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

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                                       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

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                                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.

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                                   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
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                             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.

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11

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                        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

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                      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

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                  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

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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

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                      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

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                      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

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                      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

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                       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

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                        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

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                  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

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                         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

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                   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

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                    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

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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

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     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

-------
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

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                             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.
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        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.

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     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

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        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

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                                                          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).

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                           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)  ..."
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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

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     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

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     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>

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                                                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

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                                                       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

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                                                      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

-------
     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

-------
     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

-------
     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

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              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

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      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

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              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

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     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

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                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

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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

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     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.
                                   4-3

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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.
                                    4-4

-------
     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;
                                   4-5

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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
                                      4-14

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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;


                                      4-15

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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.

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     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

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                 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

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                                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

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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

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     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

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     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

-------
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

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     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

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                                            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

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   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

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                    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

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                         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

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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

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     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

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     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

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     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

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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

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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

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     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

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     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

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     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

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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

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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

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     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

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                                              CAL GAS
Figure 5.41.  ITT Barton Probe/Extractive System.
                       5-60

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HEAT TRACED
SAMPLE LINE
                                     SAMPLING MODULE
> VENT
                                                                SAMPLE
                                                               250 CC/MIN
                                                           J
                                AMBIENT
                                  AIR
                Figure  5.42.   ITT Barton Sampling Module.

                                   5-61

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 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

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      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

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     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

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                          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

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         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

-------
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

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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

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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

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     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

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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

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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

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     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

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     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

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                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

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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

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                                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

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     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

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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

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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

-------
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

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                             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

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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

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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

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                                                            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

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                  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/




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p,.- ',
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-------
     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

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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

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                                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

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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.

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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

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     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

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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

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8-34

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                   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)
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                                    9-2

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   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

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   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

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     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

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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

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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

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 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

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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

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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

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                                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

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                          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

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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

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                                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

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                                                        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.

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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

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     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

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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

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                      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

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                                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

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                          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

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              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



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     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

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          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

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                          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

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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

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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

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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

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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

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                           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

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                                             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

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                       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

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10-18

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                         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

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10-20

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                  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

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     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

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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

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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

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                                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

-------
     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

-------
     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

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     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.
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                                                     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
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       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

-------
     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

-------
        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

-------
                                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

-------
             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

-------
     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

-------
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

-------
          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

-------
              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

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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

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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

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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

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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

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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

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 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

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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

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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

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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

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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

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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

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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

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                            13.0 BIBLIOGRAPHY


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                                    13-2

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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).


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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.
                                   13-5

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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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