supply certified permeation
devices. Table 6.5 lists those manufacturers and their addresses.
6-9
-------
TABLE 6.5
SUPPLIERS OF CERTIFIED PERMEATION DEVICES
Manufacturer
Kin-Tek
Laboratories, Inc.
Viti Metronics
Ecology Board,
Inc.
Tracer, Inc.
Analytical
Instrument
Development, Inc.
Metronics
Associates, Inc.
National Bureau
of Standards
Address
Drawer J
Texas City, Tx.
77590
(409)945-4529
2991 Corvin Drive
Santa Clara, Ca.
95051
(408) 737-0550
9257 Independence
Ave., Chatsworth,
Ca. 91311
(213) 882-6795
6500 Tracer Land
Austin, Tx.
(512) 926-2800
Rt. 41 & Newark St.
Avondale, PA.
19311
(215) 268-3181
3201 Porter Drive
Stanford Industrial
Park, Palo Alto,
CA. 94304
(415) 493-5632
Office of Standard
Reference Material
US Dept. of Com-
merce,
Gaithersburg, MD.
(301)921-2045
Pollutant
Hydrogen
Sulfide
H?S
X
X
X
X
X
X
_
Methyl
Mercaptan
CH-^SH
X
X
X
X
X
X
_
Dimethyl
Sulfide
(CHO?S
X
X
X
X
X
X
_
Dimethyl
Disulfide
(CH3)?S?
X
X
X
X
X
X
_
Sulfur
Dioxide
SO?
X
X
X
X
X
X
X
6-10
-------
6.2.1.4 Other Permeation Devices: Vials -
Permeation vials were developed to meet two specific needs. The
first was to provide a device that is a low permeator. The second was
to provide a larger reservoir containing the liquified pollutant to
enable a longer life.
The construction of the permeation vial is very simple. As shown
in Figure 6.6, the device is simply a pyrex glass container with a FEP
Teflon® plug.
Teflon plug
Permeating area
L
Glass tube •
Stainless steel bands
Teflon tube
Liquid
Figure 6.6. Construction of a Permeation Vial
The liquified pollutant is added to the vial and capped with the
Teflon® plug. As can be seen from the illustration, the only source for
the vapor to permeate is through the plug. Because the plug has a very
low permeation area, the result is a reduced amount of permeating pollu-
tant. This, coupled with a very large reservoir of liquid, enables the
vial to last longer than the permeation tubes discussed earlier.
For those pollutants with a high vapor pressure, the permeation
vial enables a method for generating a known concentration over a longer
period of time. This is particularly true for chlorine and carbonyl
sulfide. Table 6.6 lists those pollutants commercially available in
permeating vials. (Those pollutants not listed in the Table can be
specially ordered from the manufacturer).
6-11
-------
TABLE 6.6
COMMERCIALLY AVAILABLE PERMEATION VIALS
Material
C12
N02
S02
COS
Freon 12
Device
Standard Vials
High Rate Vial
Extra Life Vial
Permeation Tube
Standard Vial
High Rate Vial
Extra Life Vial
Permeation Tube
Standard Vial
High Rate Vial
Extra Life Vial
Permeation Tube
Standard Vial
Extra Life Vial
Standard Vial
Extra Life Vial
Rate (ng/min)
320
1500-7000
1500-7000
300
300
1200-5800
1200-5800
2500-11,000
50
300-1300
300-1300
600-2600
2600
2600
1000
1000
Life (Months)
72
14-3
40-9
1
91
22-5
60-13
1.2
480
89-20
240-56
7
8.7
24
24
66
Width x Length (cm)
.6x7
.6 x 8 to 12
1 x 8 to 12
.6 x 4 to 12
.6x7
.6 x 8 to 12
1 x 8 to 12
.fi x 4 to 12
.6x7
.6 x 8 to 12
1 x 18 to 12
.6 x 4 to 12
.6x7
1 x 7
.6x7
1 x 7
*A11 rates calculated at
6.2.2 Gas Cylinder Dilution System
One of the simplest and most economical systems for providing a
known concentration of pollutant gas to a monitoring system is a gas
dilution system. In essence, a gas dilution system involves mixing a
known concentration of a gas with a diluent gas to provide a known concentra-
tion of lesser value than the original. By measuring the volumetric flow
rates of each gas stream and knowing the concentration of the original
gas to be diluted, one can calculate the final concentration produced by
the following equation:
where:
Cu Ou = Cd (Ou •*
Cu = concentration of undiluted pollutant gas (ppm);
Qu = volumetric flow rate of undiluted pollutant
gas (ml/min);
Cd = final concentration of diluted gas (ppm); and
Qd = volumetric flow rate of dilution gas (ml/min).
From the above equation, it is important to know or measure the
following variables accurately in order to determine the final concen-
tration: Cu, Ou and Od- Knowing these three values and rearranging
the above equation, one can calculate the final concentration of the
diluted pollutant gas by:
Cu is normally provided by the gas manufacturer or through verification
by analysis utilizing Federal Reference Methods.
6-12
-------
One of the simplest means of measuring volumetric flows is through
the utilization of rotameters. If calibrated, rotameters provide a
direct correlation of volumetric flow notation. Figure 6.7 displays a
typical single dilution system employing rotameters.
Qu
JC
-------
In operation, the fluid to be measured passes upward through the
tapered tube, carrying the float to a position in the tube where its
weight is balanced by the upward forces of the fluid flowing past it. At
this point, a constant pressure differential across the float is reached
and is unique for each rotameter. The forces acting in the upward direc-
tion (buoyant and drag forces) exactly equal the force acting in the
downward direction (gravity), as displayed in Figure 6.9.
Buoyant force II I Drag force
Weight of float
Figure 6.9. Forces Acting on a Float
At this point, the volumetric rate can be read from the grad-
uations etched on the side of the tube.
The rotameter is a secondary standard and must be calibrated
before use. When purchased from a manufacturer, a calibration curve
is usually provided. They have either calibrated the rotameter against
a primary standard, such as a soap-bubble meter, or through knowing
construction characteristics of the meter such as tube diameter, float
dimensions, float composition and gas characteristics.
Most rotameters are used and calibrated at room temperature with
the downstream side open to the atmosphere. Correction for temperature
and pressure variations from original calibration configuration are
made by the following equation:
02 = QifPi x T?1
['2 x TlJ
Where: 02 = volumetric flow rate of sampling configuration ( 1/min);
QI = volumetric flow rate of calibration configuration
( 1/min);
?l = pressure at calibration configuration (in Hg);
?2 = pressure at sampling configuration (in of Hg);
TI = temperature at calibration configuration (°F); and
Tg = temperature at sampling configuration (°F).
Because corrections of this nature are usually cumbersome and inaccu-
rate, rotameters are usually calibrated under sampling conditions.
6-14
-------
In recent years, critical orifices have replaced rotameters in
monitoring volumetric flow. If operated properly, the critical orifice
ensures exact delivery of a gas stream within _+ 2%.
The orifice meter consists of some form of restriction located in a
tube constructed of glass, metal or other materials. Two pressure taps,
one upstream and one downstream of the orifice, serve as a means of
measuring the pressure drop. As a fluid traverses the orifice, a pressure
drop develops which can be correlated to flow rate. Figure 6.10 illu-
strates a simple orifice meter, while Figure 6.11 illustrates a typical
orifice meter calibration curve.
Upstream
Downstream
Pressure taps
Figure 6.10. Orifice Meter
\
a
z
I
Critical flow
Figure 6.11. Typical Orifice Meter Calibration Curve
6-15
-------
As the pressure drop across the orifice increases, flow rates
increase, as depicted in Figure 6.11. The region of the calibration
curve whose flow rate changes with pressure drop is termed noncritical
flow and is associated with a variable orifice meter. Within this
region of the calibration curve, one would merely set the pressure
drop across the orifice to a desired number to generate a known flow.
If the pressure drop across the orifice is increased until the
downstream pressure is equal to approximately 0.53 times the up-
stream pressure, the velocity of the gas stream becomes sonic. Even
if the pressure is increased, no increase in flow will occur. The
orifice meter has therefore become "critical." Under these conditions,
a constant flow will occur, as long as the 0.53 pressure relationship
exists.
6.3 STATIC CALIBRATION SYSTEMS
6.3.1 Cylinder Gas Concentration
The gas cylinder is probably the best example of a static calibra-
tion system. The cylinder can be made of different materials and pro-
duced in different sizes. The experience of utilizing gas cylinders as
an auditing technique has been well established in ambient air monitoring.
Highly accurate gas standards for such pollutant as S02, NOX, CO?, and CO
have been used routinely for calibration when auditing ambient air quality
monitors. Manufacturers supply gas mixtures which are routinely accompanied
with a certificate of analysis and a statement of accuracy. Accuracy
levels are generally quoted between 2-5% of the component values.
With the promulgation of Performance Specification 5, sources
subject to Subpart BB, Performance Specification for Kraft Pulp Mills,
had to install, certify and operate continuous emission monitors for
the measurement of total reduced sulfur compounds (hydrogen sulfide,
methyl mercaptan, dimethyl disulfide and dimethyl sulfide). Through the
use of permeation tubes, the regulated sources were able to generate
different concentrations of these pollutants in order to calibrate their
continuous emission monitoring systems. The permeation tube system,
however, is complex and requires certification of flowmeters, temperature
gauges and other hardware. Consequently, sources began examining the
availability of these pollutants in gas cylinders. However, due to the
reactivity and low pollutant concentrations needed, manufacture of these
cylinder gases has been limited.
Gas cylinders come in different sizes, material of construct
and weights. Depending upon its contents will greatly depend upon
material of construction. Likewise, multiple gases have been incor-
porated into one cylinder. Once again, this depends upon reactivity,
compressability and stability of the gases.
6-16
-------
Cylinders containing a pollutant gas are manufactured by adding a
known volume of gas to the cylinder, then pressurizing the cylinder with
a diluent gas to a total gas cylinder pressure. The concentration of
the gas mixture formed can be calculated by the following equation:
106/>c
~A~
ioz/>c
Cm =•
Cppm = concentration of gas mixture, ppm by volume
c% = concentration of gas mixture, percent
Vs = volume of contaminant gas
Vd = volume of diluent gases
pc = partial pressure of contaminant gas
p, = total pressure of the gas mixture
This technique of producing gas concentration is fairly accurate
to gas concentrations from 50 ppm to more than 6000 ppm, depending on
the stability of the gas mixtures.
Another technique of preparing gas cylinder standards is "by-
weight". Utilizing this technique the cylinders are evacuated, then
filled to a weight and allowed to reach equilibrium with the pollutant.
The cylinder is then filled to a final weight with diluent gas. All
weighing is performed on a high precision balance. The final concentra-
tion is determined by the weight percent of pollutant gas in the gas mix-
ture.
6.3.2 Cylinder Gas Problems
In recent years, gas manufacturers have documented problems
associated with maintaining accuracy of prepared certified gas stan-
dards. Problems which have been investigated and documented are:
o cylinder material; and
o gas stability.
6-17
-------
6.3.2.1 Cylinder Material -
The material of construction of the gas cylinders play an important
part in the long term stability of the gas concentration. When reactive
gases such as oxides of nitrogen, carbon monoxide or sulfur dioxide are
blended in a steel cylinder with an inert balance gas, the concentration
can vary with time, temperature and pressure. The mixture's instability
is random and is dependent on the condition of the individual cylinders.
It has been documented that the instability is a function of gas absorption
or reaction with the cylinder walls. Early gas cylinders were constructed
of mild steel and consequently laked long term stability. To alleviate
this problem, many manufacturers have provided gases in materials of
construction other than mild steel. They are:
o Waxed Lined
o S£eel (Cr-Mo) o Treated Aluminum
Table 6.7 illustrates the long term stability of sulfur dioxide in
different cylinder materials of construction.
TABLE 6.7
STABILITY OF SULFUR DIOXIDE (S02) IN
SELECTIVE GAS CYLINDERS
Cylinder
Type
Wax lined
Steel (Cr-Mo)
Treated
Al umi num
Original
Concentration
(ppm)
160
160
160
Analyzed After
Two Months
(ppm)
140
148
159
Analyzed After
Two Years
(ppm)
120
132
157
Another method of decreasing the reactivity between the pollutant
gas and cylinder material is to "soak" the cylinder with a high concentra-
tion of the reactive gas of interest.
The theory behind this "soaking process" is that with time all of
the gas that is going to react with or be absorbed into the cylinder
walls will do so during the conditioning period. When the cylinder is
put into its final mixing stage any further reaction or absorption will
suppossedly be precluded.
This method of preconditioning has met with only limited success.
The problem arises when one realizes that what has been absorbed can also
be desorbed. When the pressure or temperature of the cylinder changes,
the gas that was absorbed during the soaking process can desorb so that
the concentration that the cylinder delivers can actually increase.
Figure 6.12 represents analysis results on preconditioned cylinders
containing 5 ppm nitric oxide in nitrogen as the temperature and pressure
of the cylinder was varied. As can be seen from Figure 6.12, the cylinder
concentrations tend to increase as desorption takes place.
6-18
-------
Q.
a.
GRAPH OF 5ppm NITRIC OXIDE AS A FUNCTION OF DECREASING
PRESSURE. STEEL CYLINDER WAS PRECONDITIONED WITH lOOOppm
.NO IN Nz FOR 7 DAYS_
1900 1700 1500
1300 IIOO 9OO 700
CYLINDER PRESSURE-PSI6
500
300
100
Figure 6.12.
Stability of Nitric Oxide in a Pre-Treated Gas Cylinder
with Decreasing Pressure
Other techniques such as treating the cylinder surface with a
very active gas such as Silane or metal coating of the cylinder walls
were equally inefficient. Consequently, the most promising cylinder
material appears to be treated aluminum. Treated aluminum cylinder
provides a highly inert sealed surface which makes it non-reactive to
pollutant gases.
6.3.?.2 Cylinder Gas Stability -
Gas stability is one of the most serious problems associated with
certified standards. Gas stability is defined as the ability of a gas
mixture to maintain its original concentration with time, temperature
or cylinder pressure. Sulfur dioxide is a highly reactive gas which
has been found to be unstable at very low concentrations. The insta-
bility is due to:
o reaction with moisture;
o reaction with other trace gas impurities; and
o reactions with cylinder walls.
Once again, the use of treated aluminum gas cylinders has enabled
manufacturers to provide certified gas mixtures of S02 in the 0.1 -
20.0 ppm range.
6-19
-------
6.3.3 Cylinder Gas Certification Techniques
Presently, there are several types of gas standards available from
the NRS and commercial manufacturers. They are:
o National Bureau of Standards - Standard Reference Materials
(NBS-SRMs);
o Gas Manufacturers Primary Standard (GMPS);
o Gas Manufacturers Certified Reference Materials (CRMs); and
o Unanalyzed Gases
The NBS-SRMs are sold by the NBS as primary standards. These standards
are prepared environmentally on a high load, high sensitive balance, with
a tolerance of +_ 1 percent of the component. Gas Manufacturers Primary
Standards (GMPSs) are traceable to NBS-SRM's and are used to calibrate
those instruments used in certifying Gas Manufacturer's Certified Standards
(GMCSs). The Gas Manufacturers Certified Standards (GMCSs) are prepared
by a variety of gravimetric and pressure-volume temperature techniques
and analyzed by instrumentation which has been calibrated by NBS-SRM's or
GMPS's. These standards normally have a certification tolerance of _+ 3
percent. The unanalyzed standards are normally prepared in the same manner
as the GMCS's, but are not analyzed. Their certification tolerance are
normally +. 15 percent.
Table 6.8 summarizes the gas standards available and their associated
tolerances.
TABLE 6.8
GAS STANDARDS TOLERANCES
Gas Standard
NBS - SRMs
GMPS
GMCS
Unanalyzed
CRM
Tolerance
percent of the component
+ 1 %
+ 1 %
+ 3 %
T 15 %
+ 1 % of SRM
6.3.3.1
{SRMs)
National Bureau of Standards (NBS) Standard Reference Materials
Standard Reference Materials (SRMs) have been characterized by the
National Bureau of Standards for some chemical or physical property and
are issued with a Certificate that gives the results of the characteri-
zation. These results are obtained by one of the three methods of certi-
fication, i. e. measurement of the property using: (1) a previously vali-
dated reference method; (2) two or more independent, reliable measurement
methods, or (3) a network of cooperating laboratories, technically compe-
tent and thoroughly knowledgeable with the material being tested.
6-20
-------
SRM's are defined as being well-characterized and certified materials.
They are prepared and used for three main purposes: (1) to help develop
accurate methods of analysis (reference methods); (2) to calibrate measurement
systems used to: (a) facilitate the exchange of goods, (b) institute
quality control, (c) determine performance characteristics or (d) measure
some property at the limit of the state-of-the art, and (3) to assure the
long-term adequacy and integrity of quality control processes. In these
ways, SRM's help ensure the compatibility and accuracy of environmental
measurements.
Presently, NBS-SRMs needed in the pulp and paper industry are available
for oxygen (03) and sulfur dioxide (503). Table 6.9 lists those NBS-SRMs
available.
TABLE 6.9
AVAILABLE NBS-SRM PERTINENT TO THE KRAFT PULP MILLS REGULATIONS
SRM
2657
2658
2659
1661a
1662a
1663a
1664a
1693
1694
1696
Type
Oxygen in Nitrogen
Oxygen in Nitrogen
Oxygen in Nitrogen
Sulfur Dioxide in
Nitrogen
Sulfur Dioxide in
Nitrogen
Sulfur Dioxide in
Nitrogen
Sulfur Dioxide in
Nitrogen
Sulfur Dioxide in
Nitrogen
Sulfur Dioxide in
Nitrogen
Sulfur Dioxide in
Nitrogen
Certified
Component
0?
0?
0?
SO?
SO?
SO?
SO?
SO?
SO?
SO?
Nominal Concentration
2.0 mole percent
10.0 mole percent
21 .0 mole percent
500 ppm
1000 ppm
1500 ppm
2500 ppm
50 ppm
100 ppm
3500 ppm
6-21
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6.3.3.2 Certified Reference Materials (CRMs) -
Standard Reference Materials (SRMs) and Certified Reference Materials
(CRMs) are gaseous standards developed by the National Bureau of Standards
(NBS) in cooperation with the Environmental Protection Agency (EPA). The
main objective of this program was to help supply gaseous standards to
industry without depleting the SRM stock. NBS could neither increase
production nor allow "out-of-stock" situations to develop with their SRM
inventory. Consequently, a method was developed which enabled the spe-
cialty gas industry to produce accurate gas standards while maintaining
traceability to NBS-SRM's. The new CRM's would duplicate SRMs in stock
in regard to stability, homogeneity and concentration.
In brief, CRM's are certified by the manufacturer by analyzing their
concentration by an analyzer that has been calibrated with SRM's. The
idea is to calibrate the analyzer with two or three SRM's, then analyze
a "batch" of CRMs with the calibrated analyzer. This provides trace-
ability to NBS-SRM's and increases the number of reference gases available
for commercial usage.
The process by which CRM's are prepared and certified involve:
o preparation of the "batch" CRMs;
o demonstration of homogeneity and stability of the batch;
o batch analysis;
o audit by an independent lab; and
o review of procedures and analytical data by NBS.
If the CRMs meet all the requirements, then the CRMs are certified
reference gases to NBS-SRMs.
6.3.3.2.1 Preparation of CRMs -
CRM's must be prepared in gas cylinders of 10 or more at one time
by a continuous gas generating system followed by a simultaneous com-
pression system. The concentration of the gases in the cylinder must be
identical and must lie within _+ 1% of the concentration of the existing
SRM which the gas manufacturer must physically possess. This stipulation
is required because the CRM program was developed to extend the supply of
available SRMs and to minimize systematic and random errors during analysis
if the CRM is close in concentration to the SRM. (The SRM will be used
as one of the standards in developing the calibration curve for the
analyzer upon which the CRM concentration will be determined).
6.3.3.2.2 Demonstration of Homogeneity and Stability -
Homogeneity and stability of the batch of 10 gas cylinders or
more are determined by analyzing the batch soon after preparation. The
batch is then "incubated" for a period of 30 days. The batch is then
6-22
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reanalyzed and the results from the first batch are compared to the
results of the second batch to determine their stability. The difference
should be random and the algebraic sum of the difference should be small.
The homogeneity of the batch is determined by examining the differences
between the concentration of the sample gases and comparing them to the
expected differences based on the precision of the method.
6.3.3.2.3 Batch Analysis -
The concentration of each CRM (gas cylinder) in the batch is deter-
mined with an analyzer that has been calibrated utilizing the existing
SRM as one of the calibration points. The response of the analyzer to
the SRM calibration points is observed and a calibration curve is con-
structed. The CRM's concentrations are then determined by the analyzer
utilizing the calibration curve generated from the SRMs. The analysis
must confirm that the concentration of each of the CRMs lies within +_ 1%
of the concentration of the SRM that is being duplicated.
6.3.3.2.4 Audit By An Independent Lab -
Two of the CRMs produced by the manufacturer must be analyzed by an
independent lab by an analyzer that has been calibrated by SRMs. The
results of this effort are sent to NBS for evaluation.
6.3.3.2.5 Review of Procedures and Analytical Data by NBS -
The results of the manufacturers analysis of stability and homo-
geneity along with individual gas cylinder analysis are sent to NBS
for review. Concurrent with this, the independent lab sends its results
to NBS. From this information, NBS determines whether the "batch" are
certified CRMs.
6.3.3.2.6 Availability of CRMs -
Presently, thirty (30) batches of CRMs have been approved by NBS
for sale. These batches contain carbon monoxide in nitrogen or air and
nitric oxide in nitrogen. The addition of $03 in nitrogen to the avail-
able CRM list will occur late 1985. Table 6.10 lists those CRMs which
are available along with their manufacturer.
6-23
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TABLE 6.10
AVAILABLE CRMs AND THEIR MANUFACTURER
CRM Gas Type and
Concentration
Gas Manufacturer
1. Carbon Monoxide in N?
10 ppm
25 ppm
50 ppm
250 ppm
1000 ppm
2500 ppm
5000 ppm
25
50
100
250
500
1000
2500
5000
4
8
ppm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
percent
percent
10 ppm
50 ppm
50 ppm
500 ppm
5000 ppm
1 percent
2 percent
8 percent
2. Carbon Monoxide in Air
48 ppm
48 ppm
3. Nitric Oxide in
Nitrogen
100 ppm
250 ppm
500 ppm
250 ppm
Scott Specialty Gases
Scott Environmental Technology, Inc,
U. S. Route 611
Plumsteadville, Pa. 18949
Telephone: (215) 766-8861
AIRCO Industrial Gases
River and Union Landing Roads
Riverton, N. J. 08077
Telephone: (609) 829-7878
Matheson
30 Seaview Drive
Secaucus, N. J. 07094
Telephone: (201) 867-4100
Air Products & Chemicals, Inc,
P. 0. Box 351
Tamaqua, PA 18252
Telephone: (717) 467-2981
AIRCO Industrial Gases
(See above for address and telephone)
Scott Specialty Gases
(See above for address and telephone)
AIRCO Industrial Gases
(See above for address and telephone)
Scott Specialty Gases
(See above for address and telephone)
6-24
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6.3.3.3 Environmental Protection Agency (EPA) Protocol No. 1 Gases -
EPA Protocol No. 1. Traceabillty Protocol for Establishing True
Concentrations of Gases Used For Calibration and Audits of Continuous
Source Emission Monitors, provides for a direct comparison between the
calibration and audit gas standards and an NBS-SRM or gas manufacturer's
primary standard (GMPS) which is referenced to NBS-SRM. The traceability
procedure is intended to minimize errors in determining the true concen-
tration of a cylinder gas. Protocol No. 1 is very similar to the CRM
procedures except:
o Protocol No. 1 allows use of GMPS whereas CRM procedures
do not;
o Protocol No. 1 allows the user to certify his own cylinders
if he follows the protocol; and
o The gas cylinder does not have to be within +_ 1% of the
SRM (or GMPS).
6.3.3.3.1 Concentration Determination -
The procedure of determining the "true" concentration of the gas
cylinder involves the following steps:
o development of a calibration curve utilizing two
NBS-SRMs;
o daily span check utilizing NBS-SRMs or GMPs;
o cylinder analysis; and
o cylinder gas stability
Calibration Curve Development
A multipoint calibration curve is prepared monthly using two SRM
cylinder gases and a zero gas. ( The zero gas must not contain more than
1.2% of the full scale concentration of the component being analyzed).
The multipoint calibration is accomplished by diluting the highest SRM with
zero gas using a calibration flow system. The instrument response for 6
points representing 0, 10, 30, 50, 75 and of the instrument full scale is
obtained. The data is plotted and calibration curve is developed. The
instrument response for the other lower SRM, without dilution, is obtained.
The apparent concentrations from the calibration curve to the true concen-
tration of the lower SRM is compared. If the difference between the
apparent concentration and the true concentration of the lower SRM exceeds
3% of the true concentration, then the multipoint calibration procedure
must be repeated.
6-25
-------
Dally Span Check
On the day the gas cylinder is to be analyzed, the instrument response
is compared to the two SRMs (or GMPS) in the range of the calibration gas
to be analyzed and a zero gas. First, the zero gas is injected into the
analyzer and the zero adjusted to the appropriate concentration. Then
the highest SRM or GMPS is injected into the analyzer and the span valve
adjusted to the valve obtained in the most recent multipoint calibration.
Finally, the lower SRM (or GMPS) is injected into the analyzer. If the
response to the lower SRM (or GMPS) varies by greater than 3% from the
response obtained in the most recent multipoint calibration, a full
multipoint calibration must be performed. If the response to the lower
SRM (or GMPS) is within 3%, then the instrument is ready to analyze the gas
cylinder.
Cylinder Analysis
The analysis involves the direct comparison between the gas cylinder
and the SRM (or GMPS). This allows for compensation for variation in
instrument response between the time of daily span check and the time
of analysis.
The analysis is performed by alternatively injecting the calibration
gas cylinder, then the SRM (or GMPS) until three pairs of analyses have
been completed. For this, the true concentration of the cylinder gas is
determined by the following equation:
True Concentration
of
Gas Cylinder
Apparent Cone.
of
Gas Cylinder
True Cone, of SRM (or GMPS)
Appar. Cone, of SRM (or GMPS)
The mean of the three values determines the true concentration of
the gas cylinder. No one valve can differ from the mean by greater than
1.5*.
6.4 VERIFICATION OF CYLINDER GAS CONCENTRATION
Concurrent with Federal Regulation, Appendix B and F of Part 60,
Standards of Performance for New Stationary Sources, the source owner must
verify gas cylinder concentration used in the CEM program by either
purchasing cylinder gases which conform to EPA's traceability protocol or
analyze the cylinder gases by Federal Reference Methods. The traceability
procedure for gases used in calibrating and auditing continuous emission
monitors is intended to minimize systematic and random errors during the
analysis of these gases and to establish the true concentration by means
of National Bureau of Standards, Standard Reference Materials ( NBS,
SRM). As previously discussed, the procedure provides for a direct
comparison between the calibration and audit gas standards and an NBS,
SRM or a gas manufacturers primary standard (GMPS) which is referenced to
NBS, SRM.
The regulations allow for the source owner to verify his gas cylinder
concentration by utilizing the Federal Reference Methods. For S02 gas
6-26
-------
cylinders, this would Involve sampling and analysis using Federal Reference
Method 6, Determination of Sulfur Dioxide Emissions From Stationary
Sources. For H2S, Federal Reference Method 11, Determination of Hydrogen
Sulfide Content Of Fuel Gas Streams In Petroleum Refineries, is utilized.
In recent years, U. S. EPA has examined procedures for analyzing
gas cylinders utilizing Federal Reference Methods. Studies have indi-
cated an average error of +_ 5% for three consecutive measurements em-
ploying the Reference Methods. Three gas cylinder sample collection
procedures were evaluated: They were:
(1) direct pressure;
(2) vented bubbler; and
(3) evacuated flask.
Of the three procedures, the direct pressure technique appears
to be most applicable to gas cylinder concentration determination for
S02 and H2S utilizing the Reference Methods.
6.4.1 Certification of Sulfur Dioxide (SO?) Cylinder Gas -
The direct pressure technique utilizes Federal Reference Method 6
sampling equipment and analysis. The only difference is the pump is
bypassed in the meter box because the gas cylinder will provide the
pressure needed. Figure 6.13 illustrates the components of the train
assembly as used in certification of sulfur dioxide cylinder gases.
6-27
-------
Midget fritted bubbler
Manometer
U-tube
connections
Class wool
Ice bath
Thennometer
Midget impingers
Meter box assembly
rhermometer
OutletiPH /CMnlet
f
Silica gel
drying cube
_^ Transfer
line
Quick
disconnect
Figure 6.13. S02 Cylinder Gas Certification Set-up
The sampling train consists of a U-tube manometer, an impinger train
and a meter box assembly. The U-tube manometer is used to monitor system
pressure at the inlet of the first impinger.
The bubbler and impingers consist of one midget bubbler with the top
packed with glass wool connected in series with three midget impingers.
The bubbler and impingers must be connected in series with leak free
glass connections.
The metering system should consist of a vacuum gage; thermometers
capable of measuring temperature in the dry gas meter; and a dry gas meter
with 2% accuracy at the required sampling rate.
6-28
-------
In essence, a gas cylinder is certified by measuring the absorbed
S02 in the hydrogen peroxide impingers after a stated sampling period.
Chemically, during sampling, the S02 in the gas stream is oxidized
by the hydrogen peroxide impingers by the following reaction:
S02
Sulfur
Dioxide
H202
Hydrogen
Peroxide
H2S04
Sulfuric
Acid
The sample train impingers are recovered, diluted to a known volume
and titrated with standardized barium perchlorate reagent using thorin
as the indicator. The indicator changes from yellow to pink when the
endpoint is reached. Figure 6.14 displays the titration set-up for
the analysis.
Burette standardized
barium-containing
perchlorate
Flask: • 80 mL of 100% IPA
• 20-mL of sample
• 2-4 drops thorin indicatoi
Figure 6.14. S02 Analysis Set-up
6-29
-------
The titration Involves reacting the standardized barium perchlorate
with the formed sulfuric acid to precipitate barium sulfate. At this
point, the indicator is still yellow. When all of the available sulfate
($04) has precipitated as BaSO/|, the barium attacks the thorin indicator,
changing the color from yellow to pink.
Chemically, this can be expressed as:
Sulfate Reaction
Thorin
Ba(dO4
•BaSO4
yellow
solution
Barium-Thorin Reaction
SO,Na SO.Na
Ba(C104), +
Thorin
indicator
solution
6-30
-------
This reaction of the standardized barium with the sulfate ion provides
a direct correlation between the formed sulfate in the impinger and'the
S02 in the gas cylinder.
The concentration of the S02 in the gas cylinder can then be calculated
from the titration by the following equation:
_v N(V.-V.t)
Where: Cso2 = emission rate of sulfur dioxide (Ib/scf)
V, = volume of titrant required for sample (mL), Ba(ClO4)s
Vrt = volume of titrant required for blank (mL). Ba(ClO4)s
N = normality of Ba(ClO4)s (meq/mL)
Vtain = total volume of sample (mL)
Vm(0d> = volume of sample corrected to standard conditions (dscf)
V0 = volume of aliquot titrated (mL)
K, = 7.061 XlQ-5lb/meq
-X
= (7.061x10-*)
Ib/scf
The concentration of SOg, in ppm, can then be calculated from the
following equation:
SO,(ppm) = 6.01 x
Where: c*>, = SO8 concentration in Ib/scf
6.01 X 10'= conversion factor (Ib/dscf to
The analysis is performed in triplicate along with an EPA certified
vial. The average is used to determine concentration of the gas cylinder.
6-31
-------
6.4.2 Certification of Hydrogen Sulfide (HpS) Cylinder Gas
Similar to S02 procedures, H2S is determined utilizing Federal
Reference Method 11 sampling equipment and analysis. Figure 6.15
illustrates the components of the certification train assembly.
Sampling
vmlve
Vi in. teflon
' sampling line
Impinger assembly
To
atmosphere
Figure 6.15.
Cylinder Gas Certification Set-up
The sampling train consists of 5 midget impingers connected in
series, each with 30 ml capacity. The metering system should consist of
a vacuum gage, a rate meter, and a dry gas meter with 2% accuracy at the
required sampling rate. A U-tube water manometer is also used to perform
a leak rate determination.
6-32
-------
During sampling, the hydrogen sulfide gas in the gas cylinder
is scrubbed by the cadmium sulfate in the impingers to form a yellow
precipitate, CdS. Chemically, this can be expressed by the following
equation:
H2S
Hydrogen
Sulfide
Cadmium
Sulfate
Cadmium
Sulfide
H2S04
Su If uric
Adic
After sampling, the impingers are recovered into a 500-ml iodine
numbered volumetric flask containing acidified iodine solution. The
acidified iodine solution liberates the captured H2S which then reacts with
the available iodine. Chemically, the following reactions are occurring:
CdS
Cadmium
Sulfate
2HC1
Hydrogen
Chloride
Hydrogen
Sulfate
CdC]2
Cadmium
Chloride
H2S
Hydrogen
Sulfide
Iodine
Hydrogen
Iodine
s
Sulfur
The remaining iodine in the flask is titrated with standardized
sodium thiosulfate using starch as the indicator. The titration is
from a dark purple to clear endpoint.
This titration process has completed the following reaction:
Dark Blue
2Na2S2Os + I2—
Standardized
Sodium Thiosulfate
starch
Clear
2NaI
By analyzing a blank solution of acidified iodine and comparing
the titrated sample to the blank sample, the concentration of H2S in
the gas cylinder can be determined by the following equation:
6-33
-------
( VirN, - VrrNQsample - (V/rN, -
t-
»•,
Where: c«j5 = emission rate of HtS at standard conditions, gr/dscf
K. = conversion factor
(34.07 g/mole H,S)(7000 gr/lb) =02629
(2HgS eq/mole)(1000 mL/L)(453.6 g/lb)
V/r= volume of standard iodine solution = 50 mL
N/= normality of standard iodine solution, g-eq/L
Vrr = volume of standard sodium thiosulfate solution, mL
NT = normality of standard sodium thiosulfate solution g-eq/L
Vm(n
-------
7.0 COMPARATIVE STUDIES OF TRS MONITORS
7.1 INTRODUCTION
Since the early 1960s, the National Council for Air and Stream
Improvement (NCASI) has conducted several studies associated with the
development and evaluation of measurement techniques for total reduced
sulfur from pulp mill processes. Early in the evaluation, the studies
centered around manual extractive techniques. However, as continuous
emission monitors started playing a predominant role in a source emission
monitoring program, the NCASI turned its attention to their performance
and evaluation. The objective of this chapter is to examine three major
studies involving TRS CEM evaluations performed by the NCASI. The first
study was conducted in 1977 and dealt with TRS detector evaluation. The
second study, conducted in 1983, evaluated six (6) commercially available
TRS monitors. Finally, the third study involved comparison between gas
chromatography (Reference Method 16) and wet chemical (Reference Method
16A) techniques.
7.2 NCASI EVALUATION OF TRS DETECTORS - STUDY #1
The first major study by NCASI involved evaluating commercially
available TRS CEMs. The objective of this 1977 study was two fold:
(1) to observe the field performance of several TRS monitoring
detectors in reference to their accuracy, zero and span drift over a
period of time; and (2) to evaluate the performance of a properly de-
signed recovery furnace sampling system by determining its response
characteristics.
The study was conducted over a period of 3 months in two district
phases. During the first phase, the sampling system was installed and
the performance of the commercially available TRS monitor detectors was
evaluated. Those systems evaluated during this phase involved gas chro-
matography, coulometric titration and photoionization detection. During
the second phase of the study, the source gas was oxidized to S02 and
measured as S02 on a flame photometric total sulfur analyzer. Results
of that study were reported in Atmospheric Quality Improvement Technical
Bulletin No. 91, published by the NCASI.
7.2.1 Test Configuration
The objective of the study was to examine commercially available TRS
detector systems, not their extractive mechanism. As such, a common sample
extraction/conditioning system was used. The sample extraction/conditioning
system consisted of an external filtered probe, a condenser, a continuous
S02 liquid scrubber system and a sample manifold, as illustrated in Fig-
ure 7.1.
7-1
-------
PROBE
02-STAGE
CONTINUOUS
SCRUBBER
ROP-OUT BOTTLE
HEAT TRACED
TEFLON
LINE
WASTE
SO2
SCRUBBING
SOLUTION
CONOEMSATE
SCRUBBING
SOLUTION
OVERFLOW
CALIBRATION
GAS
WASTE
VACUUM SAMPLING
MANIFOLD
ACTIVATED
CARBON
Figure 7.1. Common Extraction System Used in the NCASI TRS Detector
Evaluation.
From the manifold, the gas stream was split into five individual streams
leading to the five detectors, as illustrated in Figure 7.2
PROBE
ASSEMBLY
CALIBRATION
~GAS
SAMPLE
CONDITIONING
AND
SO2 REMOVAL
1 WAST
CALIBRATION
GAS
1
1 L-
_]_ VACUUM SAMPLI
| PUMP MANIFO
1
1
1
SAMPLING'
E
— DETECTOR 1
MG
LJ —DETECTOR 2
— DETECTOR 3
•-•-"• DETECTOR 4
"STATION
Figure 7.2. Sampling Manifold Configuration Leading to Individual Detectors,
7-2
-------
The five TRS detectors under evaluation were:
o Detector 1: Gas Chromatography with Flame Photometry;
o Detector 2: ITT Barton Coulometric Titrator;
o Detector 3: Thermal Oxidation with ITT Barton Coulometric
Titrator;
o Detector 4: Photoionization; and
o Detector 5: Flame Photometry Total Sulfur Analyzer.
The gas Chromatography technique (Detector 1) with flame photometric
analysis involved analytical separation of all reduced sulfur compounds
by chromatographic columns with subsequent analysis. Detector 2 (coulo-
metric titration) involved analysis of all reduced sulfur compounds with
no pretreatment. Detector 3 configuration involved pretreatment of the
gas sample by thermal oxidation of all reduced sulfur compounds to S02,
then analysis by the,coulometric titration technique. Detector 4 (photo-
ionization technique) and Detector 5 (flame photometric technique) required
no sample pretreatment. However, due to component failure, the photoioniza-
tion technique provided little information during the test series.
Before the accuracy of the individual detector systems could be ex-
amined, NCASI evaluated the conditioning system to pass reduced sulfur
compounds and the response time of the total TRS CEM system.
7.2.2 Conditioning System Evaluation to Pass Reduced Sulfur Compounds
To determine the efficiency of the conditioning system to pass re-
duced sulfur compounds, known concentrations of H2S, CH3$H, (^3)2$ and
(CH3)2S2 were injected at the probe inlet and allowed to pass through the
conditioning system to the detectors. Fifteen (15) tests were performed
at total reduced sulfur concentrations ranging from 2.6 ppm to 5.8 ppm.
The results of this portion of the field study indicated that a properly
maintained conditioning system can pass greater than 90% of reduced
sulfur compounds at an average inlet concentration of 4.8 ppm. These
results, however, are applicable only to Kraft recovery furnaces as reported
by NCASI. Greater sample losses were experienced at lime kilns (~75% reduced
sulfur compounds pass at a ~10 ppm inlet concentration).
7.2.3 Sampling System Response Time
Sampling system response time was measured with the ITT Barton coulo-
metric titrator. The upscale and downscale values were determined accord-
ing to Performance Specification Test 2 and 3. These tests indicate an
average monitor response time of 7.2 minutes, well within the 15 minutes
allowed by the Performance Specification Test.
7-3
-------
7.2.4 Detector Accuracy and Zero/Calibration Drift
7.2.4.1 Accuracy Deteritri nation -
The accuracy of each system was compared to that of the others (in
some cases) and routinely compared to the gas chromatograph with flame
photometric detection as the reference method. To determine accuracy, the
detectors were turned on each day, zeroed with zero air and calibrated.
The accuracy tests were then determined for a test period of 8 to 14 hours.
This protocol was established by NCASI due to the calibration drift prob-
lems associated with the gas chromatograph.
The results of the accuracy tests are presented in Table 7.1. The
results indicated the Barton coulometric titrator, used in its normal mode
and in association with the thermal oxidation system, was the only system
which operated according to manufacturer specifications and within EPA
guidelines.
TABLE 7.1
NCASI DRIFT/ACCURACY EVALUATION
OF TRS DETECTORS - STUDY #1
Detector
Coulometric Titrator
Coulometric Titrator
Thermal Oxidation
System
Flame Photometric
Total Sulfur
Analyzer
Photoionization
Detector^
Range,
ppm
0-5
5-30
5-30
5-30
-
# of
Obser-
vations
326
126
119
20
-
Avg. Diff.
between
Obs.
(ppm)
0.04
0.11
0.05
- 1.34
-
% Within <-
Range, ppm
-1.5
-------
7.2.4.2 Zero and Span Drift Determination -
A 24-hour zero/span drift determination was performed, according to
Performance Specification Test 2, on the coulometric titrator detection
principle. The results of this evaluation indicated 1.27% and 9.78%
span drift values for the 24-hour zero/span determination, respectively.
7.2.5 Test Results Summary
Results of the first major study of commercially available TRS de-
tectors indicate that both the Barton coulometric titrator (operated in
its normal mode) and a thermal oxidation system used in conjunction with
the Barton coulometric titrator operated within EPA's guidelines at Kraft
recovery furnaces.
7.3 NCASI EVALUATION OF TRS DETECTORS - STUDY #2
7.3.1 Introduction
Since that evaluation, two important events occurred to cause NCASI
to initiate a second study. In 1981, EPA proposed Performance Specifica-
tion 5 which involved performance specifications associated with calibra-
tion drift and relative accuracy of installed TRS monitors. Likewise,
since the 1977 study, several new manufacturers were providing TRS moni-
tors on a commercial basis to the Kraft pulp mill industry. With very
little information associated with the newer instruments, NCASI, in June
1983, began a six-month test to evaluate available TRS CEMs.
The main objective of this 1983 study was to evaluate commercially
available TRS monitors and their detection systems. The objective was
not to evaluate the probe or conditioning system associated with each
monitoring system. As part of the study, six manufacturers of TRS
monitors were evaluated. They were:
o Candel Dynalyzer Series 300 Portable TRS Analyzer:
o ITT-Barton Model 411-S TRS Monitoring System;
o Modified Monitor Labs Model 8850 S02 Monitor;
o Sampling Technology Incorporated (STI) Model 100 TRS Monitor;
o Theta Sensors Model 7000 S02 Monitor; and
o Tracer Atlas Model 825 R-D Analyzers.
Table 7.2 lists those monitors that were evaluated and their measure-
ment principles.
7-5
-------
TABLE 7.2
NCASI EVALUATION OF TRS DETECTORS - STUDY #2
Manufacturer
Candel Dynalyzer Series
300 Portable TRS Analyzer
P.O. Box 2580
Sidney, British Columbia
ITT - Barton Model 411
TRS Monitor
P.O. Box 1882
City of Industry, CA
Monitor Labs Model 8850
S02 Analyzer
STI Model 100 TRS
P.O. Box R
Waldron, AR
Theta Sensors Portable
TRS Monitor
17635A Rowland Street
La Puente, CA
Tracor Atlas Model 856/8P5
TRS Monitor
Detection Principle
Electrochemical
Coulanetric Titrator
Fluorescent
Fluorescent
Electrochemical
Impregnated Lead Acetate
TRS Analyzed
As
S02
S02
S02
SO?
S02
Total Reduced
Sulfur
(H2S)
Conditioning System
Thermal
Oxidation
Quartz Tube
Quartz Tube
Stainless Steel
Tube
(Stainlesss Steel
Chips)
300°C
Quartz Tube
(1500°F)
Not supplied
by Manufacturer
N/A
Reduction
Furnace
N/A
N/A
N/A
N/A
N/A
Hydrogenator
Reduction
Furnace
(1000°C - 1300°C)
CTi
-------
All analyzers were evaluated in five (5) major categories:
o Operating and maintenance experience;
o Thermal oxidation furnace design and performance;
o Tests of interferences from NO and C02;
o Calibration drift test; and
o Relative accuracy test.
7.3.2 Test Program
The test program involved both laboratory and field evaluation of the
TRS monitors only and not the complete sampling system. The laboratory
evaluation occurred at the NCASI Gainesville Regional Office. The field
evaluation occurred at a local Combustion Engineering Kraft recovery
furnace with a rated capacity of 130,000 Ibs/hr of oxidized black liquor
at 65% solids. The furnace had a cascade evaporation and two wet bottom
precipitators in series. The sulfide level in the oxidized black liquor
ranged from 0 to 0.5 gm/1 as NagS. The particulate concentration in the
stack gas was normally 0.02 gr/DSCF.
The TRS CEM evaluation consisted of three major phases;
Phase 1: Survey of TRS CEMs in the industry;
Phase 2: Laboratory/field evaluation of selected monitors; and
Phase 3: Field evaluation of selected probe and gas conditioning
system.
The laboratory objectives were to operate the monitors in a controlled
environment to gain operating experience. Next, they were challenged
with different sulfur compounds to determine furnace ability to oxidize
the reduced sulfur compounds to S02« The third portion of the laboratory
test was to challenge the monitors with NO and C02 to determine their
interference potential on the monitoring systems.
The field evaluation involved both a calibration drift determination
and relative accuracy evaluation. Calibration drift and relative accuracy
were determined against Federal Reference Method 16.
7.3.2.1 Laboratory Evaluation -
One of the objectives of the laboratory evaluation was to gain ex-
perience in operating the different TRS CEMs in a controlled environment.
NCASI reported no major problems associted with operating the instruments
on a daily basis. Secondly, the monitors were checked for converter effi-
ciency (TRS -^ SOg). As illustrated in Table 7.3, problems were observed
with this portion of the evaluation. Where needed, corrective action was
taken by NCASI to improve the converter systems. The third objective of
the laboratory evaluation was to determine if other gases, i.e. NO and
C02, interfere with the individual measurement techniques.
7-7
-------
The results, summarized in Table 7.3, indicate there was no interference
associated with COg. However, several monitors showed positive interfer-
ence from NO gas. Of those monitors evaluated, the electrochemical tech-
niques showed the highest degree of interference. Table 7.3 summarizes
the results of the laboratory evaluation.
7.3.2.2 Field Evaluation -
The field evaluation involved determining the monitor's calibration
drift and relative accuracy under field conditions. A common ITT-Barton
probe/conditioning system was used to extract the flue gas sample from
the stack. The extraction system consisted of a probe, a control valve
and a vortex condenser. The probe was a thick walled Teflon® tube inside
a stainless steel liner.
The gas sample passed from the probe, through the condenser where
water is removed, through a heated trace line to a temperature controlled
instrument room. Within the instrument room, the sample passed through
five impingers in series containing potassium citrate - citric acid buffer
solution to remove SOg from the gas stream. Leaving the five impingers,
the sample gas then passed through a Teflon® filter, a sampling pump and
into a common manifold. From the manifold, the sample gas passed to
individual analyzers involved in the field evaluation.
Three reference methods were used to determine source gas TRS
concentration. The three methods were:
o Federal Reference Method 16;
o Federal Reference Method 16A; and
o NCASI Modified Federal Reference Method 16.
EPA Federal Reference Method 16 for TRS is based on a gas chromato-
graphic separation with subsequent detection of sulfur compounds by flame
photometric detection. Federal Reference Method 16A is a wet chemical
technique based on S02 separation from TRS, oxidation of TRS to SO?, then
capturing the S02 in a series of impingers containing hydrogen peroxide.
The impingers are analyzed by a barium-thorin titration for sulfates,
which are reported as TRS.
NCASI's Modified Method 16 is identical to EPA's Method 16 except that
prior to analysis by the gas chromatograph/flame photometric detector
(GC/FPD), the gas sample is passed through a thermal oxidizer and the TRS
compounds are oxidized to $03, just as in Method 16A. The sulfur compounds
are then analyzed as SOg on the 6C/FPD. All other provisions of Method
16 are followed, including removal of source gas $63, moisture, and particu-
late matter prior to analysis. The system was calibrated against a permeation
tube calibration device.
The monitors were tested in the field for calibration drift and for
relative accuracy. Calibration drift is determined by comparing monitor
response to zero and span test gases.
7-8
-------
TABLE 7.3
NCASI EVALUATION OF TRS DETECTORS - STUDY #2
LABORATORY EVALUATION
Manufacturer
Candel Dynalyzer Series
300 Portable TRS Analyzer
P.O. Box 2580
Sidney, British Columbia
ITT - Barton Model 411
TRS Monitor
P.O. Box 1882
City of Industry, CA
Monitor Labs Model 8350
S02 Analyzer
STI Model 100 TRS Monitor
P.O. Box B
Waldron, AR
Theta Sensors Portable
TRS Monitor
17635A Rowland Street
La Puente, CA
Tracer Atlas Model 856/825
TRS Monitor
Detection
Principle
Electro-
chemical
Coulometric
Titrator
Fluorescent
Fluorescent
Electro-
chemical
Impregnated
Lead
Acetate
TRS
Analyzed
As
S02
S02
S02
S02
S02
Total
Reducible
Sulfur
(H2S)
Operating and Maintenance
Experience
o slow response
o difficult to calibrate due to
sensitivity of zero/span
potentiometers.
o confusing dial settings
o occasional flow rate adjustments
o failure of si li cone tubing
o cell reach equilibrium ( 30 min)
after changing ranges.
No major problems
No major problems
—
o Flow rate sensitive
o Back pressure sensitive
o Difficult to calibrate
Converter Study
Oxidizing
Potential
Complete
oxidation
of TRS
compounds
Not able
to oxidize
all TRS
compounds
Not able
to oxidize
all TRS
compounds
Complete
oxidation
of TRS
compounds
Oxidizer
not sup-
plied by
manufac-
turer
Non app-
licable
due to
measurement
technique
Modifications
None
Additional
insulation
with quartz
wool
Use of
another oxi-
dizer during
field evalu-
ation.
None
—
Interference
Study
NO Gas
+5%
None
+1%
+0.5%
Not
tested
None
CO? Gas
None
None
None
None
Not
tested
None
-------
Performance Specification Test 5 requires that the detector span must
be checked at 90 to 100 percent of the full scale level, and the full
scale span level must be between 1.5 times the emission standard (5 ppm
for Kraft recovery furnaces) and the maximum span value (30 ppm). The zero
calibration must be checked using a test gas containing no TRS or at a
level up to 20 percent of the span level. In order for a monitor to satis-
fy the PS 5 calibration drift criteria, its calibration drift over a 24
hour period must not exceed 5 percent (1.5 ppm) of the span value (30 ppm)
for at least 6 out of 7 days.
Performance Specification Test 5 defines relative accuracy (RA) as:
where:
dj
cfj
cc
RA =
+ lccl X 100
RM
(monitor value) - (reference method value);
arithmetic mean of d-j's;
to.975 Id ;
RM = arithmetic mean of reference methods; and
n = number of tests.
PS 5 specifies that for a CEM to be acceptable, the RA must not
exceed either 20 percent of the RM or 10 percent of the standard, whichever
is greater.
According to PS 5, the RA test must include a minimum of nine RM
tests. Each RM test must be conducted within 30 to 60 minutes. More
than nine RM tests may be performed and included in the RA determination.
Additionally, if more than nine RM tests are performed, as many as three
tests may be excluded from the RA determination, as long as a minimum of
nine are included.
Table 7.4 illustrates the results of both the calibration drift
test and the relative accuracy test for the evaluated monitors.
7.3.3 Test Results Summary
A total of 47 relative accuracy tests were performed on all monitors.
Table 7.5 reflects the number of tests passed for each monitor, while
Table 7.6 displays overall performance of the TRS monitors.
Results of the study indicated the ITT Barton Coulometric Titrator
and the STI Model 100 TRS monitor produced TRS concentrations represen-
tative of the gas chromatographic reference method. Both of these
monitoring principles met Performance Specification Test Relative Accuracy
criteria (+ 20%) in approximately 90% of the tests. The other monitors
performed with less accuracy.
7-10
-------
TABLE 7.4
NCASI EVALUATION OF TRS DETECTORS - STUDY f 2
LABORATORY/FIELD EVALUATION
Manufacturer
Candel Dynalyzer Series
300 Portable TRS Analyzer
P.O. Box 2580
Sidney, British Columbia
ITT - Barton Model 411
TRS Monitor
P.O. Box 1882
City of Industry, CA
Monitor Labs Model 8850
S05 Analyzer
c.
STI Model 100 TRS
P.O. Box B
Waldron, AR
Theta Sensors Portable
TRS Monitor
17635A Rowland Street
La Puente, CA
Tracer Atlas Model 856/825
TRS Monitor
Calibration drift
Results
(5% of span value)
0-5 ppm
Passed1
Passed?
Passed2
Passed2
Passed1
No test
performed
27-30ppm
Failed1
Passed2
Passed2
Failed2
(3rd
test)
Failed1
No test
performed
Average
Relative Accuracy
Test (%) 3
Monitor Span
7.5
F
125
13
13
11
126
-
10
F
151
14
22
13
_
34
30
F
67
12
18
13
360
26
General Comments
o Analyzer tested designed for much higher
concentrations;
o Positive interference from NO (+5%).
o Cell temperature/TRS content of stack gas
affects life of monitor;
o Replacement of cell once per month.
o Limited life of hydrocarbon cutter ( -\,3 weeks );
o Response to calibration gases in oxygen different
than calibration gases in nitrogen.
o No rotameter to indicate calibration gas flowrate.
o Original monitor sold as source level S02
analyzer, 0-100 ppm. Manufacturer changed elec-
tronics, but instrument became inoperative after
4 months of testing;
o Electrochemical sensor poisoned by reduced sulfur
gases.
o Replacement of lead acetate tape and acetic acid
blubber every two weeks;
o Because monitor cycles, difficult/time consuming
to zero/span instrument;
o Condensed moisture problem associated with back
pressure vent.
1 Summary of two tests
( P= Pass; F= Fail )
2 Summary of three tests
3 Relative Accuracy Criteria ( _+ 20% );
4 Nine samples per test at each monitor span value.
-------
TABLE 7.5
NCASI RELATIVE ACCURACY TEST PASSED
Manufacturer
Candel
ITT Barton
Monitor Labs
STI
Theta Sensors
Tracor Atlas
Number of Relative Accuracy
Tests Passed1
4
34
20
35
0
2
Total
Relative Accuracy
Tests Performed
47
47
45
44
26
10
iCriteria: + 20% Relative Accuracy
TABLE 7.6
RELATIVE ACCURACY TEST RESULTS - FRACTION OF RELATIVE
ACCURACY TESTS PASSED
Instrument
9/9 Runs
9/12 Runs
ITT-Barton
Candel Analyzer
Carlton Technology
Monitor Lines
STI
Theta
Sensors
Tracor
Atlas
14/21 (67%)
0
7/21 (33%)
18/21 (86%)
0
withdrawn
18/21 (86%)
0
13/21 (62%)
21/21 (100%)
0
withdrawn
7-12
-------
8.0 THE REFERENCE METHOD
8.1 INTRODUCTION
Federal Reference Method 16, Semicontinuous Determination of Sulfur
Emissions from Stationary Sources, was promulgated February 23, 1978.
The method utilizes the principle of gas chromatography (GC) separation
of sulfur species with subsequent flame photometric detection (FPD).
Figure 8.1 illustrates the basic components of Federal Reference Method 16
analytical configuration.
HAUE nioTfuuraic DITECTDB
vuuuu
CARRIES
1
-tr
f~
v'^
t3
J— s
I
(
COLUMN \
H| <,».
|
I
,
II <
|
li
FILTIA
\\
T
POVfER
-_
— C
s/
^**^^
^^
SUPPIY
nccoRom
e o
Li H-
1 ^—^
SAMPLir.G VALVC FOil
•J5- TO GOFPD-II
Figure 8.1. Federal Reference Method 16 Analytical Configuration.
8-1
-------
As defined in Subpart A - General Provisions, of 40 CFR 60, a
"Reference Method" means any method of sampling and analyzing for an air
pollutant as described in Appendix A - Reference Methods. The Reference
Methods are promulgated by EPA to provide uniform analytical methods to
ensure consistency and accuracy in the data generated. The legal authority
for this action lies in Sections 111, 114 and 301 (a) of the Clean Air
Act. In brief, it states:
"...within 120 days after the inclusion of a category
of stationary sources in a list under subparagraph (A),
the administrator shall publish proposed regulations,
establishing Federal Standards of Performance for new
sources within such category."
The prescribed Reference Method to be used to determine compliance
with a standard is specified in the subparts associated with the affected
facility as part of the standard of performance. Within each Subpart, a
section titled: "Test Methods and Procedures" is provided to:
o Identify the Reference Methods applicable to the affected
facility subject to the respective standard; and
o Identify any special instructions or conditions to be
followed when utilizing the Reference Method.
For Subpart BB - Standards of Performance for Kraft pulp mills, the
following Reference Methods are prescribed to determine compliance:
Reference Method 1 - Sampling and Velocity Traverses for Stationary
Sources;
Reference Method 2 - Determination of Stack Gas Velocity and
Volumetric Flow Rate (Type S Pitot Tube);
Reference Method 3 - Gas Analysis for Carbon Dioxide, Oxygen,
Excess Air and Dry Molecular Weight;
Reference Method 5 - Determination of Particulate Emissions from
Stationary Sources;
Reference Method 16 - Semi continuous Determination of Sulfur Emissions
from Stationary Sources; and
Reference Method 17 - Determination of Particulate Emissions from
Stationary Sources (In-Stack Filtration Method).
Most Reference Methods involve specific equipment specifications and
procedures, and only a few methods rely on performance criteria. Reference
Method 16 is one of the exceptions to the rule. Reference Method 16 has
established criteria by which any system design can be used as long as it
meets this criteria. Consequently, certain specific equipment or proced-
ures are recognized in the method as being acceptable or "potentially"
acceptable. Those items identified in the method as acceptable options
may be used without approval from EPA. The potentially approvable options
are cited as "subject to the approval of the Administrator."
8-2
-------
8.2 FEDERAL REFERENCE METHOD 16
Federal Reference Method 16, as promulgated in the Federal Register,
Thursday, February 23, 1978, is divided into thirteen (13) sections.
Figure 8.2 outlines those sections.
FEDERAL REFERENCE METHOD 16
1.0
i.0
54
1.0
!.0
10
7JO
10
10
10
11
12
3
^m
^m
m*
^H
M
M
M
••
••
PRINCIPLES AND APn.ICMn.ITt
RANCE AND SENSITIVITY
INTERFERENCES
PRECISION AND ACCURACY
APPARATUS
REAGENTS
PRETEST PROCEDURES
CALIBRATION
SAMPLING AND ANALYSIS
"OST TEST PROCEDURES
1
CALCULATIONS J
EXAMPLE SYSTEM
BIBLIOGRAPHY i
Figure 8.2. Federal Reference Method 16 Sections.
8-3
-------
Sections 1-6 address such topics as method application, range and
sensitivity, interferences, precision/accuracy, apparatus and reagents.
It is within these sections that specific equipment or procedures are
recognized as being acceptable or "potentially" acceptable for use as the
Reference Method. The basic analytical procedure, as outlined in these
sections, is the determination of total reduced sulfur (TRS) emissions
from Kraft pulp mills utilizing gas chromatography (GC) separation with
subsequent flame photometric detection (FPD).
There are many systems and operating conditions that represent usable
methods of determining sulfur emissions employing the above principle.
These systems may differ in details of equipment and operation; however,
they may be used as alternative methods, provided that the criteria es-
tablished by the reference method are met. The basic criteria for TRS
analysis by Federal Reference Method 16 are:
o Gas chromatographic (GC) separation with flame photometric detec-
tion (FPD);
o Demonstration of no interferences from moisture condensation,
carbon monoxide (CO), carbon dioxide (C02), particulate matter
and sulfur dioxide (S02);
o Precision and accuracy evaluation of:
o GC/FPD and dilution system calibration precision not to
exceed +_ 5% from the mean of three known calibration gas
injections;
o GC/FPD and dilution system calibration drift not to exceed
10% from the mean of three known calibration injections made
at the beginning and end of any 8-hour period; and
o system calibration accuracy must be determined, through the
complete sample transport system, and a correction factor
developed to adjust the calibration accuracy to 100 percent.
o Calibration of GC/FPD with gravimetrically calibrated and certi-
fied permeation tubes;
o Calibration of dilution system;
o Losses of 835 through sample transport system not to exceed 20%;
and
o Total system must be able to detect a minimum of 1.0 ppm of
hydrogen sulfide (^S), methyl mercaptan C^SH, dimethyl sulfide
(CH3)2S and dimethyl disulfide (CH3)2S2.
8-4
-------
8.2.1 Reference Method Ifi Sampling System
Federal Reference Method 16 sample system consists of five basic
components:
o probe/SOj scrubber system;
o sample line/pump system;
o dilution system;
o analysis system; and
o calibration system.
8.2.1.1 Probe/SO? Scrubber System -
The probe must be made of inert material such as stainless steel or
glass. It should be designed to incorporate a filter (in-stack or out-of-
stack) and allow calibration gas to enter at or near the sample entry point.
Since S02 interferes with the detection of TRS compounds, it must be
removed prior to analysis by the GC/FPD. A series of scrubbers, located as
close to the probe as possible, utilizing potassium citrate - citric acid
buffer solution should be used to remove SC»2.
8.2.1.2 Sample Line/Pump -
The sample line must be made of Teflon®, no greater than 1.3 cm
(l/2in) inside diameter. All parts from the probe to the dilution system
must be thermostatically heated to 120°C. The sample pump shall be a
leak less Teflon®-coated diaphragm type or equivalent. If the pump is
upstream of the dilution system, the pump head must be heated to 120°C.
8.2.1.3 Dilution System -
The dilution system must be constructed such that all sample contacts
are made of inert materials (stainless steel or Teflon®). It must be heated
to 120°C and be capable of approximately a 9:1 dilution of the sample.
8.2.1.4 Analytical System -
The analytical system involves the gas chromatograph columns and sub-
sequent flame photometric detector. The column system must be demonstrated
to be capable of resolving the four major reduced sulfur compounds: HpS,
CHsSH, (CH3)2S and (CHsJzSg. It must also demonstrate freedom from known
interferences.
To demonstrate that adequate resolution has been achieved, the tester
must submit a chromatograph of a calibration gas containing all four of the
TRS compounds in the concentration range of the applicable standard. Ade-
quate resolution will be defined as base line separation of adjacent peaks
when the amplifier attenuation is set so that the smaller peak is at least
50 percent of full scale.
8.2.1.5 Calibration System -
The calibration system involves the permeation tube calibrator system
with flow system support and constant temperature bath.
8-5
-------
Hermetically sealed FEP Teflon® permeation tubes, one each of
CH3SH, (CH3)2Stand (0^3)282, gravimetrically calibrated and certified at a
stated temperature, will be used to generate known concentrations of pol-
lutant atmospheres to calibrate the GC/FPD system. The permeation tubes
will be placed in the constant temperature bath 24 hours prior to use to
allow for stable flow and tube equilibrium to be reached. When the temper-
ature is constant, the calibration gases will permeate through the tube wall
and mix with the diluent flow passing over the tubes. The total flow should
be accurately measured for final concentration determination.
The diluent air should contain less than 50 ppb total sulfur compounds
and less than 10 ppm each of moisture and total hydrocarbons.
8.2.1.5.1 Flow System -
The flow system should be able to measure gas flow within +2 percent.
Each flow measuring device should be calibrated after a complete series
of tests with a wet test meter.
8.2.1.5.2 Constant Temperature Bath -
A constant temperature bath is required to maintain the permeation
tubes at the calibration temperature within +0.1°C.
Once the complete system is assembled, verification of system
integrity is determined by:
o leak check procedures;
o calibration of analyzer system;
o calibration of dilution system; and
o system performance check.
These checks are covered in Sections 7.0, 8.0, 9.0 and 10.0 of the
Reference Method. In essence, these sections cover the sequence of test
procedures used during the compliance test.
8.2.2 Sample Extraction
8.2.2.1 Pretest Procedures (Section 7.0) -
The pretest procedures are optional ; however, the regulations strongly
suggest that they be incorporated into a test protocol. The pretest pro-
cedures involve:
o positive/negative leak check of the sampling train; and
o determining system performance.
The positive leak check is performed by attaching a vacuum gauge to
the probe tip, turning on the pump and pulling a vacuum of approximately
2 inches. Once the appropriate vacuum is reached, the pump is turned off
and leak rate observed as indicated by the vacuum guage. For components
after the pump, a slight positive pressure is applied to the system and
leaks are observed with the aid of a liquid solution.
8-6
-------
System performance is verified by observing and comparing all flow
meters, monitor response to changes in flow rates and other active compo-
nents of the monitoring system to baseline data.
8.2.2.2 - Calibration of Sampling Train (Section 8.0) -
Section 8.0, Calibration, deals with the preparation and validation
of the calibration curve as observed by the detector and the calibration
of the dilution system. To accomplish both of these evaluations, a per-
meation tube system is used to generate known concentrations of H2S,
CH3SH, (CH3)2S and (CH3)2$2. A typical permeation tube system used in
the field is shown in Figure 8.3.
The permeation tubes for the four reduced sulfur compounds are placed
in the constant temperature bath 24 hours prior to usage to allow the tubes
to equilibrate. Concentration, ppm, generated by the tubes of the reduced
sulfur compounds can be calculated by the following equation:
r = K |Prl
V» l\ I - r- I
Where:
C = concentration of pollutant produced in ppm;
Pr = permeation rate of tube in /jg/min;
M = molecular weight of pollutant (g/g-mole);
L = flow rate,ml/min, of air over the tubes; and
K = gas constant at 20°C and 760 mm.
Consequently, three important variables must be observed and certified
in order to ensure the production of a known pollutant. They are:
o Certification of permeation tube emission rate;
o Certification of permeation device temperature; and
o Certification of flowmeters in the calibration system.
Certificates are usually provided by the manufacturer (+2% of permea-
tion rate) for each permeation tube. The tubes are gravimetrically certi-
fied by the vendor, as illustrated in Figure 8.4.
As illustrated in Figure 8.4, the tubes are certified at a specific
temperature. The reviewer should verify the calibration of the temperature
indicating device.
Certification of flowmeters used in the calibration system should be
verified by calibration curves or measured each time by a soap bubble flow
tube and a stopwatch.
The calibration system is used to generate a series of three or more
known concentrations, spanning the linear range of the FPD (approximately
0.05 to 1.0 ppm), for each of the four reduced sulfur compounds. These
test atmospheres are used to check the analyzer system at point A and the
dilution system at point B, as illustrated in Figure 8.5.
8-7
-------
I 1 Particular
J Filter
(a) Commercially Available Portable
Permeation Calibration System.
Sample
Vent
Charcoal
Valv«
(b) Flow Schematic of
Portable Calibration System
(c) Permeation Tube Chamber
Figure 8.3. Typical Permeation Tube System.
8-8
-------
CERTIFICATE
The permeation rale of the DYNACAL* PERMEATION DEVICE lilted below
is certified traceable lo N.B.S. standards.
CHEMICflL FILL
DEVICE TVPE
LENGTH/GEOMETRV
PftRT NUMBER
METHOD OF CERTIFICATION
CERTIFICfiTION NUMBER
DIMETHVL DISULFIDE
HIGH EMISSION TUBE
10.0 CM.
107-100-0301
GRAVIMETRIC
36-21022
i NG/T1IN +/- 5
s "OCTOBER i=>83 BV
rtT 35 DEG C
wocgQ/Vletronics
INDIVIDUAL DEVICE CERTIFICATION
The gravimetric method measures the weight lou Of unit of lime it the certification temperature Traceabilnv
is thus established bv me use at temperature and weigni standardi traceable to N B S ttandaidi
•iMivUuai L«riiii'aiinr> .4 di.ra.iiQiiin«l bv 111 •njintaimn,) me devire m a cunsiant temoeraiure enambei witn a
•.. ,• -.v* 3' d'. n.iiuiji-n and 121 weighing per.odicaliy on a «.m. microanaiviical balance accurate lo ihe
••..jrcst O 0: mi) vinni o tuadv weigni lo» per unn t,me has been achieved Temoeraiure control and accuracy
ue beite- man : OOS'C reicrunced agamu temperature standards traceable to the National Bureau o> Sun
dards The wmi microanaiytical balances are routinely serviced and calibrated bv an independent service organi
ianon using N 8 S traceable weight standards Gravimetric permeation rate determinations are continued until
in« standard error ol the permeation rale meets the required accuracy at the 95% confidence level
validation of me cernlication procedures and standards at Metronics is accompiiined by routine certification of
Standard Reference Material ISRMI permeation devices obtained from ine National Bureau of Standards
Figure 8.4. Certification of Permeation Tubes.
8-9
-------
PROBE
DILUTION
SYSTEM
A
------
GAS
CHROMATOGRAPH
Figure 8.5. Calibration of Analyzer and Dilution System.
8.2.2.2.1 Calibration of Analysis System -
A series of three known concentrations, spanning the linear range of
the FPD, for each of the four reduced sulfur compounds is generated by
the calibration system. Three injects for each concentration are used to
develop a calibration curve. Each calibration pq.int is considered valid
when the mean peak area of three successive injections does not differ
by more than five percent from the peak areas contributing to the mean.
A typical chromatogram is illustrated in Figure 8.6.
H2 Flow = 50 mL/min
Air Flew =110 mL/min
N1 Flow = 25 mL/min
N22 Flow =45 mL/min
1.9b
RUH «
Attenuation = 2
Chart Speed = 1 cm/min
Trailer Tenp: 26°C
Detector Temp: 115°C
Column Temp: 50°C
Columns: 71 x 1/8" BHT 100
18" x 1/8" PPE
Event 1: 01 sec, Start, Inject
Event 2: 180 sec, Load
Figure 8.6. Typical GC Chromatogram.
7S
iEP/u3'83
RT
0 7W
1 86
TOTAL HktA=
MUL FACTOft=
ARtft TYPE
695,-J/e Hb
193640 88
S883 18
1L4 (4 L4 Cf C* -•. A ft
DUOD t • fD
MR/HT
Q 050
0 133
78 869
fl 731
8-10
-------
The peak area from each injection is measured either manually from
the strip chart or electronically through an electronic integrator. The
concentration of sulfur in the gas is proportional to the peak area as
well as peak height. From this information a calibration curve can be
generated, as illustrated in Figure 8.7.
J
2
I06
5
2
I05
_ 5
u
0}
I/I
1 2
i ^
2 5
a.
2
5
2
'°2o
'*/
/
I/
A
/'
/
/
71
/
\
i
/
/
' ax1
^
/
b
//
^
^^*
O2 O5 IO 2O 50 10 20 5O lOi
SULFUR MASS { ng )
Figure 8.7. Gas Chromatography Calibration Curve.
8-11
-------
Table 8.1 displays an example calculation addressing the 5% stipula-
tion associated with repeated injections.
TABLE 8.1
EXAMPLE CALCULATION
Calibration Point
Known Concentration3
Peak Areasb
1
2
3
1
10.5
1.36 x 107
1.32 x 107
1.33 x 107
2
6.41
5.08 x 106
5.04 x 106
5.11 x 106
3
2.92
1.19 x 106
1.17 x 106
1.19 x 106
4
1.39
3.01 x 105
3.13 x 105
3.08 x 105
Mean Peak Area0
Difference of Indivi-
dual Peak Areas From
Mean Peak Area
1
2
3
Calculated Concentration
Difference Between Known
Concentration and Cal-
culated Concentration
1.34 x 107 5.08 x 106 1.18 x 106 3.07 x 105
1.5%
1.5%
0
10.6
6.33
1.2%
2%
2%
2.89
1.40
The slope of this H2S calibration curve is 1.86
a ppm, based on permeation rates and diluent flow
D v-sec
A typical Field Calibration Data sheet addressing system calibration
is shown in Figure 8.8.
8-12
-------
CALIBRATION DATA
(Method 16)
(.1 i LIU
bourn.
D.iic
Analyst
COMPOUND II7S
PERMEATION RATE (uL/raln) £„,-. iS't. /7W
TUBE NUMBER 8, P '• Jo/o"'J* /B- 2/Y33
RETENTION TIME (sec) ' 0.6?
TIME/
DATE
to/
'706
/7Z/
J IQO
*"%
FLOW
(U
din)
Wtf
"1
Yrv
1W-
tn
CKFD
M
^«I4
D/HS
ip^os
/i.$
Krirt
«M<;
PMOS
M s
^»iH
OrtS
HMD 5
U.i
r.'-.-
p,.- ',
r/wfi
u s
M'Ji-i
Cv/\^
PMp^
KNOUN
CONC.
(ppra)
3,»1
*y,26
1.5?
o.5li
7.6?
?.«//
- //
O.ttf
5 f 3
V. fL
i.?r
Ool^
1 SJ.
?-*3
3.o4
O.lW
^.6t
^ 00
\ f
f.}f
6. S3
I. ft
->.*
f.'/l
Z.o-l
Z.lO
(.W
n&
66(7
<.(,*
v.^r
? 0'
(.TJ
; 70
/otf
5 -i~
-
3
2.DS
/.ir
-------
8.2.2.2.2 Dilution System Calibration
Using the permeation tube calibrator, a known concentration of
is injected in front of the dilution system (Point B), as illustrated in
Figure 8.9, to verify its precision at each dilution stage.
PROBE
B
DILUTION
SYSTEM
GAS
CHROMATOGRAPH
Figure 8.9. Dilution System Calibration Verification.
Three injections for each dilution must yield a precision of +5 per-
cent from the mean of the three injections. Failure to meet this criteria
indicates a problem in the dilution system which must be corrected before
proceeding.
8.2.2.3 Sampling and Analysis Procedure (Section 9.0) -
Section 9.0, Sampling and Analysis Procedures, involves a sample run
of conditioning the sampling train, extracting the sample with subsequent
S02 scrubbing, diluting the sample, then analyzing the sample by the GC/FPD.
A sample run, as defined by Reference Method 16, is composed of 16
individual analyses (injections) performed over a period of not less than
3 hours or more than 6 hours.
8.2.3 Post-test Procedures (Section 10.0)
Section 10.0, Post-test Procedures, involve determining H2S losses
through the sample transport system to develop a "correction factor" if
the sampling losses are between 0-20 percent. For sampling losses greater
than 20 percent in a sample run, the sample run is not to be used when
determining the arithmetic mean of the performance test.
8-14
-------
Sample line losses determination involves injecting a known concen-
tration of HgS [ at a level of the applicable standard (+20%)], as close to
the probe tip (Point C) as applicable, as illustrated in Figure 8.10.
PROBE
DILUTION
SYSTEM
GAS
CHROMATOGRAPH
Figure 8.10. Sample Line Loss Determination.
The sample must go through all active components of the sampling
system. The H2S concentration may be generated either by a permeation
tube system or by a cylinder gas dilution system which is traceable to
a permeation tube system.
The sample line recovery determination is calculated by the following
equation:
% Recovery = (Measured H?S, ppm) x 100
(Known H2S, ppm)
In addition to determining % recovery of the sampling train, a
recalibration of the dilution system and the GC/FPD is required after a
run or series of runs. This involves challenging the dilution system and
GC/FPD with a known concentration of H2S, generated either by the permeation
tube system or by the cylinder gas dilution system.
The calibration curve obtained prior to the run(s) is compared with the
recalibration curve. A calibration drift is then calculated by the
following equation:
Post calibration drift
determination (%)
[Monitor Response!
Lto HpS,
ppm
Known Concentration!
-I of HpS. ppm J100
(Known Cone, of H2S, ppm]
The recalibration drift for the dilution system and the GC/FPD should
not exceed +. 10%. If the drift exceeds the limits, the intervening run
or runs should be considered not valid.
8-15
-------
8.3 PROPOSED FEDERAL REFERENCE METHOD 16A - June 18, 1981
8.3.1 Introduction
On February 23, 1978, EPA promulgated Federal Reference Method 16 -
Semi continuous Determinatiuon of Sulfur Emissions from Stationary Sources.
Utilizing the principle of gas chromatography separation of reduced sulfur
species with subsequent flame photometric detection, Reference Method 16
was the method for determining compliance with an applicable TRS Standard.
Over the next several years, sources utilizing Reference Method 16 found
many disadvantages. In particular, users complained about:
o Complexity of the Method (gas chromatography with flame photometric
detection);
o Extensive setting-up requirements;
o Extremely high manpower and resources requirements;
o Difficulty with calibration technique; and
o Need for maintaining an extensive calibration system.
On June 18, 1981, EPA Proposed Reference Method 16A for determination
of total reduced sulfur (TRS) emissions from stationary sources. Different
from Reference Method 16, Proposed Reference Method 16A involves sample
extracting through an impinger train similar to Federal Reference Method 6.
Once the TRS as S02 is captured in the Proposed Reference Method 16A imping-
ers, analysis is by barium-thorin titration. Proposed Reference Method 16A
advantages over Method 16 are:
o Cheaper testing equipment;
o Easier application of methodology;
o Fewer manpower and resource requirements; and
o Easier sample analysis and calibration.
8.3.2 Train Configuration
As illustrated in Figure 8.11, Proposed Reference Method 16A sampling
train involves four basic components:
o sample extraction system;
o sample conditioning;
o impinger system; and
o meter box assembly.
8-16
-------
OXIDATION
TUBE
IS
StUHCfl
MVMITVM
TUK FURNACE
MjKMUIIf*
Figure 8.11.
Proposed Federal Reference Method 16A
Sample Train Configuration.
Sample Extraction System - The sampling probe consists of a heated
Teflon® tube sheathed in a stainless stell probe. A piece of glass
wool plug positioned at the inlet of the probe serves as the partic-
ulate control device.
Sample Conditioning System - The sample conditioning system involves
the S02 scrubber system and the combustion tube furnace. The S02
scrubber system consists of two midget impingers in series (top packed
with glass wool to eliminate entrained mist ) and charged with
potassium citrate-citric acid buffer solution. As the stack gas
bubbles through the buffer solution, S02 is subsequently removed
while TRS passses through.
The combustion furnace consists of a quartz glass tube 30.5 cm long,
heated and maintained at 815+ 15°C. This enables the oxidation of
TRS to S02.
8-17
-------
o Impinger System - The impinger train consists of three midget impingers,
in series, charged with 3% hydrogen peroxide. A fourth impinger may
follow for collection efficiency determination. In essence, the S02
gas is oxidized by the hydrogen peroxide solution to form sulfuric
acid.
o Meter Box Assembly - The meter box assembly contains the pump, rate meter
and dry gas meter for measuring total volume of gas stream sampled.
Once the complete system is assembled, the sampling and analysis pro-
cedures involve the following functions:
o Pre-test leak check (optional);
o Validation of test procedure;
o Sampling;
o Post-test leak check (mandatory);
o Purging:
o Sample recovery; and
o Sample analysis.
Since its proposal in 1981, the method has shown interferences in
sampling and analysis from particles when applied to monitoring lime kiln
stack gases. Previous work by EPA has indicated that if particulate
matter (calcium carbonate) is allowed to enter the SOg scrubber (citrate
buffer solution), it would raise its pH, this permitting HgS to be absorbed
prior to oxidation, creating a negative bias in the sampling technology.
8.3.3 Proposed Reference Method 16A Bias Evaluation
EPA evaluated five sampling parameters for biases involving Proposed
Reference Method 16A train configuration. They were:
- Probe angle;
- External filter;
- H2S filter retention;
- Sample train purge; and
- Scrubber solution pH.
Four sampling trains were used to evaluate the above parameters.
Each individual train consisted of a heated probe, filtering device, a
series of impingers and a meter box console. During sampling, the probe
and filter temperatures were maintained at approximately 107°C (225°F).
All sampling trains were run for 3 hours at a flow rate of 2 liters per
minute (liter/min) to simulate actual Proposed Reference Method 16A lime
8-18
-------
kiln sampling procedures. The study, in essence, evaluated the front
half of the Proposed Reference Method 16A sampling train.
8.3.3.1 Probe Angle Evaluation -
A series of tests were performed to evaluate the use of an angle probe
rather than a straight-in probe as recommended in Proposed Method 16A. The
test involved four simultaneous sampling trains extracting samples at a lime
kiln and evaluating the quantity of particulate matter captured by the sampl-
ing train.
Two sampling trains (AP-1 and AP-4) employed angled probes while the
other two trains (SP-2 and SP-3) employed straight probes. The results of
probe angle evaluation are shown in Table 8.2.
TABLE 8.2
PROBE ANGLE EVALUATION
Test
Run
1
Sampling
train con-
figuration
AP-1
SP-2
SP-3
AP-4
Test
time,
min.
180
180
180
180
Average
Temperature
( °F )
Probe Filter
95 (203)
109 (229)
103 (217)
104 (219)
116 (241)
121 (250)
117 (242)
123 (253)
Particulate
Matter
Catch, mg
Probe
rinse
4.5
1025
884
6.2
Filter
21.2
60.0
76.9
26.9
Total
25.7
1085
960.9
33.1
Total
Particulate
Matter Catch
in Sampling
Train,mg/Nm3
76.3
2840.3
2676.6
89.9
The results demonstrate a substantial amount of particulate matter is retained
by the Proposed Reference Method 16A sampling train utilizing a straight-end
probe. If used in this configuration, chances of particle interferences are
substantial. The angle probe rejected more particulate than the straight-end
probe.
8.3.3.2 External Filter Evaluation -
In a series of tests, EPA evaluated a 50-mm heated Teflon® filter holder
with both a micro-pore size membrane and a coarse pore size membrane. A
schematic of the filter holder is shown in Figure 8.12.
FILTER
TO
IN
TRAIN
M
SAMPLE
PROBE
O FLEXIBLE
lnj THERMOCOUPLE
Figure 8.12. 50 mm Heated Teflon® Filter Holder.
8-19
-------
The main object of the test series was to evaluate different par-
ti culate matter removal devices to improve overall sampling collection
efficiency of the Proposed Reference Method 16A train configuration.
The results of the test are indicated in Table 8.3.
TABLE 8.3
EXTERNAL HEATED FILTER EVALUATION
Test
Run
2
Sample
No.
1
2
3
4
Sampling
Train Con-
figurations
AP-T50M
AP-T50M
AP-T40C
AP-T40C
Test
Time,
min.
130
180
180
180
Sample
Volume,
Nm3 (dscf)
0.340 (12.019)
0.366 (12.940)
0.352 (12.449)
0.341 (12.052)
Particulate
Catch, mg
Probe
Rinse
6.9
5.7
8.6
6.8
Filter
17.1
17.3
10.9
16.8
Total
24.0
23.0
19.5
23.6
Concentra-
tion of
Particles
in Sampl-
ing Train
mg/Nni3
70.6
62.8
55.4
69.2
AP-T50M = Angled probe, Teflon® 50-mm filter, micro-pore size (l-
AP-T50C = Angled probe, Teflon® 50-mm filter, coarse-pore size (20-30/urn)
The micro-pore size filter particulate catch average approximately
66.7mg/Nm3, slightly more than the coarse-pore filter with an average of
62.3mg/Nm3.
8.3.3.3 Sampling Train Purge Evaluation -
As specified in Proposed Method 16A, an impinger train of citrate acid
buffer solution is used to scrub out interfering S02, while allowing H2$ to
pass. In this series of tests, EPA evaluated the ability of the scrubber
solution to pass H2S.
A series of two tests, each test composed of four simultaneous sampl-
ing trains, involving sampling a known concentration of H£S gas were con-
ducted. After each test, the impinger trains were purged with clean, dry
air before analyzing the amount of HgS retained in the citrate acid buffer
solution. After the first analysis, the trains were further purged for an
additional 4 minutes and the same impingers reanalyzed for H2S. After that
analysis, the train were again purged for an additional 4 minutes and the
impingers were once again reanalyzed for H2S.
The results, illustrated in Table 8.4, indicate that a sufficient
purge time (>10 minutes) should be allowed when using Proposed Reference
Method 16A to condition the citrate acid buffer solution to HpS source
gas concentration.
8-20
-------
TABLE 8.4
HYDROGEN SULFIDE RECOVERY CHECK
Sample
Train
No.
Test 1
1
2
3
4
Test 2
5
6
7
8
Average
H2$ Concentration,
ppml
3.76
3.76
3.83
3.81
3.69
3.39
3.59
3.62
% difference
Between first
analysis and
average2
+10.1
+12.2
+85.1
+59.6
+14.9
- 0.2
-13.4
- 6.9
Between second
analysis and
average^
+ 2.1
+ 5.0
+26.4
+12.5
+ 4.1
0.0
- 4.4
- 3.3
Between third
analysis and
average4
+ 0.3
+ 1.6
+ 8.4
+ 2.1
0.0
0.0
- 1.4
- 1.9
1 As measured by 6C-FPD over test period.
2 Analysis for H2S performed on scrubber solution after 4 min. of purging
with clean, dry air.
•* Analysis for HoS performed on scrubber solution after 8 min. of purging
with clean, dry air.
4 Analysis for HoS performed on scrubber solution after 12 min. of purging
with clean, dry air.
8.3.3.4 Scrubber Solution pH Evaluation -
Under the same sampling conditions as performed in the sample
train purge evaluation, it was determined that for best train performance,
the pH of the citrate buffer solution should be 7.
8.3.3.5 H?S Filter Retention Check -
A fifth series of tests were performed to evaluate the retention
capability of the filter holder to known concentrations of HgS. If a
filter holder is going to operate efficiently, it must allow H2S gas to pass
with very little retention. The results of that study are illustrated in
Table 8.5.
8-21
-------
TABLE 8.5
SUMMARY OF RESULTS OBTAINED FROM H2S
RECOVERY CHECKS ON BLANK FILTRATION DEVICES
Sample
type
Glass Fiber Filter,
Glass Holder
90-mm Teflon Filter
and Holder
50-mm Teflon filter
and holder
Entrapment device
Filter
code
M5
M5
M5
M5
T90F
T50M
ED
% loss
of H2Sa»b
34.0 to 34.4
19.7 to 23.4
17.8 to 19.2
1.0 to 2.8
0.6 to +1.5 (Gain)
0.1 to +0.1 (Gain)
0.5 to +1.5 (Gain)
H2S Flow
Rate, ml/minc
150
350
300
2460
100
100
100
«At 95% confidence interval.
b!00% recovery assumed if interval includes zero.
cMilliliters per minute.
The results indicate the percent of HgS gas loss utilizing the
glass filter holder is considerable at low flow rates and low at high flow
rates.
8.3.4 Recommended Design Change to Proposed Reference Method 16A
From this series of tests designed to evaluate Proposed Reference
Method 16A sampling train configuration, EPA recommends the following
design changes and operation in the proposed method:
o Probe modification involving heating (107° - 121°C) and adaption
of an upturned sampling nozzle;
o Adding an external 50-mm Teflon® filter with micro (l-2um) pore
size heated to 107° to 121°C;
o H£S sampling train recovery check periodically; and
o 10-minute conditioning period for the citrate buffer
solution.
8-22
-------
8.4 PROMULGATED FEDERAL REFERENCE METHOD 16A - MARCH 8, 1985
8.4.1 Introduction
As discussed earlier, EPA evaluated the proposed Reference Method 16A
sampling train for biases. In particular, interferences from particulate
calcium carbonate were evaluated. Due to these studies, modifications to
proposed Reference Method 16A were incorporated into the promulgated
method. They were:
o Addition of a probe nozzle;
o Use of external heated filter;
o Impinger train configuration; and
o Modification of sampling methodology.
On March 8, 1985, EPA incorporated these revisions into the promulgated
Federal Reference Method 16A.
8.4.2 Promulgated Train Configuration
Figure 8.13 illustrates the promulgated Reference Method 16A sampling
train configuration, while Table 8.6 summarizes those changes between the
proposed and promulgated versions.
8.4.3 Sampling Protocol
Sampling protocol is similar to the proposed Reference Method 16A
protocol. In essence, the following activities are involved:
o Sample train preparation;
o Pre-test leak check (optional);
o Validation of test procedure;
o Sampling;
o Post-test leak check (mandatory);
o Purging;
o Sample recovery; and
o Sample analysis.
8-23
-------
MAIM NI
ruimc
TMmocouni
tllMTIW
IMC
NIMCf
ItKI WU
mi 1111
tt
1IWIMIWI
Co
ro
TNI MM III
•nut
win
Figure 8.13. Promulgated Federal Reference Method 16A Sampling Train Configuration.
-------
oo
i
TABLE 8.6
PROPOSED AND PROMULGATED
FEDERAL REFERENCE METHOD 16A
Proposed Reference Method 16A
June 18, 1981 (46FR31904)
yi Probe
Borosilicate glass or stainless steel;
Straight-end, heated, with glass wool plug as
particulate control device ( in-stack or out-of-stack ),
Particulate Control Device
In-stack glass wool plug.
SOp Scrubber
Two midget impingers in series, top packed with
glass wool.
Furnace
Quartz tube (2.54 cm x 30.5 cm), heated at 815^ 15°C
SO? Absorber
Three midget impingers
Analysis
Barium-thorin titration
Promulgated Reference Method 16A
March 8, 1985 (50FR9578)
Teflon, heated with upturn elbow.
Out-of-stack , 50-mm Teflon filter with
micro (1-2 Mm) pore size, heated between
107° to 121°C (225°-250°F).
Three 300 ml Teflon impingers. First two
impingers contain citrate buffer solution.
Third impinger dry.
Quartz tube (2.54 cm x 30.5 cm), heated at
800°C i 100°C
Three midget impingers
Barium-thorin titration
-------
8.4.3.1 Train Preparation
The sample train is prepared by measuring 100ml of citrate buffer
solution into each of the first two impingers, (glass wool packed in the
top) for S02 removal. In addition, 3% hydrogen peroxide is added to the
following three impingers to collect the S02 produced by the oxidation of
TRS. The probe is heated to 106°C to prevent condensation and the oxi-
dizing furnace is maintained at 815°C.
8.4.3.1.1 Optional Pre-test Leak Check -
Once the sampling train is prepared, an optional leak check is recom-
mended. As demonstrated in Figure 8.14, the leak check is performed by
attaching a rotameter (0-40 ml/min) to the outlet of the dry gas meter.
The probe inlet is plugged with a vacuum gauge. The pump is turned on
until a vacuum of 250 mmHg (10"Hg) registers on the vacuum gauge. If the
leak rate indicated by the rotameter is less than 2 pecent (40 ml/min) of
the average sampling rate, then the system is leak free.
THERMOCOUPLES
TO MONITOR TEMPERATURES
Figure 8.14. Optional Pre-test Leak Check
8-26
-------
8.4.3.1.2 System Performance Check -
Once the optional pre-test leak check is performed, a system perform-
ance check 1s required. The objective is to demonstrate that the system
can properly oxidize and quantatively recover a known concentration of
HgS. A dilution system is used to generate the known concentration of
H?S, as Illustrated in Figure 8.15.
»«s Calibration Gas
Mixing
Chamber
Matched
Rotameter
to SO, Scrubbers
Figure 8.15. Field Dilution System.
This system requires no additional dry gas meter and is very simple
to use.
As with any calibration system, quality assurance 1s important. Two
major areas of quality assurance checks should be:
o Certification of gas cylinder used in the dilution system; and
o Certification of flow measuring devices.
The concentration of HgS gas should be certified by Reference Method 11,
The diluent gases should contain no more than 50 ppb of total sulfur com-
pounds and no more than 10 ppm of total hydrocarbons.
Certification of the flow measuring devices should be done against a
primary standard. If used in a matched configuration, then temperature
and pressure corrections should not apply. (If used in the above configura-
tion, then the flowmeters need not be calibrated if a 1:1 dilution is made.)
Calibrate the flow rate from both sources with a soap bubble flow
tube so that the diluted concentration of H2S can be accurately calculated.
Collect 30-minute sample and analyze in the normal manner.
8-27
-------
The system performance check specifies that the sampling system is
considered acceptable when two samples of calibration gas produce results
which do not vary by more than +5 percent from their mean, and this mean
value is within _+ 20 percent of the known value.
8.4.3.2 Sampling Activities -
After the system performance test check, actual sampling can be
conducted. To be consistent with Federal Reference Method 16, the tester
may sample under one of two options:
o Collect three 60-minute samples; or
o Collect one three-hour sample with a total gas sample volume of
120 liters either intermittently (equal samples, equally spaced)
or continuously over 3 hours.
Sampling should be performed at a rate of 2 liters/minute (+1Q%).
8.4.3.3 Post-test Activities
8.4.3.3.1 Post-test Leak Check -
As demonstrated in Figure 8.12, a post-test leak check is performed
in a similar manner to optional pre-test leak check. The criteria for
acceptance is that the leak rate, as indicated by the rotameter attached
to the outlet of the dry gas meter, should be no greater than 2 percent
(40 ml/min) of the average sampling rate.
After the mandatory post-test leak check, the sample is recovered
from the four impingers containing the hydrogen peroxide and analyzed by
barium-thorin titration. The amount of TRS in the original sample is
directly proportional to the amount of sulfate formed in the impingers.
8.4.3.3.2 Sample Recovery Test -
After sample recovery and analysis, a sample train recovery test is
required. In this test, a known concentration of H2S is introduced at
the probe tip. The obtained concentration should be within +15 percent
of the known value.
8.4.3.3.3 Sample Analysis
After sample, recover the midget impingers content into a single
container. Dilute to a known volume. Take a 40-ml aliquot, add 160 ml
of 100 percent isopropanol, and four drops of thorin indicator. Titrate
from a yellow to a pink endpoint. Analyze an EPA SOg field audit sample
with each set.
8.4.3.4 Calculations
Calculate the equivalent TRS concentration by the following equation:
CTRS(ppm) = K (Vt - Vtb) N (Vso1n / Va)
vm(std)
8-28
-------
Where: CTR$(ppm) = Concentration of TRS as SOg dry basis corrected
to standard conditions, ppm.
Va = Volume of sample aliquot titrated, ml
vm(std) = Dr.X 9as volume measured by the dry gas meter,
corrected to standard conditions, liters (dscf).
Vso]n = Total volume of solution in which the sulfur
dioxide sample is contained, 100 ml.
Vt = Volume of barium perchlorate titrant used for
the sample, ml (average of replicate titrations).
Vtb = Volume of barium perchlorate titrant used for the
blank, ml.
K = 12025 ul/meq.
N = Normality of standardized BafClO/j^
Table 8.7 illustrates the performance requirements between the Proposed
and Promulgated Reference Method 16A.
TABLE 8.7
SYSTEM PERFORMANCE SPECIFICATION
PROPOSED & PROMULGATED REFERENCE METHOD 16A
Parameter
Proposed
Reference Method
16A
6/18/81
Promulgated
Reference Method
16A
3/8/85
System Performance Check
(+20% of Calibration gas)
Citrate Scrubber Conditioning
Pre-Test Leak Check
(<2% of Sampling Rate)
Sampling Rate (± 10%)
Sampling Time
Post Test Leak Check
(<2% of sampling rate)
Purge
System Performance Check
(after 3 hours) (+. 20% of
calibration gas)
EPA Field Audit Sample Analyzed
Recovery Gas Analysis
(5% on three analyses)
Each Run
None
1 (optional)
2 liters/min
1 hour
1 (mandatory)
Need not be
performed
No
2 optional
10 min. @ 2
liters/min
1 (optional)
2 liters/min
1 or 3 hours
1 (mandatory)
15 minutes
recommended
1 (mandatory)
Recommended
Yes
8-29
-------
8.5 COMPARATIVE TESTING OF METHOD 16 (GAS CHROMATOGRAPHY) AND PROPOSED FR
METHOD 16A (WET CHEMICAL)
8.5.1 Introduction
On July 14, 1981, the United States Environmental Protection Agency
proposed Federal Reference (FR) Method 16A as an alternative to Federal
Reference Method 16. As indicated previously, the disadvantages with FR
Method 16 are:
- complexity of Reference Method 16 (gas chromatograph equipped
with a flame photometric detector);
- difficulty with calibrating with five sulfur gases;
- need for maintaining an extensive calibration system; and
- expense of Reference Method 16.
Proposed Reference Method 16A was considered cheaper and easier to
perform. Utilizing the impinger collection technique and barium-thorin
titration procedure, the method offers the following advantages over FR
Method 16:
- needed testing equipment is much cheaper;
- method is simpler;
- sampling can be performed on the stack;
- samples need not be analyzed in the field; and
- method has few interferences.
One of the major drawbacks with FR Method 16A is that all reduced
sulfur compounds are measured. The method can not distinguish between
different reduced sulfur compounds like FR Method 16. When the Kraft pulp
mill standard was developed and originally adopted, the intent was to
include all reduced sulfur compounds. However, during the emission
testing program, EPA found that four compounds- hydrogen sulfide, methyl
mercaptan, dimethyl sulfide and dimethyl disulfide - were the only signi-
ficant compounds being emitted. Consequently, FR Method 16 addressed only
those four compounds through column separation and detection. FR Method 16A,
being an impinger technique, collects all reduced sulfur compounds; there-
fore, FR Method 16A may give higher results than FR Method 16.
8.5.2 Test Configuration
With this in mind, the National Council For Air and Stream Improve-
ment ( NCASI ) decided to perform a study involved comparing FR Method 16 and
Proposed FR Method 16A to H2S calibration gas mixtures in air and to
measuring Kraft recovery furnace TRS emissions. The sampling train con-
figuration involved an ITT Barton probe/conditioning system, a heat trace
line, a series of impingers to remove S02, and a common manifold for
sample distribution.
The ITT Barton probe consists of a Teflon® tube housed inside a
stainless steel pipe. The stack gas is extracted from the source through
holes in the pipe extending into the stack. The extracted gas sample
passes through a condenser, transported by a heated Teflon® sample line
to the control room. Inside the control room, the gas stream is scrubbed
8-30
-------
of S02 by five impingers containing potassium citrate - citric acid
buffer solution maintained at a pH of 5.5 +_ 0.1. The sample then passes
a Teflon® manifold where the gas is distributed for concurrent analysis.
Federal Reference Method 16 uses the principle of gas chromatography
(GC) separation with flame photometric detection (FPD). A sample is ex-
tracted from the source and an aliquot is injected into the gas chromato-
graph.
The column in the gas chromatograph separates the sample into compo-
nent fractions, [ i.e. hydrogen sulfide (H2S), methyl mercaptan (CHsSH),
dimethyl sulfide (CH3)2S, and dimethyl disulfide (CH3)2S2)] through a
gas-solid partitioning mechanism. The column also provides for separa-
tion of carbon monoxide (CO) and carbon dioxide (C02). The separated
components of the gas stream exit the column and are detected by the
flame photometric detector. A flame photometric detector measures the
emission intensity of a high energy sulfur species at a selected wave-
length while the pollutant is burned by a hydrogen-rich flame. The
luminescent emission from burning the sulfur molecule in the flame is
directly proportional to the sulfur atoms in the gas stream.
The GC/FPD is calibrated against a permeation tube calibration
system for the four TRS compounds. The calibration procedure requires
three upscale concentrations for each of the four pollutants.
Proposed FR Method 16A utilizes an S02 scrubber, TRS oxidation furnace
and a series of impingers for absorption. In essence, a gas sample is
extracted from a stack, bubbles through a potassium citrate-citric acid
buffer solution to remove S02, oxidized remaining TRS to S02 and captured
in a series of impingers containing hydrogen peroxide. The hydrogen
peroxide oxidizes the S02 to sulfates. The sulfates are titrated by a
barium-thorin titration. The amount of sulfates present are directly
related to TRS in the sample gas. Calibration of the system is performed
by passing certified H2S in nitrogen gas through the sample train to
calculate a percent efficiency.
8.5.3 Test Results
8.5.3.1 HpS Certified Test Gas Mixture -
Known concentrations of H2$ certified gas mixtures were used to
evaluate the response of FR Methods 16 and 16A test configuration. The
results from three test runs are presented in Table 8.8.
8-31
-------
TABLE 8.8
METHOD COMPARISON: FR METHOD 16 AND PROPOSED FR METHOD
16A UTILIZING H2S CERTIFIED GAS MIXTURE
Run No.
1
2
3
Avg.
Avg. Measured TRS Concentration, ppm
FR Method 16
2.09
2.10
1.85
2.01
Proposed
FR Method 16A
2.32
2.27
1.79
2.13
Di fference,
ppm
-0.23
-0.17
+0.06
-0.11
The results indicate very little difference between the two methods.
A paired difference test was performed by NCASI on the data to test whether
the difference was significant. Results of that evaluation indicated no
significant difference - the two methods essentially provide the same results.
8.5.3.2 Kraft Recovery Furnace Test
FR Methods 16 and Proposed FR Method 16A were compared by analyzing Kraft
recovery furnace TRS Emissions. A total of eleven runs were evaluated.
Each run for FR Method 16 involves five to six injections equally spaced
over an hour. The average of those injections were used to compare to
the one hour sampling time for Proposed FR Method 16A. Table 7.8 illust-
rates the results of the method comparisons analyzing Kraft recovery
furnace emissions.
TABLE 8.9
METHOD COMPARISON: FR METHOD 16 AND PROPOSED FR METHOD 16A
KRAFT RECOVERY FURNACE
Run #
1
2
3
4
5
6
7
8
9
10
11
Average
Measured TRS Concentration, ppm
FR Method 16
2.06
3.10
5.37
3.27
1.65
1.94
0.65
2.38
2.74
2.31
3.31
2.62
Proposed FR Method 16A
2.32
2.61
5.40
3.11
2.18
1.98
0.88
2.68
2.85
2.57
3.17
2.70
Difference,
ppm
-0.26
+0.49
-0.03
+0.16
-0.53
-0.04
-0.23
-0.30
-0.11
-0.26
+0.14
-0.09
8-32
-------
A paired difference was performed on the data set by NCASI. Once
again, statistical evaluation indicated no difference between the two
techniques. A relative accuracy (RA) calculation was performed accord-
ing to the Federal Register. The relative accuracy was calculated to be
10.5 percent, well within the 20 percent limit specified in Performance
Specification Test 5. In summary, no difference was found between
Federal Reference Method 16 and Proposed Federal Reference Method 16A
by the NCASI.
8-33
-------
8-34
-------
9.0 PERFORMANCE SPECIFICATION TEST
9.1 INTRODUCTION
EPA has established requirements under 40CFR60 and 40CFR51 for certain
new and existing sources to install, operate and maintain continuous emis-
sion monitors. The initial intent of the regulations was to provide the op-
erator the ability to monitor and "fine tune" his pollutant control device.
Recently the regulations for some source categories have been modified to
include use of continuous emission monitors for compliance with State and
Federal Regulations. The Kraft pulp mill NSPS requires a continuous emis-
sion monitoring system to monitor TRS for operation and maintenance pur-
poses. Compliance with the standard is determined by Reference Methods
16 and 16A.
As part of the NSPS regulations, continuous emission monitors had to
pass a Performance Specification Test (PST) to insure they met certain
design and specification requirements. These initial tests evaluated the
performance characteristics of opacity, SOg, NOX, 02 and TRS monitors. The
evaluation of the monitoring system and compliance with the specification
had the intended purpose of insuring reliable operation of a monitoring sys-
tem once installed on the source. This was a one time certification proced-
ure. The existing regulations do not provide specific procedures related to
follow-up quality assurance evaluation.
On July 20, 1983, the U.S. Environmental Protection Agency (EPA) pro-
mulgated Performance Specification 5, "Specifications and Test Procedures
for TRS Continuous Emission Monitoring Systems in Stationary Sources," in
the Federal Register (48 FR 32986). The performance specification (PS)
evaluates the acceptability of total reduced sulfur (TRS) continuous moni-
tors as specified in the applicable regulations. The specification was
proposed under the authority of Sections 111, 114, and 301 (a) of the Clean
Air Act, as amended.
On May 25, 1983, EPA finalized rulemaking of Performance Specification
2 and 3 for S02, NOX, C02 and 02. The finalized rulemaking affected the
following facilities:
- fossil-fuel-fired steam generators
(construction commenced after Aug. 17, 1971);
- electric utility steam generating units
(construction commenced after Sept. 13, 1978);
- nitric acid plants;
- sulfuric acid plants;
- petroleum refineries;
- primary copper, zinc and lead smelters;
- Kraft pulp mills;
9-1
-------
and sources subject to Appendix P of 40 CFR Part 51. Consequently Kraft
pulp mills are subject to both Performance Specification Tests 5 and 3 and
parts of PS 2. The objective of this chapter is to discuss each of these
specifications as applied to Kraft pulp mills.
The details contained within Performance Specification 5 apply to con-
tinuous monitoring systems measuring TRS. Similarly, the details contained
within Performance Specification 3 are specific for 02 or C02 continuous
monitoring systems and those for S02/NOX monitors are found in PS 2. Basic-
ally, each of these Performance Specifications consists of a set of operat-
ing criteria that each system installation must be shown to either meet or
exceed. Table 5.1 outlines the sections for Performance Specification
Tests 2, 3 and 5.
TABLE 9.1
PERFORMANCE SPECIFICATIONS FOR
S02/NOX, 02/C02 and TRS
CONTINUOUS EMISSION MONITORING SYSTEMS
Part 60— Appendix B
Performance Specifications (added)
|—
PERFORMANCE SPECIFICATION TEST Z
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APPLICATION AMD PRINCIPLE
DEFINITIONS
INSTALLATION SPECinCATIONS I
PERFORMANCE AND EQUIPMENT
1 SPECIFICATION
PEWORNRMX SPECIFICATION
TEST PROVflHIRtS
CALIBRATION DRIFT TEST
RELATIVE ACCURACY TEST PROCEDURES
CALCULATIONS, DATA ANALYSIS
REPORTING
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PERFORMANCE SPECIFICATION TEST 1
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TOTAL REDUCED SULFUR
APPLICATION AND PRINCIPLE
\0 -J APPLICATION AND PRINCIPLE
,
APPRATUS
2O - PERFOMARCE AND EQUIPNnT SPEC.
DEFINITIONS
30 . RELATIVE ACCURACY TEST PWtEDURES
1 INSTALLATION SPECIFICATIONS
CONTINUOUS PXNITORINB SYSTEM
KRnNMNCE SPECIFICATIONS
PERFOMANCE SPECIFICATION
TEST PRDCEOUnt
CALCULATIONS, DATA ANALYSIS ADO
REPORTINB
•miOBMMR
4.0LJ BIBLIOaMPHY
9-2
-------
By Imposing these requirements on each affected monitoring system,
EPA has, in a sense, established a one time quality control check
on the installed continuous emission monitor. After both field and
laboratory evaluation programs with various brands and types of gaseous
monitoring systems, EPA developed a list of operating parameters that
were judged to be important factors in the successful operation of any
system, regardless of the brand name of the unit and indifferent to the
particular method of analysis. In addition to identifying important
operating characteristics, EPA also identified the extent of deviation or
tolerance allowable in each operational parameter. From this experience,
EPA has developed a series of specifications by which the installed CEM
must meet in order to be certified at that point in time. Table 9.2
lists those specifications for each parameter and affected facility as
applied to Kraft pulp mills.
TABLE 9.2
PERFORMANCE SPECIFICATION REQUIREMENTS
KRAFT PULP MILLS
Parameter
Specification
Performance
Specification 5
(TRS)
Performance
Specification 3
(Op/CO?)
Accuracy
Calibration Drift
(24 hour}
Recovery Furnace
(straight)
Recovery Furnace
(cross)
Lime Kiln, Digester,
Brown Stack Washer,
Evaporator, Oxidation
or Stripper Systems
Cycle of Operation
20% of Mean Valve of
Reference Method or 10%
of the applicable std.,
whichever is greater
£ 5% (l.Sppm) at each of
two points of the estab-
lished span valve of 30
ppm for 6 out of 7 days.
£ 5% (2.5ppm) at each of
two points of the estab-
lished span valve of 30
ppm for 6 out of 7 days.
£ 5% (l.Sppm) at each of
two points of the estab-
lished span valve of 30
ppm for 6 out of 7 days.
Each 15 minute period
(sampling, analysis and
data recording)
£0.5% oxygen
for 7 consecu-
tive days.
£0.5% oxygen
for 7 consecu-
tive days.
£0.5% oxygen
for 7 consecu-
tive days.
Each 15 minute
(Sampling, an-
alysis, and re-
cording)
9-3
-------
Unlike other specifications, Performance Specification Test 5 references
several sections of Performance Specification Test 2 - Specification and
Test Procedures for S02 and NOX Continuous Emission Monitoring Systems in
Stationary Sources. PS 2 discusses the mechanics of performing a PST.
PS 5 references these procedures found in PS2. The following section
discusses in detail the implications and influence of PS 2 on PS 5.
9.2 PERFORMANCE SPECIFICATION TEST 5
9.2.1 Reference to PS ?
l. Applicability and Principle.
\ I Applicability. This specification is to
be used for evaluating the acceptability of
total reduced sulfur (TRS) and whenever
specified in an applicable subpart of the
regulations. (At present these performance
specifications do not apply to petroleum
refineries, Subpart J)) Sources affected by
the promulgation of the specification shall be
allowed 1 year bevond the promulgation date
to msiail. operate, and test the GEMS. The
CEMS's may include O-i monitors which are
sub|ect to Performance Specification 3 (PS 3).
The definitions, installation specifications.
test procedures, and data reduction
procedures for determining calibration drifts
(CD's) and relative accuracy (RA). and
reporting of PS 2. Sections 2. 3. 4. 5. 8. 8. and 9
also apply to this specification and must be
consulted. The performance and equipment
specifications do not differ from PS 2 except
as listed below and are included in this
specification.
1 2 Principle The CD and RA tests are
conducted to determine conformdnce of the
CEMS with the specification
- Reference
8.0 and 9.
Section 1.0 defines applicability and
principle as it relates to Performance
Specification 5. Those sources subject
to PS5 are outlined in the Subparts
(except Subpart I) requiring monitor-
ing of total reduced sulfur (TRS).
If applicable, the source has one year
from data of promulgation, July 20,
1983, to install, operate and test the
CEMs. The test evaluation consists
of a calibration drifts (CD's) and
relative accuracy (RA) determination.
Two important principles are
discussed in Sections 1.1 and 1.2 of
PS5 which have a great impact on the
performance and evaluation of
installed TRS CEMs:
to Sections 2.0, 3.0, 4.0, 5.0, 6.0,
0 of Performance Specification 2 -
Specification and Test Procedures for S02 and
NOX Continuous Emission Monitoring Systems in
Stationary Sources.
- Conformance Specification (CD & RA) for TRS CEMs.
Within PS2, guidelines are given addressing definitions (2.0)
installation and measurement location (3.0), performance and equipment
specification (4.0), PST procedures (5.0), CEMs calibration drift prodedure
(6.0), equations (8.0) and reporting (9.0). PS2 is applicable to S02
and NOX CEMs and their certification. Within PS5, Sections 1.0 refer-
ences those sections of PS2 and therefore are applicable to TRS CEMs
certification.
9.2.2 Definition of TRS CEM System
Within Section 2.0 of PS2 we find guidance on the definitions
of continuous emission monitoring system (CEMs) and span value. Under
Section 2.1 of PS2, a CEMs is defined as:
2.1 Continuous Emission Monitoring System: "The total
equipment required for the determination of a gas con-
centration or emission rate."
9-4
-------
This definition incorporates the diluent monitor as part of the con-
tinuous emission monitoring system. As defines in Section 1.2 of PS5, the
calibration drift (CD) and the relative accuracy (RA) test are conducted
to determine conformance of the CEMs with the specification. Consequently,
the RA test is performed on the CEMs, which includes the diluent monitor.
Therefore, no individual RA test is required on the diluent monitor.
9.2.3 Span Value Definition
Secondly, guidance is given under Section 2.0 of PS5 dealing with the
definition of span value. Under Section 2.4 of PS2, it defines span value as:
2.4 Span value: "The upper limit of a gas concentration
measurement range specified for affected source categories
in the applicable subpart of the regulations."
In this context, span value is the full range of the TRS monitoring system.
For Kraft pulp mills, the span values for the TRS monitors are listed in
Table 9.3.
TABLE 9.3
SPAN VALUES
KRAFT PULP MILLS TRS/02 MONITORS
Affected
Facility
Pollutant
Span
Valve
Recovery Furnace
Straight Recovery
Cross Recovery
TRS
02
TRS
02
30ppm
20%
SOppm
20%
The span value of a TRS CEM should not be confused with the "span value1
of a gas cylinder used to evaluate an installed CEM or the internal
"span value" of a standard used to evaluate the performance of a CEM.
9.2.4 TRS CEM Installation and Measurement Location
3 1 The CEMS Installation and
Measurement Locution Install the CEMS al
an accessible locaE'HR wnere the pollutant
concpntration or emission rale measurements
are directly represeTtative or can be
corrected so ai to be representative ot the
total emissions from the affected facility or at
the measurement location cross section Then
select representative measurement points or
pdihs for mor.norng in locat-ons thdt the
CEMS will pass the RA test (see Sen-on T) If
the cause of failure to meet the RA test :s
determinr-d to be the measurement location
and a satisfactory correction technique
cannot be established, the Administrator mny
reuuire the CEMS to be relocated
Suggested medsurcmenl locations and
points or paths that are most likely tc provide
ddta that will meet the RA requirements are
listed bt'luw
Guidance is given within Section 3.1
of PS2 in reference to CEM installation
and measurement location. In essence, it
is the responsibility of the source to
verify that the TRS CEM is located at a
point that is representative or can be
corrected so as to be representative of
total emissions from the affected facil-
ity. The source must determine if strat-
ification exists at the sampling loca-
tion and if the sample extracted would be
a "representative" sample.
9-5
-------
9.2.4.1 Stratification Determination -
This is usually addressed in the permit and determined by velocity
traverse or utilization of portable TRS monitors. Gaseous samples must
be obtained from a sampling location that provides measurement which are
representative of the total effluent. The key word in determining to
what extent a sample may be considered representative is stratification.
Stratification is defined within the Code of Federal Regulations as a
condition (for any point more than 1.0 meter from a stack wall) whereby a
concentration at any point differs from the average concentration in the
stack by more than 10%. Algebraically, the existence of stratification
is verified if the following relationship is found to occur:
- "Gil >0.iO
where
C1
c-j = average concentration of component i over the stack cross-
section
C-jp = concentration of component i at the particular point p
(greater than 1 .0 meter from the wall) within the same stack
cross-section
If no stratification exists at a given cross-section, then the sample is
considered to be directly representative of the complete cross-sectional
area of that stack and, therefore, directly representative of the total
emissions. However, if stratification does exist, the sample from a given
point may not be representative of the complete cross-sectional area, but
that measurement can still be corrected to be representative of the total
emissions.
The best assurance of non-stratified sampling location is obtained by
performing a sampling traverse of the stack cross-section in question. The
existence of stratification is confirmed if the condition described by the
above equation is observed at any point farther than 1.0 meter from the
stack wall .
9.2.4.2 Traverse Points Location -
Section 3.2 of PS2, Reference Method (RM) measurement location and
traverse points, address the location of the RM Measurement point and
traverse points during Relative Accuracy (RA) testing.
3 2 Referpnce Method IRMj Measurement
Location and Traverse Points Select, as
appropriate, an accessible RM measurement
point at least two equivalpnt diameters
downstream from the nearest control device.
the point of pollutant generation, or other
point fit which a change in the pollutant
concentration or emission rate may occur.
and at least a half equivalent diameter
upstream from the effluent exhaust or control
device When pollutant concentraiion
changes are dae solely to diluent leakage
(e.g. air healer leakages) and pollutants and
diluents are simultaneously measured at the
same loc.ition, a half diameter may be used
in lieu of two equivalent diameters The
CEMS and RM locations need not be the
sjme
Then select traverse points that assure
acqi;i!>'ti:)n of representative samples over
the stack or duct cross section The minimum
requirements are as follows: Establish a
"measurement line" that passes through the
cfntroiddl area and in the direction of any
expected stratification [f this line interferes
wiih :he CEMS measurements, displace the
line up to 30 cm (or 5 oerceni of the
equivalent diameter of the cross section
whichever is less) from :he centruidal arej
Locate three traverse points at 18 7. 501) and
83 3 percent of the measurement line If the
measurement line is longer than 2 4 meters
and pollutant stratification is rot expected.
the tester may choose to locate the three
traverse points or. tne line at 0 4 i: ard20
me'ers f'orn tne staox or djc: v all T1-.
r °luiar.t concentrators are corr.L, nf-d
9-6
-------
This section of PS2 is also referenced in PS5. IN essence, it states
that during the RA testing, the RM sample is extracted from the source
by traversing the "measurement line" at three traverse points. If the
"measurement line" is 2.4 meters and pollutant stratification is not
expected, the tester may choose to locate the points on the line at 0.4,
1.2 and 2.0 meters from the stack or duct wall. If the "measurement
line" is longer than 2.4 meters, then the tester can locate the points on
the line at 16.7, 50.0 and 83.3 percent of the measurement line. This
stipulation, as recorded in PS2 and referenced in PS5, require the RM (Ifi
or 16A) to perform a sample traverse during RA determination.
9.2.5 Performance and Equipment Specification
Section 2.0, Performance and Equipment Specification, address the
performance specifications for calibration drift (CD) and relative accuracy
(RA). In particular, the calibration drift is determined separately for
the pollutant and diluent monitor. The drift test and relative accuracy
procedures provide a means of confirming the integrity of the monitoring
system on the source.
9.2.5.1 Calibration Drift -
The drift test involves introducing zero and span gas into the
monitoring system. This procedure is repeated over an 8 day period. The
monitor response is compared to the known concentrations (zero, span) to
determine calibration drift.
According to Performance Specification 5, manual adjustments to the
monitor are allowed after each determination, unless the monitor manufac-
turer specifies a shorter interval for adjustments. Specifically, the 24
hour drift test involves an established sequence of steps, as illustrated
in Table 9.4.
TABLE 9.4
ITINERARY INVOLVING CALIBRATION DRIFT DETERMINATION
Day
Procedure
3-7
8
Introduction of zero gas; adjustment of monitor to produce
a correct zero reading.
Introduction of span gas; adjustment of monitor to produce
a correct span value.
Introduction of zero gas; record monitor response; adjust to
zero, if needed.
Introduction of span gas; record monitor response; adjust to
correct span value, if needed.
Repeat sequence of steps performed during day 2.
Introduction of zero gas; record monitor response;
adjust to zero, if needed.
Introduction of span gas; record monitor response; end of
calibration drift test.
9-7
-------
Table 9.5 illustrates the Field Data Sheet for Calibration Drift Deter-
mination.
TABLE 9.5
CALIBRATION DRIFT DETERMINATION
ZERO/SPAN
Day
1
2
3
4
5
6
7
8
1
2
3
4
5
6
7
8
Date and
Time
Calibration
Value
Calibration Drift (%)
Monitor
Value
Difference
= (^Difference, ppm)
(Monitor Span value, ppn
Percent
of Span
Value
. X 100
During the Calibration Drift Test, the recorder should be offset ( 10%)
to allow for negative drift. The 24 hour drift test requires 8 sets of
zero and span measurements to facilitate 7 zero and calibration drift
determinations. The procedure prescribed by Performance Specification 2
requires adjustments to the zero and span values following the respective
zero and span measurements. Provided that this procedure is followed,
the individual zero drift values are calculated as the zero value measured
at the end of the 24 hour interval, minus the correct zero value. In the
same manner, the calibration drift is the span value at the end of the 24
hour interval minus the correct span value. The adjustment of the zero
value after the zero reading and before the span reading automatically
removes the effects of zero drift on the span measurements. Thus, no
further correction of the span measurements is necessary.
The Calibration Drift requirements are written in terms of per cent
of monitor span value for each individual day. Mathematically, this is
expressed by the following equation:
Calibration Drift (%)
_ (^Difference, ppm) {
I(Monitor span value,ppm)
X100
9-8
-------
9.2.5.2 Accuracy (Relative) -
In the majority of cases, the term accuracy refers to the extent with
which a measured value agrees with the actual or correct value. However, for
continuous monitoring systems measuring TRS, the accuracy is determined as
the degree with which the continuous monitor's measurement of the pollutant
(02 corrected) agrees with the coincident measurement of the pollutant hy an
EPA Reference Method (03 corrected). Therefore, the accuracy of the con-
tinuous monitor is not necessarily measured in terms of an actual or known
value but rather in terms of a second, independent measurement. For that
reason the accuracy specification is termed "relative accuracy", i.e.
relative to the value obtained by a Reference Method determination. As
indicated earlier, relative accuracy is calculated using three variables:
- algebraic mean difference between monitor and reference method
concentration measurements;
- 95% confidence interval (precision estimate associated with the
determination of the mean difference); and
- mean concentration of the reference method.
Mathematically, this can be expressed by the following equation:
% Relative Accuracy = |x| + C.!.QS% xiOO
where:
C.I. 95%
[RMavg]
absolute mean difference, for a series of tests,
between monitor value and reference method
value, corrected for oxygen;
2.5 percent error confidence coefficient;
Average Reference Method value, oxygen corrected,
for a series of tests.
The Reference Method TRS value and the CEM TRS value are both
corrected for oxygen, according to the following equation:
corr
meas
[m]
whereas:
C corr
C meas
X
Y =
the concentration corrected for oxygen.
the concentration uncorrected for oxygen.
the volumetric oxygen concentration in percentage to be
corrected to (8 percent for recovery furnaces and 10
percent for lime kilns, incinerators or other devices).
the measured 12 hour average volumetric oxygen
concentration.
9-9
-------
The performance specifications for TRS CEMs are addressed in terms of cal-
ibration drifts and relative accuracy for TRS and calibration drifts for
diluent monitors. In recent years, many of the performance specification
requirements for gaseous CEMs have been eliminated. Table 9.6 illustrates
the history of the performance specification requirement for each of the
pollutants.
It is interpreted by the present regulations that many of the pre-
vious requirements were more long term quality assurance oriented, therefore
would be addressed during later promulgated quality assurance regulations.
TABLE 9.6
PERFORMANCE SPECIFICATION REQUIREMENTS
REGULATORY CHANGES
Performance Performance Performance
Specification Specification Specification
2 35
(S0?/N0y) (0?/CO?) (TRS)
Parameter
Accuracy
Calibration
Error
Zero Drift
(2 hours)
Zero Drift
(24 hours)
Calibration
Drift (2 hours)
Calibration
Drift (24 hours)
Response Time
Operational
Period
19751
X
X
X
X
X
X
X
X
19832
X
-
_
X
-
X
X
X
19751
—
-
X
X
X
X
X
X
19832
X
-
_
X
-
X
X
X
19833
X
-
_
X
-
X
-
-
1. Federal
2. Federal
3. Federal
Register:
Register:
Register:
10/06/75
5/25/83
7/20/83
40
48
48
FR 46240
FR 23608
FR 32986
The mechanics of performing a relative accuracy determination involves a
series of planned steps, as outlined in Table 9.7.
9-10
-------
TABLE 9.7
PERFORMANCE SPECIFICATION TEST 5 FUNCTIONS
Time Activity
6:00 A.M I. Stratification Determination
7:00 A.M. II. Assemble Sampling Train
o Particle Removal System
o S02 removal system
o Permeation tubes in calibrator 24 hrs prior
to test?
o Chromatogram showing calibration gases
with and without C02.
o Chromatogram showing separation of S02
from reduced sulfur components?
o All measurement/flow gauge calibrated and
certificates sheets available.
8:00 A.M. Ill Pre-Test Functions
o Leak test sampling train
o Upstream of pump
o Downstream of pump
o Calibration curve generated at 3 levels for
H2S, CH3SH, (CH3)2S and (CH3)2S2
o Calibration of dilution system to develop
dilution factor using H2S.
9:00 A.M. IV Test Functions
o Insert probe into stack
o Pull sample through conditioning system for
approx. 15 mins.
o Commence traversing and sampling
o Sample run involves 16 individual analyses
over a period of not less than 3 hrs. or more than
6 hrs.
o Orsat collected
9-11
-------
TABLE 9.7 (Continued)
PERFORMANCE SPECIFICATION TEST 5 FUNCTIONS
Time
Activity
12:00 noon V. Post-Test Functions
o Leak check of total system
o Sample line loss determination using
at the level of the applicable
standard
o Correction factor developed
o Recalibration after each run, or each series
of runs made within 24-hours
o Preliminary concentration determination
1:00 VI. Repeat for other test runs
7:00 P.M. VII. Calculations
Once the Relative Accuracy test is complete, a Field Relative Accuracy
Data sheet should be completed as part of the test report. Following
is an example of a typical Field Relative Accuracy Data Sheet.
9-12
-------
Company
Address
Company Contact
I. Field Data
FIELD RELATIVE ACCURACY
DATA SHEET
Date
Analyst
Sample Location
Run #
1
2
3
4
5
6
7
8
9
Avg.
Time
Total Reduce
(P
CEM
Concentration
(0? Corrected)
id Sulfur (TRS)
m)
Reference
Method
(02 Corrected)
Difference
II. Calculation
% Relative Accuracy = |X| + C.I
xioo
III. Acceptance
x 100
Test 1
Test 2
Test 3
% Relative Accuracy < 20% of mean value of Reference Method?
~ Yes
No
% Relative Accuracy 10% of the applicable standard?
Yes
No
IV. Recovery Data
% Recovery <_ 20% ?
Yes
No
9-13
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9.3 PERFORMANCE SPECIFICATION 3 - SPECIFICATION AND TEST PROCEDURES
FOR Og AND C02 CONTINUOUS EMISSION MONITORING SYSTEMS
9.3.1 Introduction
Performance Specification Test 3 - Performance Specifications and
Specification Test Procedures for Monitors of C0£ and D£ from Stationary
Sources, was originally promulgated October 6, 1975 in the Federal Register
as part of Appendix B of 40 CFR 60. Concurrent with their promulgation,
Performance Specification Test 1 for opacity continuous emission monitors
and Performance Specification Test 2 for SOg and NOX continuous emission
monitors were also mandated.
The basic intent of the performance specifications was to evaluate
the continuous emission monitoring system on the source under field
conditions to determine its conformance with applicable specifications.
Because the Standard of Performance for Kraft pulp mills, relating
to total reduced sulfur emissions, are 12-hour average TRS concentrations
corrected to a percent oxygen, oxygen must also be monitored on a continuous
basis. The equation reflecting this requirement is:
'corr
= C
meas
21 - X
21 - Y
Where:
ccorr
cmeas
A
Y =
the concentration corrected for oxygen;
the concentration uncorrected for oxygen;
the volumetric oxygen concentration in
percentage to be corrected to (8 percent
for recovery furnaces and 10 percent for
lime kilns, incinerators, or other de-
vices); and
the measured 12-hour average volumet-
ric oxygen concentration.
As required by the regulations, fy continuous emission monitors must
pass Performance Specifications Test 3.
Basically, the performance specifications consists of a set of
operating criteria that each system installation must be shown to
either meet or exceed. These specifications were judged to be important
factors in the successful operation of any particular system. Table 9.8
illustrates the divisions of Performance Specification Test 3.
9-14
-------
TABLE 9.8
PERFORMANCE SPECIFICATION TEST 3
1.0
2.0
5JO
1.0
1.0
10
7.0
in
PERFORMANCE SPECIFICATION TEST 3
MONITORS OF C02 AND QZ
^B
^H
MM
Mi
••
^
APPLICATION AND PRINCIPLE
APPRATUS
DEFINITIONS
INSTALLATION SPECIFICATIONS
CONTINUOUS MONITORING SYSTEM
PERFORMANCE SPECIFICATIONS
PERFORMANCE SPECIFICATION
TEST PROCEDURES
CALCULATIONS. DATA ANALYSIS AND
REPORTING
1
RTRI fOCRAPUV !
9.3.2 Regulatory Changes
The performance specification requirements, when originally
promulgated, addressed drift test (2 and 24 hour) for both zero and
span, response time and operational test period. As with P$2f P$3
did not specify design criteria for C02 and 02 analyzers.
On January 26, 1981, revisions to PS3 were proposed In the Federal
Register. The difference between the 1975 promulgated specifications
and the 1981 was the addition of a relative accuracy test. U.S. EPA
felt that if the C02 or 02 analyzer was not part of the continuous
emission monitoring system, as covered under PS2, then a relative accu-
racy determination was needed.
The promulgated specifications were published in the Federal Register
on May 25, 1983. The relatives accuracy requirements were retained
for those C02 or 02 analyzers not covered under PS2. However, the 2-
hour drift test along with the response time and operational test period
were not referenced in the May 25, 1983 regulations. Table 9.9 illu-
strates the regulatory changes made between 1975 and 1983.
9-15
-------
TABLE 9.9
PERFORMANCE SPECIFICATION TEST 3
REGULATORY CHANGES
Parameter
Relative
Accuracy
Calibration
Error
Drift Test
Zero
- 2-hour
- 24-hour
Span
- 2-hour
- 24- hour
Response Time
Operational
Peri od
10/6/75 (40 FR 46268)
Promulgated
—
—
0.4% (02 or C02)
0.5% (02 or 0)3)
0.4% (02 or C02)
0.5% (02 or C02)
10 minutes (max.)
168 hours
1/26/81 (46 FR 8364)
Proposed Revision
20% of mean valve
of reference method
test data, or 1.0
present 02 or C02,
whichever is greater.
—
0.5% (02 or C02)
0.5 (02 or C02)
10 minutes (max.)
168 hours
5/25/83 (48 FR 23610)
Promulgated Revisions
20% of mean valve
of reference method
test data, or 1.0
present 02 or C02,
whichever is greater.
—
0.5% (02 or C02)
0.5% (02 or C02)
—
—
VO
HJ
CO
*Each parameter determined from a series of tests; numerical value
is the sum of the absolute value of the arithmetic mean plus the
95% confidence interval for the associated tests.
-------
9.3.3 Interpretation of Performance Specification Test 3
9.3.3.1 Principle and Application -
Performance Specification Test 3 is used for evaluation of
acceptability of Og and COg continuous emission monitors (CEM's) at
the time of or soon after installation and whenever specified in an
applicable subparts of the regulations. The specifications apply to
Og or COg, monitors that are not included under Performance Specifi-
cation 5 (PS5).
The authors of PS3 intended the regulations to apply only to those
monitors not used to report emissions in units of the standard. For
example, Kraft pulp mills report emissions in ppm of TRS, corrected to a
percent oxygen. In this configuration, the output of the TRS continuous
emission monitoring system corrects to a percent oxygen. The oxygen moni-
tor is therefore a part of the total TRS CEM system. As such, relative
accuracy of the TRS monitoring system incorporates error associated with
the 02 analyzer.
9.3.3.2 Apparatus
This section of PS3 addresses the calibration gas mixtures to be used
in evaluative calibration drift determination. In particular, the gas
cylinder concentrations should be known concentrations of carbon dioxide
or oxygen in nitrogen or air. The calibration gas mixture shall be at
two levels as indicated in Table 9.10.
TABLE 9.10
CALIBRATION GAS MIXTURE LEVELS
Range
Low Level
High Level
Op/CO?
0-20% of Span Valve
50-100% of Span Valve
Triplicate analysis of the gas mixture should be performed within
two weeks prior to use using Federal Reference Method 3.
9.3.3.3 Definitions
The total continuous emission monitoring system involves the total
equipment required for determination of C02 or 03. Since most TRS CEMs are
extractive, the system would involve the side stream of gas taken from the
main gas stream for 0? analysis, the analyzer itself and the data record-
ing system.
9-17
-------
9.3.3.4 Installation Specification -
If the 02 continuous emission monitoring system is not part of the
TRS CEM, then it shall be installed at a sampling location where measure-
ments that can be made are representative of the effluent gases sampled
by the pollutant continuous monitoring system(s). Conformance with this
requirement may be accomplished in any of the following ways:
(1) The sampling location for the diluent system shall be
near the sampling location for the pollutant con-
tinuous monitoring system such that the same approx-
imate point(s) (extractive systems) is sampled; and
(2) The diluent and pollutant continuous monitoring system
may be installed at different locations if the effluent
gases at both sampling locations are nonstratified and
there is no in-leakage occuring between the sampling points.
For TRS monitoring systems, the Og is normally taken as a side stream of
the main extractive sample. As such, both the TRS monitor and the 02
monitor would see the same gas stream. Consequently, the sampling point
location is not a critical factor.
9.3.3.5 Continuous Monitoring System Performance Specifications -
As specified in the regulations, the only specifications the 0-2 moni-
tor must meet are illustrated in Table 9.11.
TABLE 9.11
PERFORMANCE SPECIFICATION
Parameter
Drift Test
(24 hour)
Zero
Span
Relative Accuracy*
Specifications
5/25/83 48 FR 23600
0.5%
0.5%
20% of mean val ve
of reference method test
data or 1.0 percent 02,
whichever is greater
* Only applies to those 02 and C02 monitors not covered under
Performance Specification 2 (PS2).
9-18
-------
9.3.3.5.1 Accuracy (Relative) -
The Relative Accuracy (RA) test provides a means of confirming the
integrity of the 63 continuous emission monitoring system. As discussed
earlier, relative accuracy requirements are not required for installed Og
continuous emission monitors used in conjunction with pollutant monitors
to generate a value in terms of units of the standard. For Kraft pulp
mills, this involves correcting TRS emissions to a percent oxygen value.
Thus, the oxygen monitor is part of the TOTAL CEM system. Any inaccuracies
in the 02 monitors will be incorporated in the total system Relative Accu-
racy Test for the pollutant monitor.
9.3.3.5.2 Calibration Drift Test -
However, there are calibration drift requirements which are determined
separately for the pollutant and diluent monitor.
The drift test involves introducing zero and span gas into the monitor-
ing system. This procedure is repeated over an 8 day period. The monitor
response is compared to the known concentration (zero, span) to determine a
calibration drift error. The calibration gas mixture concentrations should
be those specified in Table 9.10.
According to the Performance Specification Test , manual adjustments to
the monitor are allowed at 24-hour intervals, unless the monitor manufactur-
er specifies a shorter interval for adjustments. Table 9.12 summarizes the
sequence of steps performed in a drift test determination.
TABLE 9.12
ITINERARY INVOLVING CALIBRATION DRIFT DETERMINATION
Day
Procedure
3-7
8
Introduction of zero gas; adjustment of monitor to
produce a correct zero reading.
Introduction of span gas; adjustment of monitor to
produce a correct span value.
Introduction of zero gas; record monitor response;
adjust to zero, if needed.
Introduction of span gas; record monitor response;
adjust to correct span valve, if needed.
Repeat sequence of steps performed during day 2.
Introduction of zero gas; record monitor response;
adjust to zero, if needed.
Introduction of span gas; record monitor response;
End of calibration drift test .
9-19
-------
Table 9.13 illustrates the Field Data Sheet for Calibration Drift Deter-
mination.
TABLE 9.13
FIELD DATA SHEET
CALIBRATION DRIFT DETERMINATION
Day
1
2
3
4
5
6
7
8
1
2
3
4
5
6
7
8
Date and
Time
Calibration
Value
Monitor
Value
Difference
Percent
of Span
Value
Calibration Drift (%) =
"Difference, ppm)
Monitor Span value, ppm)
X 100
During the calibration drift test determination, the recorder should be
offset (-10%) to allow for negative drift. The 24-hour drift test requires
8 sets of zero and span measurements to facilitate 7 zero and calibration
drift determinations. The procedure prescribed by Performance Specifica-
tion ?. requires adjustments to the zero and span values following the
respective zero and span measurements. Provided that this procedure is
followed, the individual zero drift values are calculated as the zero value
measured at the end of the 24 hour interval, minus the correct zero value.
In the same manner, the calibration drift is the span value at the end of
the 24 hour interval minus initial reading (before the span reading auto-
matically removes the effects of zero drift on the span measurements).
9.3.3.6 Calculations, Data Analysis and Reporting -
The calibration drift requirements are written in terms of per cent
of monitor span value for each individual day. Mathematically, this is
expressed by the following equation:
Calibration Drift ( % )
( ^Difference, ppm ) x 100
( Monitor span valve,ppm )
i
9-20
-------
10.0 EXCESS EMISSION REPORTS
10.1 INTRODUCTION
The Environmental Protection Agency (EPA) and many state air pollution
control agencies are rapidly expanding their programs involving recordkeeping
and reporting requirements in association with emission monitoring programs
and performance testing. This is due, in part, to new regulations pertaining
to new and existing sources as outlined in 40 CFR 60 and 40 CFR 51 respec-
tively. These regulations require "installation of monitoring equipment
and performance testing...." and "for periodic reports and recordkeeping
of nature and magnitude of such emissions." Likewise, Sections 113 and
114 of the Clean Air Act (CAA) as amended in 1977, involve the use of
recordkeeping and reporting requirements as a means of enforcement of
emission standards.
Historically, the reporting requirements have involved "excess emis-
sions" over and above emission standards as indicated by the continuous
emission monitor. The initial intent of the regulations was to provide
the source operators, through the use of continuous emission monitoring,
the ability to monitor and "fine tune" his pollution control device. Only
those emissions above a regulated standard were reported through the quart-
erly excess emission report (EER) to the control agency. The EER should
contains information on number of excess emission over a standard, time
and duration of those excess emissions, reason codes for excess emissions
and corrective/preventive action taken to reduce those emissions. As
personnel and money limits the feasibility of on-site inspections, the
EER becomes an important "feedback" system for both the source and the
regulatory agency. The EER becomes a tracking tool by which agency per-
sonnel can evaluate both the control equipment and CEM performance. The
EER provides a useful function for both the sources being regulated and
the regulatory agency. For the source, the benefits are:
o to help ensure upper management awareness and attention of
excess emissions through the formal requirement for source
submittal of a summary of excursions. This hopefully increases
the likelihood of the source's timely attention to the reduction
of excess emissions; and
o as a tool in preventive maintenance/risk management/cost control
programs and to flag deterioration of control equipment performance.
In cases such as fuel burning, CEM data can be used to optimize
continually the combustion process and control system performance,
thus saving money and preventing pollution at the same time.
For the regulatory agency, the benefits are:
o as a screening tool, to identify sources experiencing frequent
or continual excursions. Such sources can be subjected to add-
itional attention in the form of phone calls, inspections, etc.
10-1
-------
o in addition to identifying problem sources, to help
pinpoint specific source components for special
attention during an inspection;
o to document the severity (e.g., duration, magnitude, and
frequency) of a source's excess emissions.. For example,
HER data can provide supporting evidence of the long-term
nature of violations, negating source claims of isolated
problems;
o to document that a compliance test was performed during
"non-representative" operating conditions;
o as support for issuing a Notice of Violation (NOV);
o to establish a data base for the development of agency
policies and strategies (e.e,, acid rain strategies);
o as the basis for assessing "good air pollution control
practices;"
o as an alternative to agency inspections of sources as
delineated in the Levels of Inspection; and
o to monitor the emissions and performance of a
source subject to specific permit, consent decree,
or administrative order requirements.
Data from the excess emission report can be entered into the CEM
subset of the Compliance Data System (CDS). The CDS system forms the basis
by which EPA tracks the compliance status of regulated sources. In order to
make proper planning and budgetary decisions, periodic update of the CDS
system is mandatory. The EER becomes the vehicle (outside of on-site
inspections) by which the Agency can update the CDS system and monitor
performance of both the pollution control equipment and the source's CEM
system.
10.2 STANDARDIZED EXCESS EMISSION REPORT
In recent years, the standardized EER has not only been used to
report excess emissions, but also provide other information associated with
both control equipment and monitor performance. Such information as:
o excess drift determination;
o quarterly audit results;
o relative accuracy test;
o pollution control device operating
parameters (pressure drop, mi 11 lamps, flow rates, etc.);
o "out-of-control" situations; and
o control equipment "baseline" information
has become routine report items on the EER. With limited resources and
manpower, the EER becomes the "tracking" mechanism of monitor and control
equipment performance during periods when the control Agency personnel are
unable to perform on-site evaluations.
10-2
-------
The EER has become a major part of the enforcement program of
regulatory agencies. This new Importance has shifted the Initial Intent
of the EER as an Indicator of emissions over a standard to a "continuous
compliance" standard Indicator. Consequently, present day Interpretation
of the regulations moves the EER from a historical document to a present
day doctvnent. The present day EER form must provide needed Information
concerning "ma inter..a nee of compliance" as referenced In the regulations.
For stationary sources subject to NSPS continuous monitoring require-
ments, 40 CFR 60.7 requires submittal of a written report of excess
emission for every calendar quarter.
Historically, the reporting requirements for NSPS sources (40 CFR
Part 60) have involved a written report for any calendar quarter in which
source emissions exceed the value of the standard. The emission value,
as recorded by the CEM system (i.e., % opacity, ppm, Ib/ton, etc.) must
be recorded, as well as the duration (i.e., six minutes, 3 hours, 12
hours, etc.) of the excess emission. An excess emission is defined as
exceedance of the emission limit values over the time period specified
by the subject standard.
Similarly, 40 CFR Part 51 requires some existing stationary sources
to implement a continuous monitoring program and to provide quarterly
excess emission reports (EERs). The minimum information required in the
excess emission report is:
1. The magnitude, duration and date of excess emissions;
2. The identification of each excess attributable to startups,
shutdowns, and malfunctions;
3. The cause of any malfunction and the corrective action or
preventive measures adopted;
4. The date, time, and duration of any monitor outage for reasons
other than zero and span checks;
5. The reason for monitor outage and corrective action taken;
6. If there are no excess emissions and no monitor outages, this
information must also be reported.
Those NSPS sources required to submit EERs are listed in Table 10.1.
10-3
-------
TABLE 10.1
NSPS SOURCES REQUIRED TO SUBMIT
EXCESS EMISSION REPORTS (EERs) TO REGULATORY AUTHORITIES
Subpart
Source Category
Pollutant
Da
G
H
J
P
0
R
Z
AA
Steam Generators
Solid Fossil Fuel
Liquid Fossil Fuel
Gaseous Fossil Fuel
ELECTRIC UTILITY STEAM
GENERATING UNITS
Solid Fossil Fuel
Liquid Fossil Fuel
Gaseous Fossil Fuel
NITRIC ACID PLANTS
SULFURIC ACID PLANTS
PETROLEUM REFINERIES
FCCU
Combustion of Fuel Gases
Sulfur Recovery Plant
PRIMARY COPPER SMELTERS
PRIMARY ZINC SMELTERS
PRIMARY LEAD SMELTERS
FERROALLOY PRODUCTION
FACILITIES
STEEL PLANTS:
ELECTRIC ARC FURNACES
Opacity, SOg, NOX
Opacity, SOg, NOX
NOX
Opacity, S02 (at inlet
and outlet of control
device), NOX
Opacity, S02 (at
inlet and outlet
of control device),
NOX
NOX
NOX
S02
Opacity, CO
S02 or H2S
S02, H2S, TRS,
Opacity, S02
Opacity, S02
Opacity, S02
Opacity
Opacity
10-4
-------
TABLE 10.1 (Continued)
NSPS SOURCES REQUIRED TO SUBMIT
EXCESS EMISSION REPORTS (EERs) TO REGULATORY AUTHORITIES
Subpart Source Category Pollutant
BB KRAFT PULP MILLS
Recovery Furnace Opacity
TRS (dry basis)
Lime kiln, digester TRS (dry basis)
system, brown stock
washer system, multiple
effect evaporator system,
black liquor oxidation
system, or condensate
stripper system.
HH LIME MANUFACTURING PLANTS
Rotary Lime Kilns Opacity
For Subpart BB, Standards of Performance for Kraft Pulp Mills, EER's
must be submitted to the regulatory authority when emission levels are
exceeded for affected facilities within the subpart. Table 10.2 lists
those affected facilities in the Kraft pulp mill which require reporting
exceedances.
Similarly, 40 CFR 51 requires that all existing stationary sources,
directed to implement a continuous monitoring program, must also provide
quarterly excess emission reports (EERs). This reporting requirement, as
originally conceived in the September 11, 1974, specified not only quarterly
reporting of excess emissions but also quarterly submittal of all monitoring
results. This was later revised to require the reporting of only excess
emissions.
As defined, excess emission of TRS for each affected facility in Sub-
part BB, Kraft Pulp Mills, are defined in terms of emissions over a
standard for a twelve hour average period. The regulations do not,
however, specify the definition of a 1-hour average to comprise the 12-hour
average. As written, the average may be calculated either by:
(1) integrating over the hourly intervals; or
(2) arithmetic averaging over the hourly intervals.
10-5
-------
TABLE 10.2
KRAFT PULP MILLS
EXCESS EMISSION REPORTING REQUIREMENTS
Source Category
Subpart BB - Kraft Pulp Mills
Proposed/effective
9/24/76 (41 FR 42012)
Promulgated
2/23/78 (43 FR 7568)
Revised
8/7/78 (43 FR 34784)
i— »
i
Affected
Facility
Recovery furnace
Smelt dissolving
tank
Lime kiln
Digester, brown stack
washer, evaporator.
oxidation, or strip-
per systems
Pollutant
Particulate
Opac i ty
TRS
(a) straight recovery
(b) cross recovery
Particulate
TRS
Particulate
(a) gaseous fuel
(fa) liquid fuel
TRS
TRS
Emission Level
0.044 gr/dscf
(0.10 g/dscm)
corrected to 8S
oxygen
352
5 ppm by volume
corrected to 8%
oxygen
25 ppm by volume
corrected to 81
oxygen
0.2 Ib/ton
(0.1 g/kg)BLS
0.0168 Ib/ton
(0.0084 g/kg)BLS
0.067 gr/dscf
(0.15 g/dscm)
corrected to 10Z
oxygen
0.13 gr/dscf
(0.30 g/dscm)
corrected to 101
oxygen
8 ppm by volume
corrected to 102
oxygen
5 ppm by volume
corrected to 10
oxygen
•exceptions ; see
standards
Monitoring
Requirement
No requirement
Continuous
Continuous
No requirement
No requirement
No requirement
No requirement
Continuous
Continuous
Effluent gas incineration
temperature; scrubber liquid
supply pressure and gas
stream pressure loss
CEM
Reporting Requirements
EER for six-minute averages in excess of 35S if
period with violations are greater than 6] of
six-minute periods
EER for twelve-hour averages In excess of 5 ppm
time periods with violations are greater than
of total twelve-hour periods
EER for twelve-hour averages in excess of 25 ppr.
time periods with violations are greater than '
total twelve-hour periods
Note: BLS = BLACK Liquor Solids
EER for twelve-hour averages 1n excess of 8 ppm
EER for twelve-hour averages In excess of 5 ppm
Report for all periods greater than five minute-
combustion temperature less than 1200°F
-------
Guidance is given in Subpart D, Standards of Performance for Fossil
Fueled Fired Steam Generators (FFFSG), associated with the definition
of a 1 hour average. The regulation uses a minimum of "four equally
spaced data points" for determining an hourly average. However, no guid-
ance is given by the regulations in association to what constitutes a
valid hour of emission data.
Excess emission reporting requirements for Kraft pulp mills also
allow an accepted excess emission over the standard before it must be
reported. The exemption states:
§60.283(a)(l)(ii):
"(e) The Administrator will not consider periods of excess emissions
reported under paragraph (d) of this section to be indicative of a
violation of £ 60.11(d) provided that:
(1) The percent of the total number of possible contiguous
periods of excess emissions in a quarter (excluding periods of
startup/ shutdown, or malfunction and periods when the facility is
not operating) during which excess emissions occur does not exceed:
(i) One percent for TRS emissions from recovery furnaces*
(ii) Six percent for average opacities from recovery furnaces*
(2) The Administrator determines that the affected facility,
including air pollution control equipment, is maintained and operated
in a manner which is consistent with good air pollution control
practice for minimizing emissions during periods of excess emissions,"
The EER is used by some regulatory agencies for enforcement actions;
therefore, the report must be thorough and complete. A recent survey of
22 NSPS sources required to submit EER's to EPA regional offices revealed
that only 25 percent of the required information was reported to the
Federal or State authorities. All surveyed had omitted one or more of
the following areas of information from the EER:
1) reason for the excess emissions;
2) action taken to reduce excess emissions; and
3) any malfunctions associated with the CEM system.
Another survey showed that CEM programs with good recordkeeping
and reporting requirements also had demonstrated reliable CEM operations.
This information has prompted EPA to examine the use of "standardized"
EER's to facilitate ease and completeness of reported data. A standardized
report format for process/ control equipment and excess emission informa-
tion would provide the following benefits:
1) increase industry understanding of the EER requirements;
2) provide a correlation between "excess emission" and control
or process monitoring malfunctions;
10-7
-------
3) eliminate the need and cost for individual users and CEM
system manufacturers to design special data handling and
reporting systems;
4) reduce industries' effort in completing EERs and agencies'
workload to review the reported data; and
5) identify data reliability.
Following is an example of a "standardized" EER form for Subpart BB,
Kraft pulp mills.
10-8
-------
EXCESS EMISSION REPORT
KRAFT PULP MILLS
SUBPART BB
Continuous Emission Monitoring Data
Quarterly Report
Report Period Ending Mar 31 £J June 30 £J Sept 30 fj Dec 31 £7
Year 19_
I. General Information
1. Source
2. Address
3. Phone Number ( )_
4. Affected Facility
5. Control Device
6. Fuel Type
7. Person Completing Report (Print)_
(Signature)_
(Date)
THIS IS TO CERTIFY THAT, TO THE BEST OF MY KNOWLEDGE, THE INFORMATION
PROVIDED ON THESE FORMS IS CORRECT AND ACCURATE.
8. Person responsible for (Print)
revi ew and i ntegrity
of report (Signature)
(Title)
(Date)
10-9
-------
II. Continuous Monitor Data
Opacity
Total Reduced Sulfur
(TRS)
1. Manufacturer
2. Model No.
3. Serial No.
4. Basis for Gas Measurement
(wet or dry)
5. Averaging Time
6. Corrected to % 02 XXXXXXXXXXXXXXX
7. Zero/Calibration Values
Zero %
Cal %
8. Date of Last Performance
Specification Test Passed
9. Performance Specification
Test
Date
10. Emission Limit
11. Total Operating Time of
Source During Reporting
Period (minutes)
ppm
ppm
10-10
-------
III. Continuous Emission Monitor Excess Emission Data
Pollutant: /_/ Opacity /_/ TRS (Corrected % 03)
Process:
Excess
Emission
Period
Date
Day/Month/Year
Time
(24 hr clock)
Begin | End
Duration
(minutes)
Average Value of Emissions
During Excess
JJ % /_/ppm
Reason for
Excess Emissions
Corrective
Action
Taken
o
I
/ / No Excess Emissions During Reporting Period
-------
IV. Continuous Emission Monitor Performance Data
Pollutant: fj Opacity fj TRS
Process
Monitor
Downtime
Period**
Date
Day /Month/Year
i— >
0
I-"
ro
Time
(24 hr clock)
Begin | End
Duration
(minutes)
Reason
for
Outage
Corrective
Action
Taken
Total
Operating
Time
of Source
(minutes)
on Date of
Monitor
Downtime
Monitor*
Availability
(*)
for Date
* Monitor Availability = CEM downtime during source operating time (Min) x
Source operating time (Min)
**Include periods of monitor equipment malfunction, non-monitor CEM equipment malfunction, or unknown causes,
I~~T No CEM Downtime During Reporting Period
-------
10.3 EXCESS EMISSION AGENCY REVIEW PROCESS
Once the EER Is submitted by the source to the regulatory authority,
it should be reviewed and entered into the CDS. To assist in this effort,
the Stationary Source Compliance Division recently published a document
entitled: "Technical Guidance on the Review and Use of Excess Emission
Reports." The main objective of this document was the implementation, at
the state and regional levels, of a methodical procedure to review and
follow up on EERs.
The EER review involves a three-phase process:
o Phase 1 - Initial review and summary of EER data;
o Phase 2 - Confirmation of Phase 1 results, targeting of sources
for follow up, and data input to the CEM subset of the Compliance
Data System (CDS); and
o Phase 3 - Follow up comparison of CEM and other emission data,
with potential recommendations for additional testing or
compliance/enforcement actions.
An example of the proposed agency checklist for EERs can be found at
the end of this section.
10.3.1 Phase 1 - Initial EER Review
During Phase 1, the agency reviewer evaluates the data for entry
into the CDS. In particular, the reviewer addresses completeness and
general acceptability of the EER for the following areas:
o Submittal of EER within 30 days after the end of each calendar
quarter containing:
(1) Excess emissions; and
(2) Monitor system performance;
o Submittal of EER even if no excess emissions occurred within the
quarter;
o Verification that the excess emission report includes:
(1) The magnitude (averaged during the excess period, including
any conversion factor(s) used), date, start and ending times,
nature, cause and corrective action taken for each excess
emission; specific identification of each period of excess
that occurred during startups, shutdowns and malfunctions of
the affected facility; the nature and cause (if known) of
the malfunctions and corrective actions taken;
(2) The date, start and ending times of each instance when the
CEM was inoperative (except for zero and span checks, etc.),
and description of the nature, cause and corrective action
taken for each such period; and
(3) Total operating time of source in the quarter.
10-13
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10.3.2 Phase 2 - Targeting of Follow Up Action
Phase 2, verification of Phase 1 results, requires the control agency
reviewer to identify if:
o completion of internal check and concurrent with phase 1;
o comparison of EER data with control agency targeting criteria; and
o entry of EER data into the CEM subset of the CDS.
Spot-checking of phase 1 data to concur with its results is normally
a sufficient internal review. Once the internal check is completed, the
percent availability for the industry operating time is compared to the
agency action target level. If it does not fall within the preset target
level, then follow-up action might be appropriate. The objective is to
identify those sources which are indicating "non-compliance" more so than
other reporting sources. These "targeted" sources would constitute some
action on the part of the reviewing control agency. Once phase 2 review is
completed, the control agency should notify the source of the results, whether
positive or negative. This will help promote a cooperative effort between
the source and the control agency.
Finally, during phase 2, the data is entered into the CEM subset of
the CDS.
10.3.3 Phase 3 - Follow Up Activity
Phase 3 involves the follow up activities for those sources targeted
in phase 2 of the review process. This may be done in the office or the
field. In essence, the control agency personnel is determining the validity of
the EER, through comparisons of other available data (inspection reports,
stack test reports, etc.), to formulate a recommendation for an enforcement
action.
Once the three phase review has been completed, the reviewer then
signs the review checklist, indicating all necessary actions pertaining to
this review process have beem completed.
Following is an example of an control agency reviewer checklist for Kraft
pulp mill excess emission reports. The checklist is divided into three
sections: (1) Abbreviated Reviewers Checklist; (2) Detailed Action
Reviewers Checklist; and (3) Follow-up Action From Detailed Action.
10-14
-------
EXCESS EMISSION REPORT
KRAFT PULP MILLS - SUBPART BB
ABBREVIATED REVIEWER'S CHECKLIST
Phase 1 Review
Name
Date
Phase 2 Review/
Subset Data Entry
Phase 3 Review/
CDS Action Entry
Name
Date
Name
Date
1.0. GENERAL INFORMATION
1.1
Company
Plant/Unit
Quarter
Year
Process
1.2 Timeliness (Must be postmarked within 30 days of quarter)
(a) Date Postmarked
(b) Days Late
2.0 COMPLETENESS (For EERs which cover multiple monitors, specify monitor
when noting problem.)
2.1 Excess Emissions (EEs) Information
(a) Data Reported in Units of
Applicable Standards (ppm,
corrected to % 03,or opacity)
(b) Date and Time of Commencement
of Excess Emission
(c) Average Magnitude (ppm or
opacity)
(d) Identification of Excess
Emissions Caused by Start-
up, Shutdown, or Malfunction
(e) Nature and Cause of Malfunc-
tion
(f) Malfunction Corrective Action
or Preventive Measures Taken
(g) Affirmative Statement of NO
Excess Emissions
2.2 CEMS Performance Information
(a) Date and Time Identifying
Specific Periods During Which
CEM was Inoperative
No Problem
Problem (Describe)
10-15
-------
No Problem
(b) Nature of Corrective Action/
System Repairs or Adjustments
(c) Monitor % availability for date
calculated
(d) Affirmative Statement of NO
Period of Downtime, Repair
or Adjustment (include no
CEMS modifications)
2.3 Source Operating Time Noted
Problem (Describe)
3.0 EER DATA SUMMARY
3.1 Should This EER Be Reviewed For Possible Agency Follow-up?
Yes/No
Comments
3.2 Signature
(Pri nt)
(Date)
10-16
-------
EXCESS EMISSION REPORT
KRAFT PULP MILLS-SUBPART BB
DETAILED REVIEWERS CHECKLIST
1.0
1
1
2.0
GENERAL INFORMATION
.1 Company
.2 Plant/Unit
DATA SUMMARY FOR TRS/OPACITY
Phase 1 Review
Name
Phase 2 Review
Name
Phase 3 Review
Name
Quarter
Process
EERs (USE SEPARATE FORM FOR EACH
Date
Date
Date
Year
MONITOR
2.1 CEMS Performance Per Quarter
Causes of CEMS Downtime
Monitor Equipment Malfunction
Non-monitor CEMS Equipment
Malfunctions
(i.e. Computer, Data Recorder
etc.)
Calibration/QA Audits
Other
Unknown Causes
Average
Total Downtime
# of
Incidents
Total
Mins.
Source
Operating
Time (Min)
% Availability*
*% Availability = (CEM uptime during source operating time, min.) x
(source operating time, min.)
2.2 Emission Performance Per Quarter
Causes of Excess Emissions
Control Equipment Failures
Process Problems
Other
Average
Total Excess
Emissions
* of
Incidents
Total
Mins.
Source
Operating
Time (Min.)
% Compliance*
% Compliance = (Source Operating Time, min.) - (Excess Emissions, min.)
( Source Operating Time, min.)x 100
10-17
-------
10-18
-------
EXCESS EMISSION REPORT
KRAFT PULP MILLS-SUBPART BB
FOLLOW-UP REVIEWERS CHECKLIST
Phase 1 Review
Phase 2 Review
Phase 3 Review
1.0 GENERAL INFORMATION
1.1 Company
1.2 Plant/Unit
Name
Date
Name
Date
Name
Date
Quarter
Year
2.0 FOLLOW-UP ACTIVITY FROM DETAILED EER REVIEW
Follow-up Action
No Action
Detailed EER Review
Next Quarter
Contact Source
a. Telephone source
b. Meet with source
c. Req. addit. info.
d. Req. addit. report
e. Request corrective
action
f. Req. addit. test
g. Request alt. moni-
toring
h. Request specific
O&M/QA procedures
i. Other (Specify)
Additional Surveillance
a. VEO
b. Inspection
c. Audit
d. Compliance Test
e. Other
Enforcement
a. Warning Letter
b. § 113 NOV
c. § 113 Comp. Order
d. Init. Civil Action
f. Other (Specify)
CEMS Problems
TRS
OPACITY
Emission
Problems
TRS
OPACITY
Time-
liness
Complete-
ness
10-19
-------
10-20
-------
11.0 QUALITY ASSURANCE/QUALITY CONTROL
11.1 INTRODUCTION.
The primary objective of a Quality Assurance (QA) program for CEMs
is to ensure that all data collected and reported are meaningful, precise
and accurate within a stated acceptance criteria. The program should be
strong, but flexible enough to allow continuing evaluation of its adequacy
and effectiveness. This assessment provides an on-going corrective action
system, as illustrated in Figure 11.1 of the QA program.
Plan
Take corrective action Implement
Figure 11.1 QA/QC Assessment
Consequently, the purpose of a quality assurance/quality control
plan (QA/QC) is to describe the activities to be used in assessing the
validity of installed CEM systems.
QA/QC activities involve both routine and periodic evaluation.
Historically, these activities have been performed by the source as part
of their own quality assurance program. Source QA/QC activities vary
from source to source. Source QA/QC activities are not required by law.
The only real QA activity required by law has been the Performance Speci-
fication Test (PST). It is within the PST that the monitoring system
must pass minimum criteria standards in order for the system to be "certi-
fied". These initial tests evaluated the performance characteristics of
the installed monitor to standard reference methods. It was the intended
purpose of these procedures to ensure reliable operation of a monitoring
system once it was installed on the source. The PST provided the regula-
tory agency information concerning the operation of the total CEM system
as compared to the Reference Method. As such, the PST was a quality
assessment check of the monitoring system. Likewise, the test provided
the source operator/owner of the CEM system a means of evaluating the
system to determine its applicability to that source environment. This,
too, was a quality assessment check. What was lacking, however, was a
continued check of the system after the PST. The PST is a one time
certification procedure involving both the regulatory agency and the
source.
11-1
-------
As CEMs became an integral part of the enforcement activities of
both EPA and State/local programs, it became imperative that some form
of continued evaluation of the monitoring system occur to ensure its
continued performance and reliability. This continued evaluation would
assist the EPA and the State Agency in establishing CEM long term perform-
ance and reliability as part of their data base. Consequently, QA/QC
activities involve both source and agency functions.
The main objective of this chapter is to present various elements as
possible components of a QA/QC program associated with three organizations.
They are:
o U.S. Environmental Protection Agency;
o Industry; and
o State Regulatory Agency.
11.2 U. S. EPA, PROPOSED APPENDIX F, PROCEDURE 1
On March 14, 1984, U. S. EPA proposed Appendix F, Procedure 1, address-
ing source quality assurance requirements as applied to "all CEMS installed
under a subpart that designates CEMs as the Method for showing compliance
with emission limits on a continuous basis. The regulation would apply
to subpart Da, 40 CFR Part 60 (electric utility steam generating units for
which construction is commenced after September 18, 1978). It would also
apply to other subparts which may be proposed before or after proposal of
Procedure 1, if the subpart requires the use of gas CEMS as the performance
test method on a continuous basis." The intent of the proposed rule is to
require source owners of gas CEMs to self-evaluate periodically the moni-
tor's precision and accuracy. The proposed rule requires the source owner
or operator to:
o Develop and implement a quality control program that includes
written procedures for key CEMs operations;
o Calculate monthly data precision for each CEM from daily
span checks; and
o Perfprm a quarterly accuracy assessment of each CEM.
The CEMs data accuracy is determined by either a relative accuracy
audit (RAA), utilizing Reference Methods (RM) as specified in the Perform-
ance Specification Test (PST) or a cylinder gas audit (CGA) utilizing gases
that have been certified by comparison to National Bureau of Standards
(NBS) Gaseous Standard Reference Materials (SRMs) or NBS/EPA approved gas
manufacturer's Certified Reference Materials (CRMs). If the inaccuracy
exceeds 25 percent using the RAA or +_ 15 percent using the CGA, the CEM
is "out-of-control." At this time, the source must take corrective
action to bring the system back into compliance.
The proposed rule was designed to assess the CEM's data precision
and accuracy on an established frequency. If, through the audit evalu-
ation, the data becomes questionable, then increased quality control
11-2
-------
quality improves to within acceptable limits. Consequently, the respon-
siblity of maintaining the CEM system within an acceptable range is sole-
ly upon the shoulders of the regulated facility.
Current regulations associated with continuous emission monitors
require .';,he source coerator to perform a daily zero and span check of
the monitoring system. The regulations are not specific under Subpart A
of the General Revision of 40CFR60 as to whether this daily check is to
be observed or recorded. The regulations do state, however, that if the
daily zero and span check exceeds the applicable drift limits as speci-
fied in the Performance Specification, then the source operator must
make appropriate adjustments to bring the continuous emission monitoring
system within the drift specifications. This is the extent of quality
assurance requirements associated with current regulations. Subpart A
of the General Provision of 40CFR60 state:
"...at all times, including periods of start-up, shutdown, and
malfunction, owners and operators shall, to the extent practi-
cable, maintain and operate only affected facility in a manner
consistent with good air pollution control practice..."
Consequently, the present regulations lacks requirements for:
o Periodic assessment of CEMs data precision and accuracy;
o Requirements when CEMs corrective action must be taken; and
o Requirements for defining criteria for "unacceptable data."
Proposed Appendix F, Procedure 1, covers gas continuous emission moni-
tors used to determine compliance with emission standards on a continuous
basis. This would initially covered Subpart Da sources - Standards of Per-
formance for Electric Utility Steam Generating Units for which construction
is commenced after September 18, 1978. The proposed regulation does not
apply to those Subpart of the regulations where CEM is used as a compli-
ance test method, but is not used to show compliance on a continuous basis
(i. e. smelters). The proposed regulation does not apply to sources where
CEM is required for O&M purposes, rather than for compliance determination
(i.e. NSPS Kraft pulp mills)* The proposed regulation, consequently, would
apply only to a very narrow population of the Subparts. This does not pre-
clude, however, state and local agencies from implementing many sections
of the proposed regulation on sources covered under the State Implementa-
tion Plans (SIP). Such regulatory vehicles as source permitting, consent
decrees, variances etc. have been used successfully in the past by state
and local regulatory agencies in implementing quality assurance require-
ments on regulated facilities.
The proposed regulation is divided into three major areas of concern
associated with installed continuous emission monitors. They are:
o Quality control activities;
o Quality assurance activities; and
o Reporting requirements.
11-3
-------
11.2.1 Quality Control (QC)
Quality control involves "those activities which will provide a
quality product." Appendix F, Procedure 1 addresses this by requiring
sources to develop a source specific quality assurance/quality control
program including written procedures for continuous emission monitoring
systems. Those activities which should be addressed in the QA/QC program
are:
o Calibration technique/frequency;
o Calibration drift determination and adjustment procedures;
o Preventive maintenance procedures;
o Data recording and reporting procedures; and
o Program of corrective action for malfunctions continuous
emission monitors.
These written procedures are routinely part of a source quality assur-
ance plan. The objective of a source quality assurance plan, involving
both quality assurance and quality control, is to delineate the activities
necessary to ensure that emission monitoring data are complete, representa-
tive, precise and accurate. The quality assurance plan provides the frame-
work for implementing quality assurance and quality control activities.
Quality control procedures ensures that the data required is precise and
accurate within established limits and if found outside those limits, pro-
vides procedures for corrective action to bring the system back within
limits.
11.2.2 Quality Assurance (QA)
Quality Assurance activities are addressed in routine assessment of
CEM data involving instrument precision and accuracy.
Instrument precision is determined each calendar month using span
drift data from daily span checks. Each monitor is challenged with a cal-
ibration standard of known concentration at a span level (50-100% of span
valve) on a daily basis. The difference between the actual concentration
of the calibration standard and the concentration indicated by the monitor
is calculated daily by the following equation:
di -
XT
11-4
-------
Where: Y-j = monitor indicated concentration from the i-th pre-
cision checks; and
Xi = known concentration of the precision check reference
used for the i-th precision check.
For each month, the monthly average percent difference (dj) and the
standard deviation of the percent difference (Sj) is used to calculate the
upper and lower 95 percent probability limit [(DPI) and (LPL)]. Mathematic-
ally, this can be represented by the following equation:
UPL = "dj + 1.96 Sj
LPL = dj - 1.96 Sj
The UPL and LPL are reported on the quarterly Data Assessment Report
(DAR).
As proposed, Appendix F, Procedure 1 assesses accuracy on a periodic
basis, of an installed continuous emission monitor, by utilizing a relative
accuracy audit (RAA) and a cylinder gas audit (CGA). The accuracy assess-
ment is performed within the first two months of each calendar quarter.
The procedure for the RAA is the same as for the relative accuracy
test described in the applicable performance specification test require-
ments, except fewer sets of measurements would be required. For Kraft
pulp mills, this would involve Federal Reference Method 16 or Federal
Reference Method 16A. The relative accuracy (RA) would be calculated by
the following equation:
DA . . * led
RA = RM
Where:
RA = Relative Accuracy, % average;
|"d| = Absolute value of the mean difference between
reference method and continuous emission monitor
value over a series of tests;
|CC| = Absolute value of the confidence coefficient at
the 2.5 percent error;
RM = Average Reference Method value over a series of
tests.
Every other calendar month, a cylinder gas audit (CGA) is performed
on the installed continuous emission monitor in lieu of the RAA . The
CGA is performed by challenging the monitor (both pollutant and diluent)
with an audit gas of known concentration at two points, as illustrated
in Table 11.1.
11-5
-------
TABLE 11.1
CYLINDER GAS AUDIT VALUES
Audit Point
1
2
Audit Range
Pollutant
Monitor
20 to 30* of
Span valve
50 to 60%
of Span
valve
Diluent Monitor
CO?
5 to 8%
10 to 14%
0?
4 to 6%
ft to 12%
The monitor should be challenged at each point for a sufficient time
to assure equilibrium of the monitoring system. As good practices would
dictate, the gas should be introduced as close to the probe tip as possi-
ble and pass through all active components of the monitoring system.
Once again, the monitor response is compared to the gas cylinder concen-
tration to calculate a percent difference by the following equation:
Yi - Xj X100
d = Xj
Where:
d = % difference;
Y-J = monitor indicated concentration from the gas cylinder
audit point; and
X-j = known concentration of the gas cylinder audit point.
Provisions are provided within proposed Appendix F, Procedure 1,
addressing corrective action requirements for both span drift and
quarterly relative accuracy audits. Corrective action is required if:
o Span drift exceeds "twice" the applicable monitor
drift limit for 5 consecutive span checks ...CEM is
"out of control." If the CEM is "out of control", then:
(a) Take corrective action (C/A); and
(b) Within 2 weeks of C/A, audit CEMs with RAA or CGA
o Inaccuracy from quarterly RAA exceeds 25% or CGA exceeds +
10% ...CEMs is "out of control." If the CEM is "out of
control", then:
(a) Take C/A: and
(b) Within 2 weeks of C/A, audit CEMs with RAA or CGA.
In addition, data is determined unacceptable if:
o Data collected following "out of control" condition may
not be used as part of minimum daily requirement: and
o Any single day data when span drift exceeds 4 times the
applicable monitor drift limit may not be used as part of
minimum daily requirement.
11-6
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11.2.3 Reporting
At the end of each quarter, the monitor precision probability limits
for each calendar month and accuracy assessment results involving either
a RAA or a CGA determination are reported. In addition, the proposed
regulations require reporting of excessive span drift and inaccuracy de-
termination along with corrective action taken to bring system back under
control. This information is reported on a Data Assessment Report (DAR).
An example format is given in Figure 11.2.
11.3 SOURCE QUALITY ASSURANCE PROGRAM
11.3.1 Introduction
The primary objective of a source quality assurance program for
CEMs is to ensure that all data collected and reported are meaningful,
precise and accurate within a stated acceptance criteria. The program
should be strong enough to ensure strict adherence to all established
procedural requirements, but flexible enough to allow continuing evalua-
tion of its adequacy and effectiveness. The objectives, therefore, of a
source quality assurance program are to:
o Provide routine performance of personnel and/or equipment;
o Provide for prompt detection and correction of conditions
that contribute to the collection of poor quality data; and
o Collect and supply information necessary to describe the
quality of the data.
To accomplish the above objectives, a quality assurance program must con-
tain the following components:
o Routine training and/or evaluation of operators:
o Routine monitoring of the variables and/or parameters which
may have a significant effect on data quality;
o Development of techniques to detect defects;
o Development of methods written procedures to qualify data; and
o Action strategies to increase the level of precision in the
reported data and/or to detect equipment defects or degra-
dation.
After a QA plan is written and implemented, procedures within the
plan should point out necessary corrective action which, in effect,
revises the plan. This would provide an on-going corrective action
system.
11-7
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Figure 11.2
Data Assessment Report (DAR)
Continuous Emission Monitoring (CEM)
for
Total Reduced Sulfur (TRS)
Period Ending Date Year
1.0 General Information
1.1
1.2
1.3
1.4
1.5
1.6
Company Name
Plant Name
Source Unit No.
Monitor Location
Monitor Type/Model No.
Monitor Serial No.
2.0 Quality Assessment
271Precision (for each month in quarter)
2.1.1 Month of Quarter
2.1.2 95 Percent Probability Limit
2.1.2.1 Upper (UPL)
r 2.1.2.2 Lower (LPL)
00 3.0 Accuracy (fill in either 3.1 or 3.2)
3.1 Relative Accuracy Audit (RAA)
3.1.1 Date of Audit
3.1.2 Reference Method (RM) Used
3.1.3 Average RM Value
3.1.4 Absolute Value of Mean Difference |dj
3.1.5 Absolute Value of Confidence Coefficient |CC|
3.1.6 Relative Accuracy (RA), percent
Audit Point 1 Audit Point 2
(Low Cone.) (High Cone.)
3.2 Cylinder Gas Audit (CGA)
3.2.1 Date of Audit
3.2.2 Cylinder ID#
3.2.3 Cylinder Certification Date
3.2.4 Certification Method
3.2.5 Cylinder Concentration
3.2.6 Monitor Response
3.2.7 Difference, percent
-------
Data Assessment Report (continued)
4.0 Corrective Action
4.1 Excessive Span Drift
4.1.1 No. of Times Monitor was "Out-of-Control"
4.1.2 Corrective Action Taken
4.1.3 Results of Audit After Corrective Action
4.2 Excessive Inaccuracy
4.2.1 Corrective Action Taken
4.2.2 Results of Audit After Corrective Action
5.0 Authority
5.1 Name
5.2 Title
5.3 Address
5.4 Telephone Number
5.5 Signature
-------
The development of a quality assurance program deals not only with
daily zero/span checks, quarterly audit techniques on precision/accuracy,
but also involves the development and implementation of four (4) general
categories. They are:
1. Management;
2. Measurement;
3. Documentation; and
4. Statistics.
Management; The first step in developing a Quality Assessment/
Quality Control program is the development of a written policy stating
the objectives of quality assurance as part of the management effort. In
addition, administrative procedures applicable to all measurement systems
must be developed. The quality assurance policy and objectives should be
applicable to pending EPA regulatory quality assurance procedures.
Quality assurance reports and quality assurance graphics addressing data
quality of each CEM system should be routinely summarized for internal
distribution by the QA coordinator. Cost related items should be reviewed
and changes made to obtain high quality data for the least cost.
Measurement: The second quality assurance/quality control program
development step is the preparation of a Quality Assessment document that
illustrates step-by-step procedures for CEM system start-up and calibra-
tion, internal CEM QA checks (daily, weekly, monthly, etc.), performance
audits, system audits, calibration standards certification, CEM certifi-
cation, data validation, maintenance (non-routine and scheduled) and
intralaboratory quality assessment activities. Appendix F, Procedure 1
QA activities should be an integral part of the QA document.
Documentation: A document control system should be an integral part
of the quality assurance plan. This involves proper identification and
noted revisions of all quality assurance documents associated with the
CEM system. All log books should be numbered and identified as part of the
document control system. Users should maintain the following log books
to document all QA/QC activities associated with the CEM system.
o Monitor Log Book;
o Procurement Log Book;
o Calibration Standards Log Book;
o Laboratory Log Book;
o Excess Emission Log Book;
o Daily Monitor Log Book; and
o Periodic Audit Log Book.
The document control system should also maintain records on all monitoring
equipment (manufacturer's serial number, location), spare parts inventory,
all components and their status (repair shop, manufacturer or discarded)
and QA audit standards (NBS traceable, recertified date). A document
distribution system should be established in order to provide the latest
written procedures to all concerned personnel.
11-10
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Statistics: The statistics category includes the tasks of data reduc-
tion and calculation in order to express the data in units of applicable
standard. Statistics are essential to any adequate quality assurance
program because they provide information concerning monitor performance
(short and long term) and data validity. Corrective action begins with
statistical evaluation.
From the statistical evaluation of the monitoring data, charts can be
developed. These charts are used to detect long term trends and establish
"out of control" criteria limits. Confidence limits are identified on
the control chart so that future data values can be plotted to detect any
significant changes from past performance.
11.3.2 Source Quality Assurance Program
A source specific quality assurance program can be divided into two
major functional groups:
o Quality Assurance o Quality Control
Quality control has historically been defined as "those activities
which will provide a quality product", whereas quality assurance is "the
system of activities to provide assurance that the quality control pro-
gram is performing adequately." Duality control involves routine checks
included in normal internal procedures. Quality assurance may be viewed
as "external" quality control involving system audits, statistical evalu-
ations and other functions which are outside the normal routine functions.
Figure 7.3 illustrates the different activities associated with each
major functional group.
| Quality Assurance Program |
TQuality Assurance^
1
[Quality Control
[Precision!
o Daily Zero/Span
Check
o Control Charts
Development
[Accuracy |
o Quarterly Audits
o Control Charts
Development
[Improvement f | Control |
o Corrective
Action
Procedures
Determination of o Audit Samples Generated
Monitor "Out-of- by Gas Cylinders/Permeation
Control" Tube System
o Relative Accuracy
Audit (RAA)
o Cylinder Gas
Audit (CGA)
o Calibration
of CEMs
o Calibration
Drift Deter-
mination
o Preventive
Maintenance
o Data Recording
and Reporting
o Malfunction
Determination
Figure 11.3. Source Specific Quality Assurance Program
11-11
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The purpose of developing and implementing a source quality assur-
ance (QA) plan is: (1) to assure acceptable precise CEM data quality,
and (2) to assure acceptable CEM data recovery and system operating avail-
ability. The draft version of EPA's Appendix F to 40 CFR 60, provides
an outline of requirements for CEM Quality Assessment Plans for facili-
ties operating monitors as compliance measurement methods. Appendix F
requirements not only define data precision, accuracy, and system avail-
ability goals, but also specify that comprehensive operation and maintenance
(Q&M) and quality assurance/quality control (QA/QC) audits and measurements
be conducted. The requirements further stipulate corrective action and
alternative measurement methods when the QA/QC checks indicate that the
QA and availability goals are not achieved. A QC program defining calibra-
tion, maintenance, and corrective action must also be developed.
Consequently, the requirements of Appendix F dictate documentation
of all phases of a company's QA Plan. Included are all QA/QC, Q&M, and
recordkeeping activities. The QA Plan should also address other activi-
ties such as certification testing, QA Plan organization, and personnel
responsibilities. A standard operating procedures (SOP) manual defining
all activities, responsibilities, communication, and documentation pro-
cedures should be developed to serve as the working reference of the
QA Plan.
Following is a discussion of a typical QA Plan applicable to monitor-
ing total reduced sulfur (TRS) from Kraft pulp mills incorporates all the
requirements of Appendix F. The QC program defines and documents the O&M
(preventative and repair) procedures. Additional elements of the plan
described in this chapter include an organization plan which identifies
the responsibilities for QA Plan activities and distribution recording of
results. The QA Plan should identify when the O&M and QA/QC activity
results require corrective action or alternative monitoring methods, and
personnel responsible for implementation of these activities.
As discussed earlier, a source quality assurance program involves
a written document containing all aspects of the continuous emission
monitoring program. It defines organization and responsibility, QA/QC
activities, maintenance and corrective action procedures and other acti-
vities associated with the complete monitoring program. A typical out-
line of a document addressing a source quality assurance program is illu-
strated below.
EXAMPLE
SOURCE QUALITY ASSURANCE PROGRAM
WRITTEN DOCUMENT
1.0 Introduction
2.0 Quality Assurance Overview
2.1 General
2.2 Specific
3.0 Organization and Individual Responsibility
11-12
-------
3.1 Personnel Assignments and Responsibilities
3.1.1 Organization
3.1.2 Program Management
3.1.3 Field Operations
3.1.4 Laboratory Operations
3.1.5 Data Management
3.2 QA Responsibilities
3.2.1 Quality Assurance Coordinator
3.2.2 Field Personnel
4.0 Quality Assurance/Quality Control
4.1 Quality Assurance
4.1.1 Activities
4.1.2 Personnel Responsibilities
4.2 Quality Control
4.2.2 Activities/Corrective Action
4.2.1 Recordkeeping
5.0 Data Handling, Validation and Reporting
5.1 Data Logistics
5.2 Data Handling and Statistical Analysis
5.3 Control Charts
5.4 Data Validation Criteria
5.5 Data Reporting
5.6 Data Forms
6.0 Operation and Maintenance Program
6.1 General
6.2 Preventive Maintenance
6.3 Corrective Maintenance
6.4 Spare Parts Inventory
6.5 Maintenance Documentation
7.0 Quality Assurance Audits
7.1 Self Auditing
7.2 Corporate Auditing
8.0 Recordkeeping and Reporting Requirements
11.3.2.1 Introduction -
The introduction should contain language affirming corporate policy
to operate and maintain its facilities in strict adherence to all appli-
cable environmental rules and regulations. Likewise, a committment to
obtaining all data to demonstrate necessary activities dealing with the
continuous emission monitoring system are being performed to ensure
that all environmental measurements are of high quality.
11.3.2.2 Quality Assurance Overview -
Quality Assurance depends on the completion of all activities
stated in the quality assurance document. The objective of the quality
assurance document is to delineate those activities necessary to ensure
that emission monitoring data are complete, representative and of deter-
mined precision and accuracy. The document addresses activities as
responsible individuals, data integrity, documentation, training programs
and corrective action activities.
11-13
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11.3.P.3 Organization and Individual Responsibility -
Historically, the management of quality assurance programs have in-
corporated, at a minimum, three organizational levels. Level I, Manager
of Environmental Engineering, is responsible for the implementation of
and continued support to the QA program. Company QA policy, administrative
support, local assistance, development of strategies, system analysis,
promulgation of permit requirements and interface between source and
regulatory agencies are some of the other functions of Level I.
Level II, Quality Assurance Coordinator, is responsible for the
implementation of the quality assurance program. The Quality Assurance
(QA) Coordinator develops and carriers out the Quality Control Programs,
including statistical procedures and techniques, which will help the
source meet agency requirements. In addition, the QA coordinator schedules
and performs non-routine audits and quarterly audits, evaluates new QA
procedures for applicability, evaluates data quality and maintains related
quality control charts and records. It is the QA coordinator's responsi-
bility to respond to quality control problems and coordinate those activi-
ties with Level I. In addition, the QA coordinator should prepare monthly
and quarterly reports to summarize:
o Reliability of the CEM system and its components;
o Quality of data generated;
o CEM problem areas;
o Corrective actions taken and their results; and
o Quarterly excess emission reports.
This information is then submitted to Level I, Manager of Environ-
mental Engineering, for approval and distribution.
Level III involves the CEM operator who ensures that good quality
data is obtained from the CEM system.
Daily quality assurance zero/span checks with associated documen-
tation, preventative maintenance procedures, sample collection, and
data reporting all fall within the responsiblity of the CEM operator.
Table 7.2 summarizes the quality assurance elements associated
with each level of responsibility.
11-14
-------
TABLE 11.?
RESPONSIBILITIES OF LEVELS I, II. AND III
IN A SOURCE QA/QC PROGRAM
Level I and Level II Level II and III Level III
Supervisor & Supervisor & Operator
QA Coordinator Operator
o Document Control/ o Corrective o Preventive
Revisions; Action; and Maintenance;
o OA Policy & Objective; o Procurement o Data Reporting;
o Organization; Quality Control; o Calibration; and
o Quality Planning; o Document Control.
o Training;
o Ouality Cost;
o Interlaboratory
Testing;
o Audit Procedures;
o Data Validation; and
o Quality Reports to
Management.
A table should be established identifying CEMs program participants,
name, title, address and telephone number along with responsibilities.
An example is given in Table 11.3.
A key element to the successful implementation of the CEM OA Plan
is the organization of personnel and activities. The SOP manual should
define all OA/QC, maintenance, data reduction, documentation (record-
keeping), and communication activity responsibilities and identify the
personnel (by job category and by name) assigned each of these respon-
sibilities.
A matrix of all personnel and activities associated with each major
element of the plan (Q&M, OA/QC, data reduction) shall be prepared. With-
in this matrix, each individual activity should have associated documen-
tation and communication responsibility defining what information is to
be documented, where it will be filed, and who must be informed, verbally
or in writing, of the results of the activity.
The mechanisms which initiate each activity should be identified with-
in the matrix as scheduled as well as within the malfunction mechanisms.
The frequency of scheduled activities such as preventative maintenance and
QA audits should be specified. Malfunction initiated activities such as
repair maintenance, OA audits following maintenance, and operating alterna-
tive measurement methods should be ordered or requested. The requesting
person or organization should be specified within the matrix.
In addition, flow charts should be constructed indicating "flow"
of information between individuals within the CEM program. An example
of a "typical" flow chart is given in Figure 11.4.
11-15
-------
TABLE 11.3
CLEAN PAPER COMPANY
SOURCE QUALITY ASSURANCE PROGRAM
PROGRAM PARTICIPANTS AND RESPONSIBILITIES
Level
CEM Program
Participant
Name, Title, Address
Telephone No.
Responsibility
Plant Manager
Mr. Bob Timson
Clean Paper Company
Pine Bluff, North Carolina
(919) 877-3611 (ext. 923)
o Responsible for
total plant
operation;
Plant Operations
Supervisor
Environmental
Engineering
Mr. Jim Limb
Clean Paper Company
Pine Bluff, North Carolina
(919) 877-3611 (ext. 813)
Mr. Jerry Figure
Clean Paper Company
Pine Bluff, North Carolina
(919) 877-3611 (ext. 714)
o Data review and
verification;
o Maintain com-
pliance status
(modify operations
if necessary);
o Ensures compliance
with environmental
regulations;
Directs activities
over engineering
department, including
implementation of
QA program;
-------
TABLE 11.3 (continued)
CLEAN PAPER COMPANY
SOURCE QUALITY ASSURANCE PROGRAM
PROGRAM PARTICIPANTS AND RESPONSIBILITIES
CEM Supervisor
Mr. Tom Electron
Clean Paper Company
Pine Bluff, North Carolina
(919) 877-3611 (ext. 622)
Responsible for all
operation and main-
tenance activities for
installed CEMs;
Responsible for imple-
mentation of the QAS
Program;
May also be respon-
sible for Quality
Assurance activities;
"2
CEM-QA Coordinator
Mr. Pete Exact
Clean Paper Company
Pine Bluff, North Carolina
(919) 877-3611 (ext. 561)
Responsible for all
QA source activities
associated with the
CEM program;
Implements and performs
weekly, monthly, and
quarterly QA checks;
III
CEM Instrument
Specialist
Mr. Scott Work
Clean paper Company
Pine Bluff, North Carolina
(919) 877-3611 (ext. 400)
o CEMs maintenance and
calibration;
o Maintain instrument
logs;
o Report instrument
problems.
-------
00
QA/Audlt Results
JT
1
1
i
•Aud1t/OJ
(Feed F<
I
I
\ Reports ENVIRONMENTAL
intard) ENGINEERING
1^ MANAGER
-
SOURCE MONITORING
DIRECTOR
QA Coordinator
JA^Audlt Results (Feedback)
H
1
1
1
Check Calculations 1 _
1 Coopare Results 1 T
Kith
CEM/QA SOURCE TESTING CEN Dati
QA Engineer ^
DATA SERVICES
Engineer
CEH Data J
"^ QC Engineer
1^ Sanple Analysls/Prellorinary Calculattc
T Audit Saopjes
1
AMBIENT
MONITORING
DIRECTOR
Laboratory Services
Laboratory Supervisor
1 A
1 1
J
Figure 11.4. Personnel Flow Chart Within Source QA Program
-------
TABLE 11.4
QA/OC ACTIVITIES ASSOCIATED
WITH MONITOR PRECISION AND ACCURACY
OA/QC Activities
Pyrpose
Limits
Corrective Action
Relative Accuracy
Assess relative accuracy
Cylinder Gas
Check -1
(Single Point)
Cylinder Gas
Check -2
(Multipoint)
System Appraisal
Assess calibration error
Assess response time
Assess precision
Assess calibration error
Assess Calibration error
Walkthrough
Check
Assess general condition
of gas monitoring systems
20%
+_ 5%
15 minutes
5%
5%
5%
No readily
apparent
problems
1. CEM O&M group repairs as required.
2. CEM Data Services evaluates effect
on data.
3. CEM QA group performs repeat audit
(RAA) after corrective action.
1. CEM O&M group repairs as required.
2. CEM Data Services evlauates effect
on data.
3. CEM QA group performs repeat audit
(CGA-1) after corrective action.
1. CEM O&M group repairs as required.
2. CEM Data Services evaluates effect
on data.
3. CEM QA group performs repeat audit
(CGA-1) after corrective action.
1. CEM O&M group repairs as required.
2. CEM Data Services evaluates effect
on data.
3. CEM QA group performs repeat audit
after corrective action.
1. CEM OA Coordinator establishes need
for and implements appropriate
correction action.
2. CEM OA Coordinator may initiate
another appropriate audit.
-------
11.3.2.4 Quality Assurance/Quality Control
As illustrated in Figure 7.3, quality assurance/quality control
functions are performed to enable the source to determine the precision
and accuracy of an installed CEM system. This may involve a simple
walkthrough check, observing gauges etc. or it may involve a complete
relative accuracy check. The performance of each activity enables the
source operator to evaluate the system and, if need be, perform a higher
level of QA/QC checks if deficiencies are note. Table 7.4 lists the
various QA/OC activities involving monitor precision and accuracy.
The walkthrough and system appraisal check are the least time consum-
ing functions of a source QA/QC program. Gauges, valves, temperature set-
tings etc. are recorded on the daily checklist and compared to "baseline"
values. The general condition of the CEM system is assessed and compared
to historical data. If deficiencies are observed, appropriate action is
taken.
The most common QA/OC activity performed on a source CEM system is
the daily zero/span check. The daily zero/span check allows the operator
to challenge the monitor with a known concentration of gas and observe the
monitor response.
The results of the daily zero/span calibration check should he
recorded on the daily checklist. The calibration check is an excell-
ent indicator of its proper operation. The individual performing the
daily maintenance should be aware of the system operation as demonstrated
by the calibration checks. Maintenance performed without reviewing the
instrument response to daily calibration is only partially effective. As
daily calibration values are recorded, trends develop and the maintenance
technician becomes familiar with the expected operating parameters for
the day. Results outside those expected operating parameters should
indicate not only the problem but the probable cause of that problem.
The daily calibration values provide a starting point for troubleshooting
wherever a problem is indicated.
11-20
-------
From the zero and span checks, control limits can be calculated
(95% probability limits) and recorded on a monitor-specific control
chart, as illustrated in Figure 11.5.
70
60
50
~40
Q
Ul
DC
UJ
Q
o:
o
UJ
K
512
10
MAY
JUNE
JULY
AUGUST
SEPTEMBER
Figure 11.5. Control Chart for Daily Zero/Span Checks
11-21
-------
As discussed in Appendix F, when the limits have been exceeded, a
multipoint calibration, using span gases should be initiated. The pro-
cedures/data forms used in the multipoint check should be part of the
Standard Operating Procedure (SOP) Manual.
Each CEMS analyzer must be calibrated at least every 24 hours.
Currently, the only two options for calibrating a TRS CEM system are
gravimetrically certified permeation devices and cylinders of TRS that
have been analyzed. The accuracy of those two methods of calibration
will reflect directly upon the accuracy of the data generated, and have
been discussed fully in Chapter 6.0.
If the calibration is performed by permeation devices, a number of
parameters are important to the accuracy of calibration. One of the most
important is the determination of the emission rate of the permeation
device. The weight loss is normally determined by weighing the devices
routinely for a period of four to six weeks, during which time the devices
are maintained at a constant temperature to ensure a constant permeation
rate. The weight loss of the permeation device should be determined over
a period of time such that the plot of weight loss versus time should give
a slope with a confidence coefficient of greater than 95 percent. This
normally results in an inaccuraacy of less than +_ 2 percent. If the source
does not wish to determine weight loss, then purchase of a certified permea-
tion tube from several manufacturers is available.
The permeation rate of a device varies significantly with temperature.
A 1°C change in temperature of the permeation device will affect the emis-
sion rate by approximately 10 percent. It is, therefore, necessary to
maintain the temperature of the permeation device during use at the same
temperature of calibration (_+ 0.1°C) to ensure the emission rate will be
constant (+ 2 percent) under normal circumstances.
Assuming a constant temperature, the permeation rate (mass/time) is
constant. The concentration of gas varies inversely and linearly with the
gas flow across the devices. Precise flow control is normally maintained
by means of mass flow controllers or precision rotameters with pressure
regulation.
The most common method of calibrating TRS continuous emission monitor-
ing systems is the use of hydrogen sulfide in nitrogen. The concentration
of HgS in nitrogen should be in the range of the analyzer (approximately
80 percent of span) or a higher concentration that requires dilution before
use. Most commonly, a high concentration cylinder (1,500 to 3,000 ppm) is
purchased and diluted approximately 100 fold for daily calibration. The
advantage of using a high concentration gas is that only a small amount
is required to calibrate the system and the gas will last much longer. The
disadvantages of using a high concentration gas is that an accurate dilu-
tion system is required to continually provide the same dilution. When
high concentration gases are used, not only must the user be concerned
with the accuracy of the concentration in the cylinder, but also the
accuracy of the dilution.
11-22
-------
11.3.2.5 Data Validation and Reporting -
Criteria for data invalidation have been addressed in drafts of
Appendix F - Procedure 1, Quality Assurance Requirements for gas CEM's, and
it is likely that some version of these criteria will be retained when
Appendix F is promulgated in its final form. If this proves to be the case,
invalid data will bs defined in relation to two monitor conditions:
(1) Breakdown; and
(2) "Out of Control".
Excessive span drifts and excessive errors in relative accuracy are
cited as causes of monitor breakdown and out of control. Accordingly, the
quality assurance plan should provide for identification of these criteria.
Many monitors and data recording systems incorporate aids to data
validation such as flagging operational parameters and monitor calibrations
which are outside acceptable limits. The CEM operator should check all
flagged items daily for reasonableness and communicate with the quality
assurance coordinator on questionable items.
Control charts for monitor calibration should validate monitor pollu-
tant results and should be checked weekly by the QA coordinator.
To validate the Data Acquisition System (DAS) calculations of
results, 10% of the first month's strip chart monitor data should be
reviewed and evaluated. If the results compare within 3% of the DAS, the
DAS should be considered correct. On a continuing basis, 5% to 10% of the
overall data output of each CEM system should be evaluated in this manner.
11.3.2.6 Operation and Maintenance Program -
A comprehensive operation and maintenance (O&M) program coupled with
routine quality assurance (QA) checks are vital elements of a successful
CEM program. They provide the necessary documentation to evaluate the
precision, accuracy and representativeness of the source measurement
system. The gathering and processing of invalid data is historically
coupled with improper operation and/or lack of maintenance of CEM systems.
This, in turn, leads to excessive monitor downtime. Under many Subparts
of 40CFR60, a specified minimum data capture is required. Consequently,
a well documented O&M/QC program serves both industry and regulatory
agencies.
The appropriate procedures for a O&M/QC program are monitor-
specific and site-specific. The program should include the following
basic elements:
o Documentation of instrument system operating parameters
using standardized forms and control charts;
o Daily zero and span calibration checks for confirming that
the instrument calibrations are maintained within control
limits;
o Validation of data reduction process from raw data
collection through reporting;
11-23
-------
o Determination of the accuracy and precision of
collected data;
o Performance of quarterly independent audits; and
o Periodic maintenance procedures and practices.
Appropriate quality assurance checks must be monitor specific and
source specific. Documentation should involve a step-by-step approach
to the daily quality assurance checks with instructions for action to be
taken if the appropriate response is not obtained. At a minimum, routine
quality assurance checks should address the following topics:
o Set of procedures for monitor specific daily zero/
span function;
o Guidance for corrective action;
o Control charts; and
o Hocumentation involving monitor log book for routine
entry and routine/major maintenance entries.
Figure 11.6 illustrates a typical source specific troubleshooting
guide, while Figure 11.7 illustrates a source trouble report/work
request form.
The same individual who performs the daily zero/span checks should
be responsible for routine adjustments te the monitoring system when
discrepancies are noted. Long-term monitor performance should deter-
mine the appropriate frequency of various QC activities. Adequate
records must he maintained to document these activities.
It is essential to develop monitor and site specific instructions
for the routine quality assurance activities required by both manufac-
turer and Appendix F to ensure proper operation of the CEM system.
Quality assurance activities of zero/span checks are to be performed
daily, as specified in the Standard Operational Procedure Manual (SOP).
-------
Troubleshooting Guide
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-------
TROUBLE REPORT/WORK REQUEST
Ball PoUH P«n • PT«M I
a MM
a OnOnMr
STATW
Q i. m
a a.
a x
a *
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a &
a r.
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PART 111 JOB cavipLEnaw REPOHT
/C^AA Ext ISS I g>»AS
Figure 11.7. Source Trouble Report/Work Request
11-26
-------
11.3.2.6.1 Routine Maintenance -
Periodic checks of the CEMS and its operation are mandatory. Even
though a system may provide excellent quality data initally, without
routine maintenance and system checks, the quality of the data will un-
doubtedly degenerate with time.
Maintenance checklists are one of the tools management can use to
ensure that the proper preventive maintenance is being completed. The
checklist should provide a place to record all settings and indicators
of proper operation, indicate the items to be checked and provide a place
to document repairs and replacement of parts. The checklist should list
daily, weekly and monthly checks of various maintenance items, and it
should be system specific because each system will require slightly
different gauge settings and meter readings for proper operation. The
proper recording of maintenance items provides a history to correlate
outages and potential problem areas. Table 7.5 illustrates an example
of a source QA maintenance timetable.
11.3.2.6.2 Preventive Maintenance -
The Operation and Maintenance section of a quality assurance
program should contain the following:
o A concise, simplified trouble shooting guide and diagnostic
chart to assist operators in identifying monitor problems;
o Established verbal and written lines of communication to
assure prompt notification to maintenance, physical plant
and environmental management of monitor operating problems;
o A maintenance request form with routing priority assignment,
and job completion follow-up and failing to assure management
awareness of monitor operational status.
o An on-going training program to ensure that the maintenance
staff is technically capable of instrument repair;
o Develop a spare parts inventory and stock replenishment program
based on suppliers' recommendations and available information on
likely modes of failure; and
o Review major repair and parts supply services available from
vendors, parts distributors, repair centers, etc. and implement
the best available.
Table 11.6 illustrates a CEM preventative maintenance guide.
11.3.2.7 Quality Assurance Audits -
Quality assurance audits are independent checks made by the auditor
to evaluate the quality of data generated by the total monitoring system
(sample collection, sample analysis and data processing). These audits
are performed independent from and in addition to normal quality control
11-27
-------
TABLE 11.5
SOURCE QUALITY ASSURANCE PROGRAM
TOTAL REDUCED SULFUR
MAINTENANCE TIMETABLE
Activity/ Checks Frequency
Calibration System Check
Permeation Bath Temperature Check
Strip Chart Paper Check/Inking
Printer Paper and CRT check
Hoses, Gauges and Valves
Flowmenter Checks
S02 Scrubber Check
Oxi di xing Cell and Sample Line Heat Check
Sample Line Pressure
GC Oven Temperature
Calibration Gas Pressure/Flowrates
Permeation Tube
Sample Gas Flow Rates
Condenser Water Temperature
Analyzer/Dilution Air Check
Data Processor Maintenance
Sample Dew Point
Voltage Checks
Service Sample/Purge Pump
Vaporizer Filter
Probe Inertial Filter
Charcoal in Clean Air Supply
Replace Filters
Vacuum Pump Oil
Vacuum Pump Diaphragms
Vacuum Pump Disc Valves and Gaskets
Sample Interface Enclosure
Gas Connections
Sample Transport Lines
Recorder Maintenance
Zero Air System Check
Daily
X
X
X
X
X
X
X
X
X
X
X
Weekly
X
X
X
X
X
X
X
Montlhly
X
X
X
X
X
X
X
Quarterly
X
X
X
X
X
X
X
X
Semi -
Annually
X
Annually
X
00
-------
TABLE 11.6
EXAMPLE RECOMMENDED PREVENTATIVE MAINTENANCE SCHEDULE
STI TRS CEM SYSTEM
07:30:15 JULY 1 1984
RECOMMENDED PREVENTATIVE MAINTENANCE SCHEDULE
DAILY VALUE/CHECK INITIALS
1. Check 0;:i diner temperature - 150O F •*•/- 5O
2. Checl- Dilution Control pressure gauges:
a. Sample? pressure - 20 PSTG _ _
b. Dilution air pressure - 3O PSIG
c. Calibration gas pressure - 3O PSIG _ 2. ~
d. Calibration dilution air pressure - 3O PSIG _ _
3. Check sample bypass flow meter - 1.5 1/min
4. Liquid level in SO2 scrubber water reservoir.
Fill within one half inch of top.
5. Check SCI2 backflush pressure gauge - 3O PSIG
6. Check air dryer indicator column - deep blue
7. Checl- air dryer outlet pressure - 60 PSIG
8. Check sample pump outlet pressure - 3O PSIG
9. Check steam pressure gauge at probe - 25 PSIG
10. Check sweep air pressure in probe box - 10 PSIG
11. Check calibration report - within limits _ Z"
12. Check printer paper ~
Weekly
1. Chect sample Dcwpoint at bypass flowmeter vent. (Sample dewpoint
will be approx. 10 degrees F. greater than the dewpoint of the inst.
air) Maintenance on the Sampling or Dry air systems is indicated if
the sample dewpoint js greater than -15 degree F. _ _
2. Check calibration gas cylinder pressure. The H2S cyTrnBer must 5e ~~
replaced when the1 pressure is below 3OO PSIG
Monthly
i. Change the vapciri r-or filter
2. Change the inert i al filter ZZ_Z Z_ _Z ~Z_Z
3. Clean the probr> erluctor
4. Repack the 5O2 Bcribber columns Z
5. Checl the calibration gas flow rates and enter the new~computea vaTue
into the? computer
6. Visual inspection o-f the Protar>/Condi 11 oner Ass.
Quarterly
1. Change t.<-impio pump diaphragms
2. Change sample* pump disc valves and gasket
3. Change *O* r i nrj seals on probe? barrel connectors
This preventive maintenance schedule may not apply to all TRS CEM systems.
11-29
-------
checks by the system operator. They provide an independent means for
determining the precision of the reported data, the adequacy of the mon-
itoring operation and maintenance procedures, and thp effectiveness of
the quality control system. Both announced and unannounced audits should
he scheduled. The audits provide a routine quality control check on the
monitoring system and a quantitative performance evaluation to determine
compliance with monitoring regulations and emission limitations.
11.3.2.7 1 Dynamic Audit -
Proposed Appendix F, Procedure 1, specifies relative accuracy audits
every other quarter and cylinder gas audits quarterly. Specific gas con-
centrations are specified with appropriate actions required if excessive
inaccuracy occurs. Quarterly audits are conducted in order to assess the
accuracy of the CEMs in accordance with the provisions of Appendix F,
Procedure 1. The CEMs should be audited at two audit points according to
the following schedule:
Audit
Point
1
2
Audit Range
Pollutant Monitor
20 to 30% of monitor
calibration full scale
50 to 60% of monitor
calibration full scale
Diluent Monitor
C02 02
5 to 8% 4 to 6%
by volume by volume
10 to 14% 8 to 12%
by volume by volume
Only audit gases that have been certified by comparison to National Bureau
of Standards (NBS) gaseous Standard Reference Materials (SRMs) or use of
gases that have been certified by EPA Traceability Protocol No. 1 should
be used as part of the quarterly audit program.
The performance audit procedures are monitor specific to qualify and
quantify the validity of the CEM system. For the gas cylinder audit, the
percent difference is calculated and reported by the Quality Assurance
Coordinator to the Manager, Environmental Engineering.
For the Relative Accuracy Audit (RAA), the relative accuracy is
determined by adding the absolute value of the mean difference between
the monitor and the reference method plus the 2.5% error confidence
coefficient divided by the Reference Method.
11.3.2.7.2 Federal Reference Method 16 -
Federal Reference Method 16 can be used as a quality assurance check.
Quality control as specified in EPA Method 16 should be followed. Gravi-
metrically certified permeation devices should be used to calibrate the
GC before and after each three hours of testing. The permeation tube de-
vices should be housed in a constant temperature bath whose temperature is
certified to +I°C with reference to an NBS traceable standard. The gas
flow across the devices should be measured each time of use with a soap
bubble flow tube.
11-30
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The recovery of HgS through the TRS sampling and analysis system
should he determined before and after each three hours of sampling. If
the loss of H£S through the system exceeds 20 percent, the data should be
invalidated. For system losses of 20 percent or less, the data from the
source can be corrected by the mean recovery value obtained before and
after tre three hou^s of sampling.
Before beginning Reference Method 16, the span of each CEM should be
adjusted to approximately 30 ppm HgS. The gas used to calibrate the CEM
should be analyzed with the GC using certified permeation devices as a
reference. The concentration of the CEM calibration gas should be based
on the GC results regardless of the concentration specified by the vendor.
The response of each CEM should be evaluated using a known concentra-
tion of H2S. The sample should be injected at the probe and drawn through
the complete sampling and analysis system. The response from the CEMS
should be within +5 percent of the known concentration.
Quality assurance testing should be completed in a stepwise fashion.
If the analyzer appears to be operating incorrectly during any step, the
problem should be identified and corrected before proceeding. Relative
accuracy testing should be initiated only after all preliminarey quality
control has been completed.
Gravimetrically certified permeation devices should be used as refer-
ence for the Referenced Method testing. One device for each compound should
be obtained. Each device should be certified at a standard temperature by
the vendor.
Calibration of the gas chromatograph for the reference method testing
before and after each three hours of analyses should be performed. An HgS
recovery check on the system before and after each three hour and after each
run is also important. If the minimum recovery specified by EPA Method 16
is not met, discarding the data as invalid is appropriate. If the minimum
system recovery is obtained, then one should correct the results by the
amount of the system loss before reporting the reference data.
A cylinder of approximately 10 ppm HgS in nitrogen should be used to
perform the recovery studies. Agreement between the reference method and
the CEM should be within 5% or the system should be checked before initi-
ating the Relative Accuracy testing.
11.3.2.7.3 Portable HyS CEMs -
In addition to RAA and gas cylinder evaluations a portable system
may be used to assess the long term performance of all installed TRS CEMs.
The use of portable CEMs by Kraft pulp mills has increased over the
last several years. Portable CEMs enable the source to measure regulated
emissions while minimizing time and manpower expenditures required by the
Federal Reference Methods. Portable CEMs allow real time monitoring and
decisions on corrective actions to commence immediately. The real bene-
fits and applications of portable CEMs are:
11-31
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o Stratification testing before permanently mounting CEMs on
stacks or ducts;
o Parallel monitoring during periods of questionable operation
by regulated CEMs;
o Diagnostic tool to check accuracy of installed CEMs and
control equipment malfunction; and
o Compliance monitoring during "out-of-control" conditions of
regulated CEMs.
11.3.2.8 Recordkeeping -
As part of a source quality assurance program, the following records
associated with the continuous emission monitoring system should be main-
tained. They are:
o Monitor Logbook;
o Calibration Forms;
o Precision Assessment Forms;
o Audit Forms; and
o Strip Charts and Daily Computer Printouts.
Each of these records is discussed below.
11.3.2.8.1 Logbooks -
An instrument logbook should be maintained at the monitoring site by
the Instrument Specialist. All activities related to the CEMs (maintenance,
calibration, etc.) should be recorded on the logbook form, as illustrated
in Table 11.7. Each entry in the logbook should include the date, a brief
description of the activity, and the individual's initials.
If corrective action is needed, then the operator completes a TRS CEM
Problem Communication Memo as illustrated in Table 11.8. This is then
submitted to the CEM QA Coordinator or the CEM Supervisor for corrective
action. The CEM OA Coordinator should maintain these records chronologic-
ally in a 3-ring binder. This provides documentation on when a problem
was first detected and the need for corrective action to resolve the
problem.
11.3.2.8.2 Calibration Forms -
Each time a calibration is performed the Instrument Specialist
completes the Precision Calculation Form, as illustrated in Table 7.9.
The form documents when calibrations are conducted and whether adjust-
ments were made. The completed form is submitted to the CEM OA Coordi-
nator who maintains a chronological record in a 3-ring binder.
11-32
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TABLE 11.7
TOTAL REDUCED SULFUR
CONTINUOUS EMISSION MONITORING
SYSTEM LOGBOOK
DATE
ACTIVITIES OR MAINTENANCE
BY
11-33
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TABLE 11.R
TOTAL REDUCED SULFUR
CEMS PROBLEM COMMUNICATION MEMO
From:
To: Date:
Problem Definition & Recommendation
Signed_
Corrective Action Taken
Completion Date Signed_
11-34
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PERIOD
TABLE 11.9
TOTAL REDUCED SULFUR
PRECISION CALCULATION FORM
PARAMETER_
UNITS
I
oo
en
Date
CEMS
Measured
Cone.
(Yi)
Precision
Check
Cone.
(Xi)
Percent
Difference
(
-------
11.3.2.8.3 Precision Assessment Forms -
An assessment of the CEMS precision is made by the CEM QA Coordinator each
quarter. The precision calculations are performed using the form shown
previously. The completed forms should be maintained by the CEM Supervisor
and available for review.
11.3.2.8.4 Audit Forms -
As discussed earlier, a corporate self-audit should be conducted
quarterly by the CEM QA Coordinator. Records of the quarterly audits
should be maintained at the corporate offices by the Assistant Program
Manager. The audit records would include the accuracy calculation forms
and any notes or comments about the audit.
11-36
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11.4 CONTROL AGENCY QUALITY ASSURANCE/QUALITY CONTROL ACTIVITIES
11.4.1 INTRODUCTION
Control agency quality assurance/quality control (OA/QC) activities
are an integral part of an inspection program as outlined in Chapter 4.
QA/QC activities for agency personnel involve all aspects of the phase
and level compliance program. As discussed in Chapter 4, the phase pro-
cess was administrative activities associated with the initial application
and certification of the installed TRS CEM system. Figure 11.8 illustrates
the three tiers associated with the phase process.
Phase I
Phased
Figure 11.8. Control Agency Phase Diagram
After completion of phase III, the level approach begins. Similar
to the phase approach, the level approach has four tiers, as illustrated
in Figure 11.9.
Level II
Level III
Level IV
Figure 11.9. Control Agency Level Diagram
The phase and level audit procedure have been designed so that each
activity indicates whether or not the CEM system has achieved the neces-
sary level of compliance before starting the next phase.
11-37
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Consequently, control agency OA activities are a major part of a source
CEM program; from initial installation through performance certification
to continuous compliance.
11.4.2 Control Agency QA Activities Involving the Phase Program
The phase process were administrative activities involved with
initial CEM system application, performance testing and final approval.
The type of activities at each phase are:
Phase I - Control agency initial approval of CEM application as
required through the source permit;
Phase II - Control agency observation of Performance Specification
Testing (PST) of the installed CEM system; and
Phase III- Control agency review of the PST report, with final
approval or disapproval.
11.4.2.1 Phase I QA Activities -
Under Phase I, the control agency is ensuring that the source TRS CEM
program meets all regulatory requirements. In particular, control agency
QA/QC activities, at this level, involve implementation of
o Management Control System (MCS);
o Standard Operating Procedure Manual (SOP); and
o Source Quality Assurance (QA) Program within the permit.
11.4.2.2 Phase II QA Activities -
Control agency QA activities associated with Phase II involves observa-
tion of the Performance Specification Test (PST) for monitor certification.
For the agency inspector, this would involve reviewing sampling and
analytical procedures performed by the source or its representative uti-
lizing Federal Reference Method 16, 16A or equivalent. OA activities are
not only limited to sampling methodology, but also to observation of pro-
cess and control equipment during certification.
11.4.2.3 Phase III QA Activities -
Phase III QA activities consists of reviewing the Performance Speci-
fication Test report. The reviewer should make a determination of the
acceptability of the test results and procedures. This determination
should support a final approval, or disapproval of the Performance Speci-
fication Test Report.
To assist the agency in performing these OA activities during the
phase program, several "Inspection" forms have been developed.
11-38
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They are included in the supplement to this manual, entitled "Technical
Assistance Document for Monitoring Total Reduced Sulfur (TRS) from Kraft
Pulp Mills - Inspection Forms." The QA inspection forms which address
the phase program are:
o Federal Reference Method 16 Observation Checklist;
o Federal Reference Method 16A Observation Checklist;
o Performance Specification Test Report - General Review
Checklist; and
o Performance Specification Test Report - Detailed Review
Checklist.
11.4.3 QA Activities Associated with Control Agency Level Program
The level program begins after completion of the phase program.
QA activities associated with the level program extend from excess
emission report review to stack test compliance determination. The
type of activities at each level are:
Level I - Control agency records reviewing involves excess
emission reports, previous inspection reports, source
"working" file and permit review;
Level II - "Walk through" evaluation involving review of monitor
recordkeeping (maintenance, monitor and control equipment
logs), monitor fault indicator review, monitor internal
zero/span check, strip chart review and electronic checks;
Level III - Evaluation of installed CEMs through external audit tech-
niques involving neutral density filters for opacity mon-
itors and gas cylinders/permeation tubes for gas monitors;
and
Level IV - Comparative evaluation of installed CEMs through performance
testing utilizing Federal Reference Methods or portable CEMs.
11.4.3.1 Level I QA Activities -
Level I control agency QA activities involve reviewing excess emis-
sion report for data accuracy and completeness. The inspector observes
trends and exceedences as reported on the standardized excess emission
report (Chapter 10). If discrepancies or inconsistances are noted, then
quality control (OC) activities are initiated. To aid the inspector on the
various QA activities associated with Level I, a checklist has been
developed, entitled: "Excess Emission Report, Kraft Pulp Mills Reviewer's
Checklist."
11.4.3.2 Level II QA Activities -
Level II agency OA activities are associated with evaluating the
TRS CEM system at the regulated facility. The inspector performs a
"walk through" QA inspection, beginning with records review and ending
11-39
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at the probe tip. The Level II QA activities involves review of record-
keeping and reporting activities, strip chart/data processor review, TRS
CEM daily zero/span checks, remote display review, control equipment review
and probe assembly evaluation. In essence, the QA "walk through" inspec-
tion correlates information from Level I review and comparing it to the
Level II data.
To assist the inspector in the Level II QA activities, a Field
Inspection Notebook has been developed as a supplement to this manual.
The main objective of this notebook is to cover, in detail, the QA
activities covering the level section of an Agency Inspection Program.
11.4.3.3 Level III QA Activities -
Level III QA activities involves a complete evaluation of the TRS
CEM system by challenging it with certified pollutant gas concentrations
Multiple concentration gases are injected, as close to the probe tip as
possible, and the monitor responses is compared to the certified gas
values. From this evaluation, a calibration error is determined. If the
error falls outside calibration drift performance specification values,
then the monitoring system is "out of control". This would initiate some
form of corrective action by the regulated facility.
As discussed in Chapter 6.0, Generation of Standard Test Atmosphere,
there are two techniques available to the inspector for generating known
pollutant concentrations of total reduced sulfur (TRS) compounds. They are:
o Dynamic Calibration Systems; and
o Static Calibration Systems.
Dynamic calibration systems, utilizing either permeation tubes or
gas cylinder dilution systems, provide the greatest flexibility in
checking the precision and linearity of an installed TRS CEM system.
Permeation tubes can be certified gravimetrical ly while reduced sulfur
gases can be acquired at higher concentrations in gas cylinder, therefore
circumventing many of the problems associated with low concentration
reduced sulfur cylinder gases.
Different from dynamic audit systems, static audit systems do not
involve diluting the gas concentration to a known value. Using a static
audit system, the standard pollutant gas must be in the concentration
range of the analyzer. This makes it very difficult, however, for the
static audit system because NBS-SRM's are not available in the reduced
sulfur compounds of interest. This limitation makes the dynamic calibra-
tion system more applicable as a QA activity.
11.4.3.3.1 Permeation Tube Audit System -
A permeation tube audit system consists of a clean air supply
certifiable permeation tubes, constant temperature bath and a mixing
chamber, as illustrated in Figure 11-10.
11-40
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Figure 11.10. Typical Permeation Tube Audit System
By maintaining the flow constant across the tube and temperature
of the bath constant, various concentrations of pollutant atmospheres can
be generated by varying the diluent gas flow. This provides versatility
as a QA auditing technique. Chapter 12, Equipment Selection, lists
several manufacturers which sell commercially available portable permea-
tion tube dilution systems.
11.4.3.3.2 Gas Cylinder Audit System -
The simplest and most economical QA audit system for providing a
known concentration of pollutant gas to a monitoring system is the sin-
gle dilution system, as illustrated in Figure 11.11.
11-41
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Qu
JC
•T
JL
-
F«
<
•^ F
lj
fi
i,
'lowmeter
•^ Mix
Mixing chamber
Test mixture
r*tfl ^ Control valve
f
Component Diluent
gas
gas
Figure 11.11. Gas Cylinder Audit System
In operation, a simple dilution system involves mixing a known
concentration of pollutant gas with a diluent gas to provide a lesser
known concentration of gas at the outlet. Utilizing the system in Figure
11.11, the outlet gas concentration can be calculated by the following
equations:
cu °u = cd
where:
Cu = concentration of undiluted pollutant gas (ppm);
Ou = volumetric flow rate of undiluted pollutant
gas (ml/min);
CQ- = final concentration of diluted gas (ppro); and
Qd = volumetric flow rate of dilution gas (ml/min).
In this configuration, both the flows of the pollutant and dilution
gases can be adjusted to provide a wide variation of pollutant gas con-
centrations. A 50:50 dilution is preferable, however, if matched rotameters
are used. Likewise, flow rates can be verified by use of a bubble flow meter.
Utilizing this system, the auditor must be concerned with the calibra-
tion of the flow measuring devices used in the system to ensure an accurate
production of pollutant gas is obtained. Figure 11.12 displays field use
"matched" rotameters in a control agency gas cylinder audit system.
11-42
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Figure 11.12.
Use of Matched Rotameters In A Control Agency Gas
Cylinder Audit System
Restricted or critical orifices have been used in one or both of the
gas cylinder channels to provide an accurate flow measurement. Operated
properly, critical orifices can lower the percent error associated with
flow measurement technique. Figure 11.13 illustrated the use of a critical
orifice in the pollutant gas line as a flow metering device.
11-43
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Critical
orifice(s)
Glass
manifold
exhaust
vent
To analyzer
Figure 11.13. Use of A Critical Orifice in A Control Agency OA Audit System
In this configuration, the auditor need only to adjust the flow of
the zero gas cylinder to produce various pollutant gas outputs, as calcu-
lated by the following equations:
Cu Ou = Cd (Ou
where:
Cu = concentration of undiluted pollutant in gas
cylinder (ppm);
Qu = rated flow of critical orifice (ml/min);
Cd = final concentration of diluted gas (ppm); and
Od = volumetric flowrate of dilution gas (ml/min).
Recently, the Research Triangle Institute developed a portable test
atmosphere generating device. The device was designed to be:
o Compact, lightweight and self-contained;
o Limited operating controls; and
o Constructed so easy maintenance could be performed.
The portable test atmosphere generating device is based on the
principle of gas phase dilution utilizing critical or restricted orifices
as flow controllers. This technique is advantageous because higher con-
centrations of test cylinder mixtures are available, thus providing better
gas stability. In addition, variable output of pollutant gas concentrations
are easily generated by use of the toggle switches. This eliminates the
need for flow measurements if the orifices are critical.
11-44
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A pictorial illustration of the basic portable test atmosphere
generating device is shown in Figure 11.14.
POLLUTANT GAS PRESSURE
GAUGE AND REGULATOR
POLLUTANT CAS INLET
DILUENT QAS INLET
SAMPLE PORT
POLLUTANT CAS f IOW PORT
DILUf NT GAS PRESSURE
GAUGE AND Rf GUlAIOfl
POLIUTANT CAS POLLUTANT GAS
RESTRICTOR FLOW TEST
TOGGLE VALVES VALVE
Figure 11.14. Portable Test Atmosphere Generating Device.
The system provides a mechanism, whereby, quantities of the pollu-
tant gas and diluent gas are mixed and exited out the sample port. The
flow rate of each gas is controlled by maintaining a predetermined pres-
sure drop across the orifices. Variation in exit gas concentration are
obtained by switching the pollutant gas between three separate orifices.
In operation, the pollutant gas is introduced to the system from the
pressurized cylinder through a bulkhead fitting, then flows through a
porous plug particle filter to a pressure regulator. The pollutant gas
then flows through the critical orifices to the mixing flask where dilu-
tion with zero air occurs. The critical orifices are so designed to give
various flows so a multipoint calibration curves can be generated.
Figure 11.15 illustrates the internal components of the portable test atmos-
phere generator.
11-45
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POLLUTANT
OAS
DILUEMT
OAS
fllTER
PRESSURE GAUGE
REGULATOR
STAINLESS STEEL CRDtt
TOGGLE VALVES
POROUS PLUG Rtsinirions
PRESSURE GAUGE
FllTER ' POROUS PLUG RESTRICtOn
REGULATOR /^—
SAMPLE PORT O r~^
Figure 11.15. Internal Schematic of Portable Test Atmosphere Generator
The zero air (diluent gas) may he either cylinder air or generated
from a zero air system. Like the pollutant gas, it also passes through
a bulkhead fitting, a porous plug particulate filter, a pressure regulator
and a flow restrictor before entering the mixing flask.
Seven (7) upscale concentrations can be generated by use of the
toggle valves independently or in combination of each other.
11.4.3.4 Level IV QA Activities
Level IV OA activities involve recertification of the installed CEM
system utilizing Performance Specification Test 5 and 3. The role of the
control agency during this level is to observe the extraction and computa-
tion of emissions from the source during testing. At this time, additional
"baselining" of the control equipment and continuous emission monitoring
system can be performed. The QA forms used during Phase II, Performance
Specification Test (PST) 5, are applicable during Level IV DA activities.
11-46
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12.0 EQUIPMENT SELECTION
12.1 INTRODUCTION
The monitoring of total reduced sulfur compounds from Kraft Pulp
Mills can be performed by either wet chemical or continuous emission
monitoring instrumentation. As demonstrated in the previous Sections,
each method exhibits both strengths and weaknesses. The wet chemical tech-
niques are simplier to use, but care must be taken during all aspects of
the procedures to insure an accurate "value".
Continuous emission monitors offer instantaneous analysis, but with
limitations. In the past, criticism of CEM's have been that they are
unreliable and perform poorly in a source environment. Indeed, many of
the CEM's have performed well in the Laboratory; but once placed on or
near a source, performance declines. This has been due, in part to the
inexperience of source personnel in the operation and maintenance of the
CEM systems. Most available systems on the market perform with the EPA's
Performance Specification guidelines when a committment by the source is
made to properly maintain the monitoring system. Recent data indicates
when a source lacks this committment to its monitoring program, perform-
ance declines. Even the best built monitors, however, without a good opera-
tion and maintenance program, do not provide the reliable data needed for
complying with air pollution regulations. Especially with monitoring
reduced sulfur compounnds, many of the analytical techniques require spe-
cialized training.
12.2 VENDOR LIST
The objective of this chapter is to provide a list of vendors to the
reader to assist in the selection of a total reduced sulfur monitoring
system, whether wet chemical or continuous. The list was compiled from
trade literature, vendor fliers, trade shows and personnel contacts. As
with any list, it is never complete and is always outdated due to manu-
facturers reorganizing. The lists are provided only as a guideline to
equipment and monitor selection.
12.2.1 Gas Manufacturers
G C Industries, INC.
20361 Prairie St. Unit 4
Chatsworth, CA 91311
(818) 701-7072
Scott Environmental Technology, Inc.
Rt. 611
Plumsteadville, PA. 18949
(215) 766-8861
Ideal Gas Products
P.O. Box 709
Edison, N.J. 08818
(800) 225-1706
M G Scientific Gases
2460 Blvd. of the Generals
Valley Forge, PA 19482
(215) 630-5492
Matheson Gas Products, Inc.
30 Seaview Dr.
Secaucus, N-) 07094
(201) 867-4100
Scott-Martin, Inc.
2001-H Third St.
Riverside, CA. 92507
(714) 784-1240
12-1
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Gas Manufacturers (continued)
VICI Metronics
2991 Corvin Dr.
Santa Clara, CA 95051
(408) 737-0550
Arco Industrial Gases
575 Mountain Avenue
Murray Hill, NJ 07974
(201 ) 464-8100
12.2.2 Oxygen Analyzers (0?)
Dynatron, Inc.
Box 745
Wallingford, Ct. 06492
(203) 265-7121
Econics Corp.
540 Dakmond Parkway
Sunnyvale, CA 94086
(408)738-8500
Teledyne Analytical Instruments
Box 1580
City of Industry, CA 91749
(818) 961-9221
Whittaker Environmental Products
12fi26 Raaymen Street
North Hollywood, CA 91605
(818) 765-6622
Delta F. Corp.
Walnut Hill Park
Woburn, MA. 01801
(617) 915-6536
Westinghouse Electric Corp.
Combustion Control Division
Box 901
Orrville, DH 44667
(415) 837-4622
Milton Roy Co.
Hays Republic Division
4333 S. Ohio St.
Michigan City, IN 46360
(219)879-4441
AlphaGaz
Box 149 Woods Road
Cambridge, Md. 21613
(301) 228-6400
1-800-638-1197
Ideal Gas Products
977 New Durham Road
Box 709
Edison, NJ 08818
(201) 287-8766
Datatest, Inc.
6850 Hibbs Lane
Levittown, PA 19057
(215) 913-0668
Sybron Corp.
Analytical Products Division
221 Rivermoor St.
Boston, MA 02132
(617) 469-3300
Hague International
3 Adams Street
South Portland, ME 04106
(207) 799-7347
Cleaver-Brooks Division
Aqua-Chem. Inc.
Box 421
Milwaukee, WI 53201
(414) 962-0100
Environmental Products
12626 Raymer Street
North Holywood, CA 91605
(213) 765-6622
Environmental Measurement
Research Corporation
17 N. 32nd. St.
Billingtons, Montana 59101
(406) 252-4450
Neotronics N.A. Inc.
Box 370
Gainesville, Ga. 30503
(404)535-0600
12-2
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Gas Manufacturers (continued)
Cosa Instrument Corp.
70 Oak Street
Norwood, NJ 07648
(201) 767-6600
Lear Siegler, Inc.
74 Inverness Dr.
Englewood, CO 80112
(303) 792-3300
Ametek/Thermox Instrument Division
150 Freeport Road
Pittsboro, Pa. 15238
(412) 828-9040
EXO Sensors, Inc.
1220-B Simon Circle
Anaheim, CA 92806
(714) 632-8289
Thermo Electron Corp.
108 South Street
Hopkinton, Mass. 01748
(617) 435-5321
Anarad, Inc.
534 E. Ortega St.
Santa Barbara, CA 93103
(805) 963-6583
Yokogawa Corporation of America
2 Dart Road
Shenandoah, Georgia 30265
(404) 253-7000
Yokogawa Corp. of America (YEW)
2 Dart Road
Shenandoah, Georgia 30265
(404) 253-7000
12.2.3 Hydrogen Sulfide Analyzers (H?S)
Bitel Manufacturing
2835 Laguna Canton Rd.
Laguna Beach, CA 92652
(714) 494-2012
Texas Analytical Controls
4434 Bluebonnet Dr.
Stafford, TX 77477
(713) 491-4160
Teledyne - Hastings, Inc.
Newcombe Ave.
Hampton, VA 23669
(804) 732-6531
Infrared Industries
Instruments Division
Santa Barbara, CA
(R05) 684-4181
Delphi Instruments, Inc.
3030 Red Hat Lane
Whittier, CA 90601
(213) 692-9021
Beckman Instruments
Process Instruments Division
2500 Harbor Blvd.
Fullerton, CA 92634
(714) 871-4848
Bendix Corporation
P. 0. Drawer 831
Lewisburg, WV 24901
(304) 647-4358
Bailey Controls Company
29801 Euclid Ave.
Wickliffe, OH 44092
(216) 585-6818
Land Combustion Inc.
3392 Progress Drive, Suite E
Bensalem, PA 19020
(215) 244-1100
Teledyne Analytical Instruments
16830 Chestnut St.
City of Industry, CA 91749
(818) 961-9221
Delta F. Corp.
Walnut Hill Park
Woburn, MA 01801
(617) 935-6536
12-3
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12.2.3 Hydrogen Sulfide Analyzers (H?S) (contd.)
Neotronics N.A. Inc.
Box 370
Gainesville, Ga. 30503
(404) 535-0600
DuPont Company
Analytical Instruments Division
Concord Plaza
McKean Bldg.
Wilmington, DE 19898
(302) 772-5481
InterScan Corp.
P. 0. Box 2496
21700 Nordhoff St.
Chatsworth, CA 91311
(818) 882-2331
Jerome Instruments Corporation
Old High School
P. 0. Box 336 Hwy. 89A
Jerome, Arizona 86331
1-800-952-2566
12.2.4 Condenser (Refrigerated Moisture)
Hankison Corporation
1000 Philadelphia St.
Cannonsburg, Pa. 15317
Deltech Engrg. Inc.
Century Park
P. 0. Box 667
New Castle, DE 19720
(302) 328-1345
12.2.5 Pumps
KNF Neuberger, Inc.
P. 0. Box 4060
Princeton, NJ 08540
(609) 799-4350
Cole-Parmer Instrument Co.
7425 North Oak Park Ave.
Chicago, 111. 60648
(312) 647-0272
Air Dimensions, Inc.
P. 0. Box 867
Lansdale, Pa. 19446
(215) 368-5060
Houston Atlas Inc.
9441 Baythorne Dr.
Houston, TX 77241
(713) 462-6116
Candel Industries Limited
9365 W. Sannich Rd. Box 2580
Sidney, B.C. Canada V8L-4C1
(604) 656-0156
Tracer Atlas, Inc.
9441 Baythorne Drive
Houston, Texas 77041
(713) 462-6116
Sierra Monitor Corporation
1050 K East Duane Avenue
Sunnyvale, CA 94086
(408) 746-0188
Gen Cable Apparatus Div,
5600 W. 88th Ave.
Westminister, CO 80030
(303) 427-3700
Howel1 Labs, Inc.
54 Harrison Rd.
Bridgton, ME 04009
(207) 647-3327
Thomas Industries
1419 Illinois Ave.
Sheboygan, Wis. 53081
(414) 457-4891
Contamination Control, Inc.
Forty Foot and Tomlinson Rds.
Kulpsville, PA 19443
(215) 368-2200
Science Pump Corporation
1431 Ferry Ave.
Camden, N.J. 08104
12-4
-------
12.2.6 Combustion Tube (Quartz) for Thermal Oxidation Oven
Class Craft, Inc. Fisher Scientific Co.
Rt. 1, Box 83 535 Alpha Drive
Micanopy, Fl. 32667 Pittsburg, PA 15238
(904) 466-3412 (412) 562-8543
Southern Scientific Applied Test Systems, Inc.
Rt. 1, Box 83 348 New Castle Road
Micanopy, Fl. 32667 P. 0. Box 1529
(904) 466-3412 Butler, PA 16001
(412) 283-1212
12.2.7 Filter
Ferro Corp. Fisher Scientific Co.
Electro Div. 585 Alpha Dr.
P. 0. Box 389 Pittsburgh, PA 15238
601 W. Commercial St. (412) 562-8543
E. Rochester, NY 14445
(716)586-8770 Mil lipore Corp.
Ashby Rd.
BGI, Inc. Medford, MA 01730
58 Guinan St. (800) 225-1380
Waltham, Mass. 02154
(617) 891-9380
Pall Trinity Micro Corp.
Rt. 281
Cortland, NY 13045
(607) 756-7535
12.2.8 Scrubbers - Teflon Continuous & Batch SC>2
Savillex Corp.
5325 Highway 101
Minnetonka, MN 55343
(612) 938-7727
12.2.9 Thermal Oxidation Oven
Fisher Scientific Co. Lydon Bros. Corp.
585 Alpha Dr. 85 Zabriskie St/P.O. Box 708
Pittsburgh, PA 15238 Hackensack, NJ 07602
(412) 781-3400 (210) 343-4334
Batson, Louis P. Co. Thermovation Engineering
P. 0. Box 3978 P. 0. Box 24211
Greenville, SC 29608 Cleveland, OH 44124
(803) 242-5262 (216) 291-1236
CEM Corp. US Testing Co., Inc.
P. 0. Box 9 1415 Park Ave.
Indian Trail, NC 28079 Hoboken, NJ 07030
(704) 821-7015 (701) 792-2400
Trent, Inc.
201 Leverington Ave.
Philadelphia, PA 19127
(215) 482-5000
12-5
-------
12.2.10 Air Bath for Teflon Permeation Tubes
Analytical Instrument Development, Inc.
Rt. 41 and Newark Rd.
Avondale, PA 19311
(215) 268-3181
U. S. Testing Co., Inc.
1415 Park Ave.
Hoboken, NJ 07430
(201) 792-2700
12.2.11 Aspirator (Teflon) and Aspirated Gas Sampler
Lockwood & McLorie, Inc.
P. 0. Box 113
Horsham, PA 19044
(215) 675-8218
Metronics Associates, Inc.
3201 Porter Dr.
Stanford Industrial Park
Palo Alto, CA 94304
(415) 493-5632
12.2.12 Dynamic Gas Analyzer Calibration
Vici Metronics
2991 Corvin Drive
Santa Clara, CA 95051
(408) 737-0550
Matheson Gas Products, Inc.
30 Seaview Dr. Box 1589
Secaucus, NJ 07094
(201) 867-4100
Exemplar Design Engineering, Inc.
4422 D Catlin Circle
Carpinteria, CA 93013
(805) 684-0527
Demaray Scientific
Instruments, Ltd.
S. E. 1122 Latah St.
Pullman, WA 99163
G. C. Industries
20361 Prairie Street
Unit #4
Chatsworth, CA 91311
(818) 701-7072
12.2.13 Gas Permeation Tubes
Kin-Tek Laboratories, Inc.
Drawer J
Texas City, TX 77590
(409) 945-4529
Gas Technologies
555 Rreen PI.
Woodmere, NY 11598
(516) 873-6413
Science Pump Corp.
1431 Perry
Camden, N.J. 08104
(609) 963-7955
Teledyne Hastings Raydist
Box 1275
Hampton, Va. 23661
(804) 723-6531
Candel Industries Ltd.
Box 2580
Sidney, B.C., Canada V8L-4C1
(604) 656-0157
Enviro Electronic Services Inc. (EESI)
P. 0. Box 452
Greenfield, IN 46140
(317) 462-2614
Ecology Board, Inc.
9257 Independence Ave.
Chatsworth, CA 91311
(213) 882-6795
12-6
-------
12.2.13 Gas Permeation Tubes (contd.)
Vici Metronics
2991 Corvin Drive
Santa Clara, CA 95051
(408) 737-0550
Analytical Instrument Development, Inc.
Rt. 41 and Newark Rd.
Avondale, PA 19311
(215) 268-3181
G. C. Industries, Inc.
20361 Prairie St.
Unit #4
Chatsworth, CA 91311
(818) 701-7072
12.2.14 Sample Conditioner Systems
Environmental Products
12626 Raymer St.
N. Hollywood, CA 91605
(213) 765-6622
Exemplar Design Engineering, Inc.
4422 D. Catlin Dr.
Carpinteria, CA 93013
(805) 684-0527
Thermo Electron Corp.
108 South Street
Hopkinton, Mass. 01748
(617) 435-5321
Anarad, Inc.
534 E. Ortega St.
Santa Barbara, CA 93103
(805) 963-6583
DuPont Company
Analytical Instruments Division
Concord Plaza
McKean Bldg.
Wilmington, DE 19898
(302) 772-5481
Lear Siegler, Inc.
74 Inverness Dr., East
Englewood, CO 80112
(303) 770-3300
Columbia Scientific Industries
P. 0. Box 9908
Austin, TX 78766
(512) 258-5191
Tracer, Inc.
6500 Tracor Land
Austin, TX
(512) 926-2800
Metronics Associates, Inc,
3201 Porter Drive
Stanford Industrial Park
Palo Alto, CA 94304
(415) 493-5632
Candel Industries, Inc.
P. 0. Box 2580
Sidney, B. C. V81 4C1
(604) 656-0157
Sampling Technology, Inc.
P. 0. Box B Highway 80E
Waldron, Arkansas 72958
Analon
P. 0. Box 416
S. Bedford St.
Burlington, MA 01803
(617) 272-9002
Carton Technology
P. 0. Box 26818
San Diego, CA 92126
(619) 578-5040
Acurex
555 Clyde Ave.
P. 0. Box 7555
Mountainview, CA 94039
Western Research
1313 44th Ave., N. E.
Calgary, Alberta, Canada T2E 6L5
(403) 276-8806
Research Triangle Institute
P. 0. Box 12194
Research Triangle Park, NC 27709
(919) 541-6000
12-7
-------
12.2.14 Sample Conditioner Systems (contd.)
KVB
18006 Skypark Blvd.
P. 0. Box 19518
Irvine, CA 92714
(714) 250-6200
Environmental Measurement Research
Corporation (EMRC)
17 N. 32nd Street
Billings, Montana 59101
(406) 252-4450
12.2.15 Probes
Anarad, Inc.
534 E. Ortega St.
Santa Barbara, CA 93103
(805) 963-6583
Teledyne Analytical Instruments
168030 Chestnut St.
City of Industry, CA 91749
(213) 961-9221
DataTest
6850 Hibbs Lane
Levittown, PA 19057
(215) 943-0668
Acurex Corp.
555 Clyde Ave. Box 7555
Mountainview, CA 94039
(415) 964-3200
Lear Siegler, Inc.
74 Inverness Drive, East
Englewood, CO 80112
(303) 770-3300
Combustion Engineering (CE)
Process Analytics
P. 0. Drawer 831
Lewisburg, West Virginia 24901
(304) 647-4358
Mott Metallurgical Corp.
Farmington Industrial Park
Farmington, Conn. 06032
(203) 677-7311
DuPont Company
Analytical Instruments Division
Concord Plaza
McKean Bldg.
Wilmington, RE 19898
(302) 772-5481
Western Research
1313 44th Ave., N.E.
Calgary, Alberta, Canada T2E 6L5
(403) 276-8806
Candel Industries
Box 2580
Sidney, B. C., Canada V8L 4C1
(604) 656-0157
12.2.16 Stack Testing Equipment (Impingers, Sampling Train, Meter Box
Assembly)
Nutech Corp.
2806 Cheek Road
Durham, N. C. 27704
(919) 682-0402
Anderson Samplers, Inc.
4215-C Wendell Dr.
Atlanta, Ga. 30336
(404) 691-1910
Sierra/Misco Inc.
1825 Eastshore Highway
Berkeley, CA 94710
(415) 843-1382
Research Application Co.
P. 0. Box 265
Cambridge, Mass. 21613
(301) 228-9505
12-8
-------
12.2.16 Stack Testing Equipment (Impingers, Sampling Train, Meter Box
Assembly) (contd.)
KVB Equipment Corp.
18006 Sky park Blvd.
P. 0. Box 19518
Irvine, CA 92714
Lear Siegler, Inc.
74 Inverness Dr., East
Englewood, CO 80110
(303) 792-3300
NAPP, Inc.
8825 N. Lamar
Austin, TX 78753
Precision Scientific Co.
3737 W. Cortland St.
Chicago, 111. 60647
Analytical Instrument Development, Inc.
Rt. 41 and Newark Road
Avondale, PA 19311
(215) 268-3181
12.2.17 Heat Trace Lines
Technical Heaters, Inc.
710 Jessie Street
San Fernando, CA 91340
(818)361-7185
12.2.18 Pressure Gauges and Manometers
Fisher Scientific Company
585 Alpha Drive
Pittsburgh, Pa. 15238
(412) 781-3400
Airco Welding Products
(Distributors in most states)
12.2.19 Regulators
Linde Specialty Gases (Model CRB 330)
Airco Industrial Gases
Union Landing & River Rds.
Riverton, N. J. 08077
(609) 829-7878
Matheson Gas Products
P. 0. Box E
Lyndhurst, N. J. 07071
(201) 935-6660
Korz Instruments, Inc.
20 Village Square Box 849
Carmel Valley, CA 93924
(408) 659-3421
Savillex Corp.
5325 Highway 101
Minnetonka, Minn. 55343
(612) 934-4050
Western Research and Development
1313 44th Ave. NE
Calgary, Alberta, Canada T2E 6L5
Thomas Scientific
Vine St. at 3rd, Box 779
Philadelphia, PA 19105
(215) 574-4500
Acurex Corp.
Energy & Environmental Division
485 Clyde Ave.
Mt. View, CA 94042
Samuel Moore & Co.
(Dekoron Division)
Industrial Park
Mantua, OH 44255
(216)274-2276
Matheson Gas Products
P.O. Box E
Lyndhurst, N.J. 07071
(201) 935-6660
Ideal Gas products
P. 0. Box 709
Edison, N. J. 08810
1-800-225-1706
12-9
-------
12.2.20 Flowmeters, Rotameters
Aalborg Instruments & Controls
2 Melnick Dr.
Monsey, NY 10952
(914) 352-3171
Ametek Schutte & Koering Div.
2233 State Rd.
Cornwells Heights, PA 19020
(215) 639-0900
12.2.21 Flowmeters, Mass
Brooks Instrument Div.
407 W. Vine St.
Hat field, PA 19440
(215) 362-3500
Kurz Instruments Inc.
P.O. Box 849
Carmel Valley, CA 93924
(408) 659-3421
12.2.22 Pumps. Diaphragm
Air Dimensions Inc.
P.O. Box 867
Lansdale, PA 19446
(800) 423-6464
B.A. Bromley Inc.
340 Main St.
Springfield, MA 01105
(413) 736-4280
Blue White Industries
14931 Chestnut St.
Westminster, CA 92683
(714) 893-8529
Bran & Lubbe Inc.
512 Northgate Pkwy
Wheeling, IL 60090
(312) 520-0700
Capital Controls Co., Inc.
P.O. Box 211
Colmar, PA 18915
(215) 822-2901
Warren Rupp-Houdaille Inc.
800 N Main St.
Mansfield, OH 44905
(419) 524-8388
AquaMatic Inc.
2412 Grant Ave.
Rockford, IL 61103
(815) 964-9421
Blue White Industries
14931 Chestnut Street
Westminster, CA 92683
(714) 893-8529
M. 6. Scientific Gases
2460 Blvd. of the Generals
Valley Forge, PA 19482
(215) 630-5492
Texas Nuclear Corp.
P.O. Box 9267
Austin, TX 78766
(512) 836-0801
Chem-Tech Inti
92 Bolt St/PO Box 1476
Lowell, MA 01853
(617) 453-4020
Gorman-Rupp Co., The
305 Bowman St.
Mansfield, OH 44902
(419) 755-1011
ITT Marlow Pumps
P.O. Box 200
Midland Park, NJ 07432
(201) 444-6900
KNF Neuberger Inc.
P.O. Box 4060
Princeton, NJ 08540
(609) 799-4350
Mec 0 Matic Co., The
P.O. Box 43390
St. Paul, MN 55164
(612) 739-5330
Wisa Precision Pumps
235 W. First St.
Bayonne, NJ 07002
(201) 823-3694
12^10
-------
12.2.22 Pumps, Diaphragm (contd.)
Nil den Pump & Eng. Co.
22069 Van Buren St.
Colton, CA 92324
12.2.23 Pumps. Sampling
Aerovironment Inc.
825 Myrtle Ave.
Monovia, CA 91016
(818) 357-9983
Air Dimensions Inc.
P.O. Box 867
Landsale, PA 19446
(800) 423-6464
Allweiler Pump Inc.
5410 Newport Ave., #40
Rolling Meadows, IL 60008
(312) 892-9194
Fluid Metering Inc.
29 Orchard St/PO Box 179
Oyster Bay, NY 11771
(516) 922-6050
Geo. Engineering Inc.
100 Ford Rd., Bldg. 3
Denville, NJ 07834
(201) 625-0700
Gil Ian Instrument Corp.
8 Dawes Hwy.
Wayne, NJ 07470
(201) 831-0440
Gilson Medical Electronics Inc,
3000 W. Beltline Hwy.
Middleton, WI 53562
(608) 836-1551
Precisionaire
235 W. First St.
Bayonne, NJ 07002
(201) 823-3699
12.2.24 Valves, Metering
DCL Inc.
P.O. Box 125
Charlevoix, MI 49720
(616) 547-5600
Zimpro Inc.
Military Rd.
Rothschild, WI 54474
(715) 359-7211
BVS Inc.
Rt. 322 W. & Poplar Rd.
Honey Brook, PA 19344
(215) 273-2841
Barnant Co.
28W092 Commercial Ave.
Barrington, IL 60010
(312) 381-7050
Brails ford A Co., Inc.
670 Milton Rd.
Rye, NY 10580
(914) 967-1820
QED Environmental Systems
P.O. Box 7269
Ann Arbor, MI 48107
(313) 995-2547
Robbins & Myers Inc.
1345 Lagonda Ave.
Springfield, OH 45501
(513) 327-3553
Roth Pump Co.
P.O. Box 910
Rock Island, IL 61201
(309) 787-1791
Science Pump Corporation
1431 Ferry
Camden, NJ 08104
(609) 963-7955
Wisa Precision Pumps
235 W First St.
Bayonne, NJ 07002
(210) 823-3694
M. G. Scientific Gases
2460 Blvd. of the Generals
Valley Forge, PA 19482
(215) 630-5492
12-11
-------
12.2.24 Valves. Metering (contd.)
Hammel Dahl & Jamesbury Cntrls. Co.
175 Post Rd.
Warwlch, RI 01888
(401) 781-6200
Viler Engineering
P.O. Box 7269
Burbank, CA 91510
(818) 843-1922
12.2.25 Valves - Needle
Cajon Company
32550 Old South Miles Rd,
Solon, OH 44139
(216)248-0200
Hoke, Inc.
Tenakill Park
Cresskill, N.J. 07626
(201)568-9100
Fluorocarbon
P.O. Box 3640
(1432 S. Allec St.)
Anaheim, CA 92803
(714)956-7330
Malema Engineering Corp.
500 NE 25th St.
Pompano Beach, FL 33064
(305)942-0880
Mueller Steam Specialty
P.O. Box 1569
Lumberton, NC 28359
(919)738-8241
Nupro Company
4800 E. 345th St.
Willoughby, OH 44094
(216)951-7100
Whitney Research Tool Company
5679 Landregon St.
Oakland, CA 94662
Parker Hannifin Corp.
P.O. Box 4288
Huntsville, AL 35802
(205)881-2040
Scientific Systems Inc.
1120 W . College Ave.
State College, PA 16801
(814)234-7311
Vlier Engineering
PO Box 7269
Burbank, CA 91510
(818)843-1922
12.2.26 Carbon Dioxide and Carbon Monoxide Analyzers
Anarad Inc.
534 E. Ortega St.
Santa Barbara, California 93103
(805)963-6583
Datatest Inc.
6850 Hibbs Lane
Levittown, PA 19057
(215)943-0668
Lear Siegler, Inc.
74 Inverness Dr.
Englewood, CO 80112
(303)792-3300
Syconex Corp.
1504 Highland Ave.
Duarte, CA 91010-2831
(818)359-6648
Du Pont Company
Analytical Instruments Division
Concord Plaza
McKean Building
Wilmington, DE 19898
(302)772-5431
Measurex Corp.
One Results Way
Cupertino, California 95014
(408)255-1500
12-12
-------
12.2.26 Carbon Dioxide and Carbon Monoxide Analyzers (contd.)
Teledyne Analytical Instruments
16830 Chestnut Street
City of Indsustry, CA 91749
{23)961-9221
Horiba Instruments Inc.
1021 Duryea Ave.
Irvine, CA 92714
(714)540-7874
Westinghouse Electric Corp.
Combustion Control Division
Box 901
Orrville, OH 44667
(415)837-4622
1-800-628-1200
Land Combustion
3392 Progress Dr. Ste E
Bensalem, PA 19020
(215)244-1100
Dynatron Inc.
Barnes Ind Park Box 745
Wallingford, CT 06492-5847
(203)265-7121
Econics Corp.
540 Dakmond Parkway
Sunnyvale, California 94086
(408) 738-8500
12.2.27 Fittings
Crawford Fitting Company
29500 Solon Road
Solon, OH 44139
(216)248-4600
Fluorocarbon, Process Systems Div,
P.O. Box 3640
(1432 S. Allec St.)
Anaheim, CA 92803
(714)956-7330
Beckman Industrial Corp.
2500 Harbor Blvd.
Fuller-ton, CA 92634
(714)871-4848
Infrared Industries Inc.
P.O. Box 989
Santa Barbara, CA 93102
(805)684-4181
Thermo Electron Corp.
Box 459
Waltham, MA 02254
(617)890-8700
CEA Instruments
16 Chestnut St.
Emerson, NJ 07630
(201)967-5660
Servomex
Analytical Products Division
Sybron Corporation
221 Rivermoor St.
Boston, MA 02132
(617)469-3300
Rosemount Analytical
Uniloc Division
2400 Barranca Road
P. 0. Box 19521
Irvine, California 92714
Fluoroware, Inc.
Jonathan Industrial Center
Chaska, MN 55318
(612)448-3131
12-13
-------
12.2.28 Flow Controllers
Brooks Instruments
407 W. Vine St.
Hatfield, PA 19440
{215)368-2000
12.2.29 Portable Gas Chromatographs
Byron Instruments Inc.
520 S. Harrington St., Dept. PED
Raleigh, NC 27601
(919)832-7501
HNU Systems Inc.
160 Charlemont St.
Newton, MA 02161
(617)964-6690
Tracer Atlas Inc.
9441 Baythorne Dr.
Houston, TX 77041
(713)462-6116
Van'an Assoc/D-070
611 Hansen Way
Palo Alto, CA 94303
(415)493-4000
Xentech Inc.
6662 Hayvenhurst Ave.
Van Nuys, CA 91406
(818)787-7380
Horiba Instruments
1021 Duryea Avenue
Irvine, California 92714
(714) 540-7874
12.2.30 SO? Analyzers
Envi ronmental Measurement Research
Corporation (EMRC)
17 N. 32nd Street
Billings, Montana 59101
(406)252-4450
Teledyne Analytical Instruments
16830 Chestnut St.
City of Industry, California 91749
Thermo Electron Corp.
108 South Street
Hopkinton, Mass. 01748
(617) 435-5321
Condyne Instruments Co.
4851 Del Monte Rd.
La Canada, CA 91011
(619)829-7878
Hewlett-Packard
P.O. Box 10301 MS 20B3
Palo Alto, CA 94303
(415)857-5731
Microsensor Technology Inc.
47747 Warm Springs Blvd.
Fremont, CA 94539
(415)490-0900
Foxboro Analytical
Box 5449
South Norwalk, CT 06856
(203) 853-1616
Baseline Industries
P.O. Box 649
Lyons, Colorado 80540
(303)823-6661
Sentex Sensing Technology
553 Broad Avenue
Ridgefield, N.J. 07657
Whittaker Environmental Products
12626 Raymer Street
North Hollywood, California 91605
(213)765-6622
Columbia Scientific Industries
P. 0. Box 9908
Austin, Texas 78766
(512)258-5191
Candel Industries, Inc.
P. 0. Box 2580
Sidney, B. C. V81 4C1
(604)656-0157
-------
12.2.30 SO? Analyzers (contd.)
Anarad, Inc.
534 E. Ortega St.
Santa Barbara, CA 93103
(805) 963-6583
DuPont Company
Analytical Instruments Division
Concord Plaza
McKean Bldg.
Wilmington, OE 19898
(302) 772-5481
Lear Siegler, Inc.
74 Inverness Dr., East
Englewood, CO 80112
(303)770-3300
Acurex
555 Clyde Ave.
P.O. Box 7555
Mountainview, CA 94039
KVB Equipment Corp.
18006 Sky park Blvd.
P. 0. Box 19518
Irvine, CA 92714
(714) 250-6200
12.2.31 TRS CEM Systems
Anacon
P.O. Box 416
South Bedford Street
Burlington, MA 01803
Applied Automation, Inc.
Pawhuska Road
Bartlesville, OK 74004
(918)676-6141
Bendix Corporation
(New Conbustion Engineering)
Envi ronmental & Process
Instruments Division
P. 0. Drawer 831
Lewisburg, WV 24901
(304)647-4358
Candel Industries Limited
9865 West Saanich Road
P. 0. Box 2580
Sidney, B. C. Canada V8L-4C1
(604)656-0157
Sampling Technology, Inc.
P. 0. Box B Highway 80E
Waldron, Arkansas 72958
Anal on
P. 0. Box 416
S. Bedford St.
Burlington, MA 01803
(617)272-9002
Carlton Technology
P. 0. Box 26818
San Diego, CA 92126
(619)578-5040
Western Research
1313 44th Ave., N.E.
Calgary, Alberta, Canada T2E 6L5
(403)276-8806
Monitor Labs Inc.
10180 Scripps Ranch Blvd.
San Diego, CA 92131
(619)578-5060
Thermo Electron Corp.
108 South Street
Hopkinton, Mass. 01748
(617)435-5321
III Barton Instruments
900 S., Turnbull Canyon Rd.
P. 0. Box 1882
City of Industry, CA 91749
Lear Siegler, Inc.
74 Inverness Drive East
Englewood, CO 80110
(404)763-8003
Sampling Technology, Inc.
P. 0. Box B
Waaldron, AR 72958
Theta Sensors, Inc.
17635-A Rowland St.
City of Industry, CA 91748
(213)965-1539
12-15
-------
12.2.31 TRS CEM Systems (contd.)
Charlton Technology, Inc.
P. 0. Box 26818
San Diego, CA 92126
(619)578-5040
Columbia Scientific
Industries Corporation
P. 0. 9908
Austin, TX 78766
(800)531-5003
(512)257-5181 (in Texas)
Eitel Manufacturing, Inc.
2835 Laguna Canyon Road
Laguna Beach, CA 92651
Westinghouse Electric Corporation
Combustion Control Division
Box 901
Orrville, Ohio 44667
(216) 682-9010
Syconex Corporation
1504 Highland Avenue
Duarte, California 91010-2831
(818) 359-6648
Elf Technologies, Inc.
103 East 37th Street
New York, New York 10016
Datatest, Inc.
6850 Hibbs Lane
Levittown, PA 19057
(215) 943-0668
Tracor Atlas, Inc.
9441 Baythorne Dr.
Houston, TX 77041
(713)462-6116
Western Research
1313-44 Avenue North East
Calgary, Alberta
Canada T2E6L5
(403)276-8806
Environmental Measurement Research
Corporation (EMRC)
17 N. 32nd Street
Billings, Montana 59101
(406) 252-4450
Measurex Corporation
One Results Way
Cupertino, California 95014
(408) 255-1500
Horiba Instruments
1021 Duryea Avenue
Irvine, California 92714
(714) 540-7874
MDA Scientific, Inc.
1815 Elm Dale Avenue
Glenview, Illinois 60025-1394
1-800-323-2000
12-16
-------
13.0 BIBLIOGRAPHY
1. "Environmental Outlook - 1980," US Environmental Protection Agency,
Council on Environmental Quality, Washington, D. C. EPA 600/8-80-003,
July 1980.
2. W. T. Winberry, Jr., "Source Sampling & Analysis of Gaseous Pollutants,"
U. S. Environmental Protection Agency, Air Pollution Training Institute,
Course Manual 468, EPA 450/2-81-009, May 1981.
3. "Observer's Checklist Package for Environmental Protection Agency
Reference Test Methods and Continuous Emission Monitor Certification,
(Draft)," U. S. Environmental Protection Agency, Office of Air Quality
Planning & Standards, Research Triangle Park, NC, EPA 340/1-80-009,
June 1980.
4. "Performance Specification Tests for Pollutant and Diluent Monitors:
Reporting Requirements, Report Format, and Review Procedures," U.S.
Environmental Protection Agency, Stationary Source Enforcement Series,
EPA 340/1-83-013, January 1983.
5. "Guidelines for the Observation of Performance Specification Tests of
Continuous Emission Monitors," U. S. Environmental Protection Agency,
Stationary Source Enforcement Series, EPA 340/1-83-009, January 1983.
6. "Preliminary Air Pollution Survey of Odorous Compounds," U. S. Department
of Health, Education and Welfare, Public Health Service, National Air
Pollution Control Administration, October 1969.
7. "Preliminary Air Pollution Survey of Hydrogen Sulfide," U.S. Department
of Health, Education & Welfare, Public Health Service, National Air
Pollution Control Administration, October 1969.
8. "Operation and Maintenance of Kraft Recovery Boilers and Associated
Electrostatic Precipitators Subject to the New Source Performance
Standards for Kraft Pulp Mills," U. S. Environmental Protection Agency
Emission Standards & Engineering Division, Research Triangle Park,
NC, Feb. 1983.
9. "Kraft Pulp Mill Inspection Guide," U. S. Environmental Protection Agency,
Office of Air Quality Planning & Standards, Research Triangle Park,
NC, EPA 340/1-83-017, January 1983.
10. "Preparation of a Draft Air Compliance Inspection Manual (Final
Report)," U. S. Environmental Protection Agency, Stationary Source
Compliance Division, Office of Air Quality Planning & Standards,
Washington, D. C. November 1984.
11. "Development of Guideline Document for State Operating and Maintenance
Recordkeeping Programs," U. S. Environmental Protection Agency, Sta-
tionary Source Compliance Division, Office of Air Quality Planning &
Standards, Washington, DC, March 1981.
13-1
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12. "Control of TRS Emissions from Existing Kraft Pulping Mills," U. S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards, Research Triangle Park, NC, EPA 450/2-78-003b, March 1979.
13. "Control Techniques for Sulfur Oxide Emissions from Stationary
Sources," U. S. Environmental Protection Agency, Office of Air Quality
Planning & Standards, Research Triangle Park, NC, EPA 450/3-81-004.
14. "A Study to Improve EPA Methods 15 and 16 for Reduced Sulfur Compounds,"
U. S. Environmental Protection Agency, Environmental Monitoring &
Support Laboratory, Research Triangle Park, NC, EPA 600/4-80-023,
April 1980.
15. "Review of New Source Performaance Standards for Kraft Pulp Mills,"
U. S. Environmental Protection Agency, Office of Air Quality Planning
& Standards, Research Triangle Park, NC, EPA 450/3-83-017, Sept. 1983.
16. "Standards Support & Environmental Impact Statement Vol. 1: Proposed
Standards of Performance for Kraft Pulp Mills," U. S. Environmental
Protection Agency, Office of Air & Waste Management, Research Triangle
Park, NC, EPA 450/2-76-014a, Sept. 1976.
17. "Environmental Pollution Control, Pulp and Paper Industry, Part 1,
Air," U. S. Environmental Protection Agency, Technology Transfer
Series, EPA 7625/7-76-001, Oct. 1976.
18. Paul Kenling & Jeremy Hales, "Air Pollution & The Kraft Pulping
Industry," U.S. Department of Health, Education & Welfare, Public Health
Service, Division of Air Pollution, Nov. 1963.
19. "Atmospheric Emissions from the Pulp & Paper Manufacturing Industry,"
U. S. Environmental Protection Agency, Office of Air & Water Programs,
Office of Air Quality Planning & Standards, Research Triangle Park,
NC, EPA 450/1-73-002, Sept. 1973.
20. "Survey of Kraft Mill Gaseous Emissions Using Gas Chromatographic
Techniques," Technical Bulletin No. 16, National Council of the Paper
Industry for Air and Stream Improvement, 260 Madison Avenue, New
York, NY, Oct. 1962.
21. "A Method of Measuring the Concentration of Sulfur Compounds in
Process Gas Streams," Technical Bulletin No. 28, National Council of
the Paper Industry for Air and Stream Improvement, 2670 Madison
Avenue, New York, NY, Sept. 1965.
22. "Current Practices in Thermal Oxidation of Noncondensible Gases in
the Kraft Industry," Technical Bulletin No. 34, National Council of
the Paper Industry for Air and Stream Improvement, 260 Madison Avenue,
New York, NY, Oct. 1967.
23. "Sampling and Analysis of Airborne Gaseous Effluents Resulting from
Sulfate Pulping," Technical Bulletin No. 1, National Council of the
Paper Industry for Air and Stream Improvement, 260 Madison Avenue,
New York, Sept. 1957.
13-2
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24. "Methods for the Determination of Sulfur Compounds in Pulp Mill
Effluent Gases," Technical Bulletin No. 5, National Council of the
Paper Industry for Air and Stream Improvement, 260 Madison Avenue,
New York, NY, Sept. 1958.
25. "A Manual for Adsorption Sampling and Gas Chromatographic Analysis of
Kraft Mill Source Gases," Technical Bulletin No. 13, National Council
of the Paper Industry for Air and Stream Improvement, 260 Madison
Avenue, New York, NY., Sept. 1960.
26. "Manual for the Sampling and Analysis of Kraft Mill Recovery Stack
Gases," Technical Bulletin No. 14, National Council of the Paper
Industry for Air and Stream Improvement, 260 Madison Avenue, New
York, NY, Oct. 1960.
27. "A Guide to the Use of Permeation Tubes as Primary Standards for
Instrument Calibration," Technical Bulletin No. 47, National Council of
the Paper Industry for Air and Stream Improvement, 260 Madison Avenue,
New York, NY, May 1970.
28. "A Guide to the Design, Maintenance and Operation of TRS Monitoring
Systems," Technical Bulletin No. 89, National Council of the Paper
Industry for Air and Stream Improvement, 260 Madison Avenue, New
York, NY, Sept. 1977.
29. "Observation of Field Performance of TRS Monitors on a Kraft Recovery
Furnace," Technical Bulletin No. 91, National Council of the Paper
Industry for Air and Stream Improvement, 260 Madison Avenue, New
York, NY, Jan. 1978.
30. "A Laboratory and Field Study of Reduced Sulfur Sampling and Monitoring
Systems," Technical Bulletin No. 81, National Council of the Paper
Industry for Air and Stream Improvement, 260 Madison Avenue, New
York, NY, Oct. 1975.
31. Banchero, J. T. and F. H. Vernoff. "Predicting Dew Point of Flue
Gases." Chem. Eng. Progress, 1974, Vol.. 70, pp. 71-72.
32, Robinson, E. and R. C. Robbins. Source Abundance and Fate of Gaseous
Atmosphrlc Pollutants, Sanford Research Institute Project PR 6735,
February 1968.
32. Cullis, C. F. and M. F. R. Mulcahy. "The Kinetics of Gaseous Sulfur
Compounds, Combustion and Flame." 1972, Vol. 18, p. 225.
33. W. G. DeWees, D. J. von Lehmden, and C. Nelson. "Quality Assurance
Handbook for Air Pollution Measurement Systems, Volume III: Stationary
Source Specific Methods," U. S. Environmental Protection Agency. EPA
600/4-77-027b, August 1977.
34. "Evaluation of Stationary Source Performance Tests," Observation
and Evaluation of Performance Test Series D. PEDCo Environmental,
Inc., Durham, NC, U. S. Environmental Protection Agency, Office of
Air, Noise and Radiation, EPA Series 1-200, July 1982.
13-3
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35. Cheney, 3. 1., W. T. Winberry, and J. B. Homolya. "A Sampling and
Analytical Method for the Measurement of Primary Sulfate Emissions,"
J. Environ. Sci. Health, 1977, Vol. A12, No. 10, P. 549.
36. D. Flint. "The Investigation of Dew Point and Related Condensation
Phenomena in Flue Gases," J. Inst. Fuel, 1948, Vol. 21, P. 248.
37. Dietz, R. N., R. F. Wieser, and L. Newman. "Evaluation of a Modified
Method of Flue Gas Sampling Procedure," Workshop Proceedigns on Pri-
mary Sulfate Emissions from Combustion Sources, Volume 1: Measurement
Technology, EPA 600/9-78-020a, August 1978.
38. "Air Compliance Inspection Manual," U. S. Environmental Protection
Agency, Stationary Source Compliance Division, Washington, DC, December
1984, (DRAFT).
39. "Environmental Pollution Control - Pulp and Paper Industry - Part I
(Air)," EPA 625/7-76-001, October 1976.
40. Hawks, R. and G. Saunders. "Kraft Pulp Mill Inspection Guide," EPA
340/1-83-017, February 1983.
41. Wilson, M. L., D. F. Elias, R. C. Jordan and 0. G. Durham. "Atmospheric
Samping," Air Pollution Training Institute, U. S. Environmental Protec-
tion Agency, EPA 450/2-80-004, September 1980.
42. "Industrial Guide for Air Pollution Control," EPA 625/6-78-004, June 1978.
43. Vincent, E. J. and R. D. Blosser, "Atmospheric Emissions From the Pulp
and Paper Manufacturing Industry," U. S. Environmental Protection Agency,
EPA 450/1-73-002, September 1973.
44. Shreve, R. N., The Chemical Process Industries, McGraw-Hill Book
Company, Inc., 1945.
45. "Control Techniques for Sulfur Oxide Emissions From Stationary
Sources," U. S. Environmental Protection Agency, EPA 450/3-81-004,
April 1981.
46. Eaton, W. C., "Use of the Flame Photometric Detector Method for
Measurement of Sulfur Dioxide in Ambient Air," EPA 600/4-78-024, May
1978.
47. "Evaluation of Method 16A Particulate Filtration - Summary Test
Report," PEDCo Environmental, Inc., Contract No. 68-02-3760, Assignment
No. 3, PN 3585-3, U. S. Environmental Protection Agency, Research
Triangle Park, NC, February 1983.
48. Brenchley, D. L., C. D. Turley and R. F. Yarmac, Industrial Source Sampling,
Ann Arbor Science, 1973.
49. Richards, J. R., "Baseline Techniques for Air Pollution Control Equipment
Performance Evaluation," U. S. Environmental Protection Agency, Station-
ary Source Compliance Division, Washington, DC, February 1983, (DRAFT).
13-4
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50. "Review of New Source Performance Standards for Kraft Pulp Mills,"
EPA 450/3-83-017, September 1983.
51. Hendrickson, E. R., J. E. Roberson and J. B. Koogler. "Control of
Atmospheric Emissions in The Wood Pulping Industry." Final Report,
Contcact No. CP" 22-69-18, J. E. Sirrine Company, March 1970.
52. "Continuous Emission Monitoring Evaluation Procedures," W. T.
Winberry, Jr., U. S. Environmental Protection Agency, Stationary
Source Compliance Division, Washington, DC. (DRAFT), June 1984.
53. "Field Inspection Notebook," W. T. Winberry & D. Decker, U.S.
Environmental Protection Agency, Stationary Source Compliance Division,
Washington, DC, Contract 68-01-6312, Work Assignment #62 and 99,
October 1983.
54. "Memorandum on Inspection Procedures (April 22, 1979)," from the
Assistant Administrator for Enforcement to the Regional Administrators,
Surveillance and Analysis Division Directors, and Enforcement Division
Directors, U. S. Environmental Protection Agency, published in The
Environmental Reporter, Bureau of National Affairs, Inc., Washington,
DC, 6-8-79.
55. Clean Air Act. (42 U.S.C. 7401 et seq., as amended by the Air Quality
Act of 1967, PL 90-148; Clean Air Amendments of 1970, PL 91-604;
Technical Amendments to the Clean Air Act, PL 92-157; PL 93-15, April 9,
1973; PL 93-319, June 24, 1974; Clean Air Act Amendments of 1977,
PL 95-95, August 7, 1977; Technical Amendments to the Clean Air Act,
PL 95-190 November 16, 1977). Published in the Environmental Reporter,
Bureau of National Affairs, Inc. Washington, D. C., 12-23-77.
56. Memorandum on "Criteria for Neutral Inspections of Stationary Sources
under Title I of the Clean Air Act - - - Final Guidance," from the
Director of Division of Stationary Source Enforcement to Enforcement
Division Directors, Region I-X. Office of Enforcement. U. S.
Environmental Protection Agency. October 29, 1980.
57. Quarles, Perrin. "State and Local Government Surveillance Targeting
Techniques," Draft Report, Perrin Quarles Associates, Inc. Environ-
mental Protection Agency Contract No. 68-01-6312, Task No. 92. June 26,
1984.
58. Memorandum on "Regional Office Criteria for Neutral Inspections of
Stationary Sources -- Amended Guidance," from the Director of Division
of Stationary Source Enforcement to Enforcement Division Directors,
Region I-X. Office of Enforcement. U. S. Environmental Protection
Agency. May 13, 1981.
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13-6
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14.0 INDEX
Agency Level Program 4-1 4-9 through 4-20
Agency Phase Program 4-1, 4-2, 4-3, 4-4, 4-5, 4-6, 4-7, 4-8, 4-9, 11-38
Air Driven Eductor 5-22
Appendix F, Procedure 1, 11-2, 11-3
B
Bendix TRS Analyzer 5-74, 5-75, 5-76, 5-77, 5-78, 5-79
C
Calibration Drift 8-15, 9-3, 9-7, 9-20, 11-6
Candel Industries Limited 5-41, 5-42, 5-43
Certification 6-27, 6-32
Certified Reference Materials 6-22
Charlton Technology TRS System 5-43, 5-44, 5-45, 5-46
Clean Air Act 3-1, 3-3, 3-5, 4-1, 4-4, 4-11
Closing Conference 4-19
Code of Federal Regulations 3-7, 3-13, 3-21, 3-26
Columbia Scientific Industries 5-46, 5-47, 5-48
Conditioning System 5-15, 5-70, 5-78, 8-17
Control Device 4-18
Cbulometric 5-30
Dimethyl Disulfide 1-3, 2-17
Dimethyl Sulfide 1-3, 2-17
Dynamic Calibration 6-1
Electrocatalytic 5-88
Electrochemical Transducer 5-25, 5-43, 5-86
EPA Protocol No. 1 Gases 6-25, 6-26
Excess Emission Report 4-2, 4-9, 4-11, 4-15 10-1, 10-2, 10-3, 10-4, 10-9,
10-15, 10-16, 10-17, 10-18, 10-19
Extractive Monitoring System 5-2, 5-3
Federal Reference Method 16 8-1, 8-3, 11-30
FEP Teflon 6-4
Filter 8-18, 8-19
Flame Photometric 5-28, 5-49
Flame Photometric Detector 7-3, 7-4
Fluorescence 5-26
Gas Chromatography 5-32, 5-33, 5-65, 8-11
Gas Cylinder 6-16, 6-17
Gas Cylinder Audit System 11-41, 11-42, 11-43
Gas Manufacturers Certified Reference Materials 6-22
Gas Manufacturers Primary Standard 6-22, 6-23
14-1
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H
Hydrogen Sulfide 1-2, 1-3, 2-17, 6-32
I
Implementation Plans 3-6
In-situ Monitoring System 5-2
ITT-Barton Titrator 5-57, 5-58, 5-59, 5-60, 5-61, 5-62
Kraft Process 2-1
L
Lag Time 5-12
Lear Siegler 5-52, 5-53, 5-54, 5-55, 5-56
Logbooks 11-32, 11-33, 11-34, 11-35
M
Management Control System 4-6
Methyl Mercaptan 1-3, 2-17, 2-19,
Monitor Location 9-5, 9-18
N
National Bureau of Standards 6-7, 6-8
National Bureau of Standards - Standard Reference
Materials 6-20, 6-21
Neutral Sulfite Semichemical 2-5
New Source Performance Standards 3-2, 3-19, 3-26, 3-30
0
Orifice Meter 6-15,
Oxygen Analyzers 5-84, 5-85, 5-86, 5-87, 5-88, 5-89, 5-90, 5-91
Paramagnetic 5-89, 5-90, 5-91
Particulate Filtration 5-5, 5-77
Performance Specification Test 3, 9-14
Performance Specification Test 5, 9-1, 9-4, 9-11
Performance Specification Testing 4-2, 4-3, 4-8, 4-9, 9-1
Permanent File 4-9, 4-10
Permeation Dryer 5-16
Permeation Tubes 6-1, 6-2, 6-3, 6-4, 8-7, 8-8
Permeation Tube Audit System 11-40
Permeation Tube Rate 6-5
Permeation Vials 6-11
Permit 4-4, 4-5
14-2
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P (Contd.)
Portable H2$ CEM 11-31
Portable Test Atmosphere Generating Device 11-45
Precision 11-19
Prevention of Significant Deterioration 3-3, 4-5
Preventive Maintenance 11-27, 11-28, 11-29
Probe 5-8
Promulgated Federal Reference Method 16A, 8-23
Proposed Federal Reference Method 16A, 8-16, 8-17
Pulp Mill Population 2-6
Pumps 5-20, 5-21, 5-22, 5-23, 5-24
Quality Assurance 4-8, 11-1, 11-4, 11-11, 11-12, 11-13, 11-20
Quality Control 11-4, 11-20
Relative Accuracy 9-9, 9-19, 11-5, 11-19
Rotameter 6-13, 6-14
Sample Line 5-8, 5-9, 5-10, 5-11
Sampling Technology Inc. TRS CEM System 5-68, 5-69, 5-70, 5-71, 5-72, 5-73
Single Dilution System 6-12, 6-13, 6-14
S02 Scrubber 5-17, 5-18, 8-17
Span Valve 9-4, 9-5
Standard Operating Procedure (SOP) Manual 4-6
Standards of Performance for Kraft Pulp Mills 3-31
State Implementation Plan 3-4, 3-14, 3-21, 3-23
Stratification 9-6, 9-18
Sulfur 1-1
Sulfite Process 2-4
TFE Teflon 6-4
Tracor Atlas 5-50, 5-51
Troubleshooting 11-25, 11-26
TRS Oxidizer 5-18, 5-19, 8-17
W
Walk-through Inspection 4-12
Western Research TRS CEM 5-63, 5-64, 5-65, 5-66, 5-67
Working File 4-9
14-3
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14-4
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