### D. Harris September 22, 2015 Correspondence to R. Kaplan



# Exhibit C

USEPA Mercury CEMS Report

# Long-Term Field Evaluation of Mercury (Hg) Continuous Emission Monitoring Systems: Coal-Fired Power Plant Burning Eastern Bituminous Coal and Equipped With Selective Catalytic Reduction (SCR), Electrostatic Precipitator (ESP), and

Wet Scrubber:

Field Activities From November 2004 to September 2005

Final Report

Volume 1 (of 3)—Text

For U.S. Environmental Protection Agency

EPA Contract GS-10F-0127J

MRI Project No. 110489

November 29, 2006

# Long-Term Field Evaluation of Mercury (Hg) Continuous Emission Monitoring Systems: Coal-Fired Power Plant Burning Eastern Bituminous Coal and Equipped With Selective Catalytic Reduction (SCR), Electrostatic Precipitator (ESP), and

Wet Scrubber:

Field Activities From November 2004 to September 2005

Final Report

Volume 1 (of 3)—Text

For U.S. Environmental Protection Agency Office of Air Quality Planning and Standards Air Quality Assessment Division Measurement Technology Group Research Triangle Park, North Carolina 27711

Attn: Mr. Bill Grimley

EPA Contract GS-10F-0127J

MRI Project No. 110489

November 29, 2006

### iii 

# Preface

This report was prepared by Midwest Re search Institute (MRI) for the U.S. Environmental Protection Agency (EPA) unde r Contract No. GS-10F-0127J. Mr. Bill Grimley is the EPA Project Manager. Field wo rk activities for the report were performed from November 2004 through September 2005. This report was prepared on a follow-up contract as the original cont ract expired in September, 2005.

The test program was conducted in MRI’s Applied Engineering Division, with Mr. John Hosenfeld serving as MRI’s Project Leader. In th is report, MRI presents a summary of activities surr ounding installation of merc ury Continuous Emissions Monitoring System (Hg CEMS), certificati on results including the final Relative Accuracy Test Audit (RATA), and the long-term monitoring phase.

M IDWEST 

### R ESEARCH 

### I NSTITUTE



### John Hosenfeld Project Leader

Approved:

Roger Starnes

Director

September 29, 2006

### iv

### v 

# Contents

Preface........................................................................................................................ ........ iii Figures........................................................................................................................ ....... vii

Tables......................................................................................................................... ........ ix

Section 1. Introduction................................................................................................... 1-1 1.1 Study Overview......................................................................................... 1-1 1.2 Performance Testing.................................................................................. 1-2

1.3 Test Site..................................................................................................... 1-3 1.4 Summary of Systems Evaluated................................................................ 1-3 1.5 Test Program Organization........................................................................ 1-5

Section 2. Durability, Availabili ty, and Maintenance of CEMS ................................... 2-1 2.1 Durag ......................................................................................................... 2-4 2.2 Forney/Genesis.......................................................................................... 2-5

2.3 Horiba........................................................................................................ 2-6 2.4 Opsis.......................................................................................................... 2-6

2.5 Tekran........................................................................................................ 2-7

2.6 Thermo ...................................................................................................... 2-8 2.7 Summary.................................................................................................... 2-9

Section 3. Sampling ....................................................................................................... 3-1

3.1 Process Data .............................................................................................. 3-1 3.2 Flue Gas Sampling Location ..................................................................... 3-1 3.3 Ontario Hydro Method .............................. Error! Bookmark not defined. 1

3.4 Reference Gases .................................................................................... 3-111

Section 4. Certification Test Results.............................................................................. 4-1

4.1 Phase 1 Certification Test Results............................................................. 4-1

4.2 Phase 2 Certification Test Results........................................................... 4-31

Section 5. Quality Assurance/Quality Control............................................................... 5-1 5.1 Phase 1 Certification Testing..................................................................... 5-1 5.2 Phase 2 Certification Testing................................................................... 5-11

Section 6. Hg CEMS Conclu sions and Recommendations ........................................... 6-1 6.1 Performance Findings................................................................................ 6-1

6.2 Conclusions and Recommendations.......................................................... 6-1

### vi Appendices

Volume 2: Phase 1 Supporting Data Appendix A—Plant Process Data Appendix B—Sample Traceability Appendix C—Ontario Hydro Sampling Data Appendix D—Sampling Equipment Calibration Data Appendix E—Mercury Analysis Re sults (Oxford Laboratories) Appendix F—Hg CEMS Relative Accuracy Test Data Appendix G—Part 75 Appendix K Method Test Data Appendix H—Glossary of Acronyms

Volume 3: Phase 2 Supporting Data Appendix A—Plant Process Data Appendix B—Sample Traceability Appendix C—Ontario Hydro Sampling Data Appendix D—Sampling Equipment Calibration Data Appendix E—Mercury Analysis Re sults (Oxford Laboratories) Appendix F—Hg CEMS Relative Accuracy Test Data Appendix G—Long-Term Monitoring Da ta: Daily Calibration Error Results Appendix H—Long-Term Monitoring Data: Weekly System Integrity Results Appendix I —Glossary of Acronyms

### vii 

# Figures

Figure 1-1. Test Program Organization...................................................................... 1-6 Figure 2-1. Phase 1 and 2 Long- Term Monitoring Periods...................................... 2-10 Figure 3-1. Layout of Sampling Ports and Hg CEMS and Other Sampling Systems During Phase 1 RATA Test..................................................... 3-33 Figure 3-2. Layout of Sampling Ports and Hg CEMS and Other Sampling Systems During Phase 2 RATA Test....................................................... 3-4 Figure 3-3. Sampling Location at the Unit #1 Stack North Inlet Duct..................... 3-55 Figure 3-4. Hg CEMS Sampling Conf iguration During Phase 1 RATA ................. 3-66 Figure 3-5. Hg CEMS Sampling Conf iguration During Phase 2 RATA ................. 3-77 Figure 3-6. Ontario Hydr o Sampling Train .............................................................. 3-99 Figure 3-7. Ontario Hydro Sa mple Recovery Scheme ........................................... 3-100 Figure 4-1. Phase 1 OH Gaseous Ph ase Mercury Concentrations............................ 4-18 Figure 4-2. Decision Tree for Blank Corrections ..................................................... 4-20 Figure 4-3. Summary of RA Phase 1 Tests .............................................................. 4-22 Figure 4-4. Phase 1 RA—OH Versus Forney/Genesis............................................. 4-23 Figure 4-5. Phase 1 RA—OH Versus Horiba........................................................... 4-24 Figure 4-6. Phase 1 RA—OH Versus Tekran .......................................................... 4-24 Figure 4-7. Phase 1 RA—OH Versus Thermo ......................................................... 4-25 Figure 4-8. Tekran Hg 0 

### Spiking................................................................................ 4-31 Figure 4-9. Phase 2 OH Gaseous Ph ase Mercury Concentrations............................ 4-67 Figure 4-10. Decision Tree for Blank Corrections ..................................................... 4-68 Figure 4-11. Phase 2 Summary of RA Tests .............................................................. 4-70 Figure 4-12. Phase 2 RA—OH Versus Durag............................................................ 4-71 Figure 4-13. Phase 2 RA—OH Versus Opsis............................................................. 4-71 Figure 4-14. Phase 2 RA—OH Versus Tekran .......................................................... 4-72 Figure 4-15. Phase 2 RA—OH Versus Thermo ......................................................... 4-72 Figure 6-1. Phase 1 and 2 Long- Term Monitoring Periods........................................ 6-4

### viii

### ix 

# Tables

Table 1-1. Summary of Certificatio n and Relative Accuracy Test

Performance Criteria................................................................................ 1-2 Table 1-2. Phase 1 Summary of Hg CEMS Evaluated.............................................. 1-3 Table 1-3. Phase 2 Summary of Hg CEMS Evaluated.............................................. 1-4 Table 2-1. Summary of Phase 1 Maintenance Events for Hg CEMS (Nov 2004-Feb 2005)............................................................................... 2-2 Table 2-2. Summary of Phase 2 Maintenance Events for Hg CEMS (Mar-Sept 2005)....................................................................................... 2-3 Table 3-1. Phase 1 Average Plant CEM Data ........................................................... 3-2 Table 3-2. Phase 2 Average Plant CEM Data ......................................................... 3-22 Table 3-3. Elemental Mercury Cylinders.............................................................. 3-122 Table 4-1. Summary of Phase 1 CE MS Certification Criteria and Performance (Excluding RATA) ............................................................. 4-1 Table 4-2. Forney 7-Day Calibra tion Error Test—Phase 1....................................... 4-2 Table 4-3. Horiba/Nippon 7-Day Ca libration Error Test—Phase 1.......................... 4-3 Table 4-4. Horiba/Nippon Li nearity Test—Phase 1 ................................................. 4-4 Table 4-5. Horiba/Nippon System Integrity Test—Phase 1...................................... 4-4 Table 4-6. Horiba/Nippon Measur ement Error Test—Phase 1................................. 4-5 Table 4-7. Horiba/Nippon Zero/U pscale Drift Tests—Phase 1 ................................ 4-5 Table 4-8. Tekran 7-Day Calibra tion Error Test—Phase 1....................................... 4-6

Table 4-9. Tekran Linear ity Test—Phase 1 .............................................................. 4-6 Table 4-10. Tekran System In tegrity Test—Phase 1 .................................................. 4-7 Table 4-11. Tekran Cycle Time—Phase 1 .................................................................. 4-7

Table 4-12. Tekran Measurement Error Test—Phase 1.............................................. 4-8 Table 4-13. Tekran Zero/Upscal e Drift Tests—Phase 1 ............................................. 4-8 Table 4-14. Thermo 7-Day Calibra tion Error Test—Phase 1 ..................................... 4-9

Table 4-15. Thermo Linear ity Test—Phase 1............................................................. 4-9 Table 4-16. Thermo System Integrity Test—Phase 1 ............................................... 4-10 Table 4-17. Thermo Cycle Time—Phase 1............................................................... 4-10

Table 4-18. Thermo Measurement Error Test—Phase 1 .......................................... 4-10 Table 4-19. Thermo Zero/Upscale Drift Tests—Phase 1.......................................... 4-11

Table 4-20. Phase 1 RA Test Run Times .................................................................. 4-12 Table 4-21. Phase 1 RA Test Stack Sampling Data.................................................. 4-13

Table 4-22. Phase 1 RA Test Ontari o Hydro Mercury Analysis Results ( μ g).......... 4-14 Table 4-23. Phase 1 RA Total OH Mercury Concentrations .................................... 4-15

Table 4-24. Phase 1 Gaseous -Phase OH Mercury .................................................... 4-16 Table 4-25. Phase 1 Duplicate OH Train Relative Deviation ................................... 4-17 Table 4-26. Phase 1 Summary of All RA Results for All CEMS ............................. 4-21 Table 4-27. Phase 1 RA Results for Forney/Genesis ................................................ 4-25

Table 4-28. Phase 1 RA Results for Horiba (All 12 Runs) ....................................... 4-26

Table 4-29. Phase 1 RA Results for Tekran (All 12 Runs)....................................... 4-27 Table 4-30. Phase 1 Initial RA Results for Thermo (All 12 Runs)........................... 4-28

Table 4-31. Phase 1 RA Results for Appendix K Method ........................................ 4-29 Table 4-32. Comparison of Sorbent Trap and Hg CEMS Data (12/16/04)............... 4-30

### x Table 4-33. Tekran Elemental Mercury Sample Spikes............................................ 4-30 Table 4-34. Summary of Phase 2 CE MS Certification Criteria and Performance (Excluding RATA) ........................................................... 4-32 Table 4-35. Durag 7-Day Calibration Error Test—Phase 2...................................... 4-33 Table 4-36. Durag Linear ity Test—Phase 2.............................................................. 4-34 Table 4-37. Durag System In tegrity Test—Phase 2.................................................. 4-35 Table 4-38. Durag Cycle Time—Phase 2 ................................................................. 4-36 Table 4-39. Durag Measurement Error Test—Phase 2 ............................................. 4-37 Table 4-40. Durag Zero/Upscal e Drift Tests—Phase 2 ............................................ 4-38 Table 4-41. Opsis 7-Day Calibra tion Error Test—Phase 2....................................... 4-40 Table 4-42. Opsis Linear ity Test—Phase 2............................................................... 4-42 Table 4-43. Opsis System In tegrity Test—Phase 2................................................... 4-43 Table 4-44. Opsis Cycle Time—Phase 2 .................................................................. 4-44 Table 4-45. Opsis Measurement Error Test—Phase 2.............................................. 4-45 Table 4-46. Opsis Zero/Upscal e Drift Tests—Phase 2 ............................................. 4-46 Table 4-47. Tekran 7-Day Calibra tion Error Test—Phase 2..................................... 4-48

Table 4-48. Tekran Linear ity Test—Phase 2 ............................................................ 4-50 Table 4-49. Tekran System In tegrity Test—Phase 2 ................................................ 4-51 Table 4-50. Tekran Cycle Time Test—Phase 2 ........................................................ 4-52

Table 4-51. Tekran Measurement Error Test—Phase 2............................................ 4-53 Table 4-52. Tekran Zero/Upscal e Drift Tests—Phase 2 ........................................... 4-54 Table 4-53. Thermo 7-Day Calibra tion Error Test—Phase 2 ................................... 4-55

Table 4-54. Thermo Linear ity Test—Phase 2........................................................... 4-56 Table 4-55. Thermo System Integrity Test—Phase 2 ............................................... 4-57 Table 4-56. Thermo Cycle Time—Phase 2............................................................... 4-57

Table 4-57. Thermo Measurement Error Test—Phase 2 .......................................... 4-58 Table 4-58. Thermo Zero/Upscale Drift Tests—Phase 2.......................................... 4-59

Table 4-59. Phase 2 RA Test Run Times .................................................................. 4-60 Table 4-60. Phase 2 RA Test Stack Sampling Data.................................................. 4-61

Table 4-61. Phase 2 RA Test Ontari o Hydro Mercury Analysis Results ( μ g).......... 4-62

Table 4-62. RA Total OH Me rcury Concentrations.................................................. 4-64

Table 4-63. Phase 2 RA Gaseous-Pha se Mercury From OH Testing ....................... 4-65 Table 4-64. Phase 2 Duplicate OH Tr ain Relative Deviation (RD).......................... 4-66 Table 4-65. Phase 2 Summary of All RA Results for All CEMS ............................. 4-69 Table 4-66. Phase 2 RA Results for Durag ............................................................... 4-73 Table 4-67. Phase 2 RA Results for Opsis ................................................................ 4-74

Table 4-68. Phase 2 RA Results for Tekran.............................................................. 4-75

Table 4-69. Phase 2 RA Results for Thermo............................................................. 4-76 Table 4-70. IRM Daily Hg Tests During RATA....................................................... 4-77 Table 5-1. Summary of Phase 1 CE MS Certification Criteria.................................. 5-3 Table 5-2. Phase 1 Calibration, QC Procedures, and Criteria for Ontario Hydro Sampling Equipment ....................................................... 5-4

Table 5-3. Phase 1 Test Criteria fo r Emission Measurement and Data Quality...................................................................................................... 5-5

Table 5-4. Phase 1 RA Bla nk Analysis Results ........................................................ 5-6

Table 5-5. Percent Difference for Ph ase 1 Mercury Analysis Results...................... 5-8

### xi Table 5-6. Phase 1 RA Spike and Audit Sample Results.......................................... 5-9 Table 5-7. Phase 1 Continuing OH Calibration Check Standards .......................... 5-10 Table 5-8. Summary of Phase 2 CE MS Certification Criteria................................ 5-13 Table 5-9. Phase 2 Calibration, QC Pr ocedures, and Criteria for Ontario Hydro Sampling Equipment .................................................................. 5-14

Table 5-10. Phase 2 RA Test Criteria for Emission Measurement and Data Quality........................................................................................... 5-16

Table 5-11. Phase 2 Bla nk Analysis Results............................................................. 5-17

Table 5-12. Percent Difference for Ph ase 2 Mercury Analysis Results.................... 5-18 Table 5-13. Phase 2 RA Spike and Audit Sample Results........................................ 5-19 Table 5-14. Phase 2 Continuing OH Calibration Check Standards .......................... 5-21 Table 6-1. Summary of CEMS Certifi cation Criteria and Performance ................... 6-3

### xii

### 1-1 

# Section 1.

Introduction

1.1 Study Overview

The US Environmental Protection Agen cy (EPA) has recently promulgated regulations for mercury (Hg) emissions from co al-fired electric utilities, which include provisions for use of mercury Continuous Emission Monitoring Systems (Hg CEMS) as well as other monitoring approaches (FR 5/18/05, 70(95), 28606). The implementation of Hg CEMS could be enhanced greatly by the co llection of data demonstrating application of monitoring technologies to the source category. As a re sult, EPA conducted the field testing described to evaluate Hg CEMS t echnologies on a long-term continuous basis.

The purpose of this field test program was to collect data to assess the ability of commercially available Hg CEMS to provide reli able and accurate data over an extended time period, while meeting certification, dur ability, data availability, and setup/maintenance requirements. In particular, data were collected to assess the ability of the Hg CEMS to satisfy the requirements of Performance Specification 12A (PS-12A) and

the 40 CFR Part 75 mercury monitoring provi sions (FR 5/18/05, 70(95), 28606).

This report presents a summary of the certification test results and other information collected from November 2004, through Sept ember 2005. The test facility was a coalfired utility boiler burning eastern bituminous co al and equipped with a selective catalytic reduction (SCR) system with ammonia inject ion that is operated during ozone season (May 1 through September 30), an electrostatic precipita tor, and a wet limestone

scrubber.

The work was separated into two phases, Phase 1 and Phase 2. Phase 1 field work was performed from November 2004 th rough February 2005 and consisted of:

• 

### Installation and shakedow n of four mercury Con tinuous Emission Monitoring Systems (Hg CEMS);

• 

### Phase 1 certification testing during the fi rst two weeks of continuous Hg CEMS operation (with Relative Accuracy Test Audit [RATA], February 22 - 26);

• 

### Evaluation while the selec tive catalytic reduc tion (SCR) system was bypassed;

and

• 

### Information gathering on the Hg CEMS operation, durability, and maintenance.

Phase 2 field work was performed from March through September 2005 and

consisted of:

• 

### Installation of two additional Hg CEMS in early May (in addition to the four which were previously in operation);

• 

### Phase 2 certification testing after more than a month of continuous operation by the additional two Hg CEMS (with RATA July 7-12);

### 1-2 • 

### Removal of two Hg CEMS when vendors el ected to have their systems removed from the test program;

• 

### Evaluation while the SCR was in operation; and

• 

### Information gathering on the Hg CEMS operation, durability, and maintenance.



## 1.2 Performance Testing

Table 1-1 summarizes the certification test acceptance criteria used during this test program. Sorbent trap monitoring was conducted according to 40 CFR Part 75 Appendix K (Appendix K) by RMB Associates, and the da ta are provided in a separate report. Dynamic spiking and data collection were also performed using the Tekran Hg CEMS to assess potential crite ria for a draft instrumental test me thod for mercury; results of this test are provided in Se ction 4.1.3 of this report.

Table 1-1. Summary of Certificat ion and Relative Accuracy

Test Performance Criteria

Activity Frequency Gas type Performance

criteria Reference 7-day Calibration

Error. Check at 2 pts, zero and upscale. a Once per day for 7- day consecutive days Elemental

mercury ≤ 5% of span; or, if spanned at lowest range of

10 μ g/m 3 , then

≤ 1 μ g/m 3 Part 75, App A, Section 3.1; (FR 5/18/05, 70(95), 28691)

Linearity Check at 3 pts: low, mid, and high. b Performed in nonrepetitive triplicates. Once, at beginning of

certification test Elemental

mercury ≤ 10% of ref tag value; or

≤ 1 μ g/m 3

, whichever is less

restrictive Part 75, App A, Section 3.2; (FR 5/18/05, 70(95), 28691)

System Integrity. Check at 3 pts: zero, mid, and high. b Once, at beginning of

certification test Oxidized

mercury ≤ 5% of span Part 75, App A, Section 3.2; (FR 5/18/05, 70(95), 28691) and PS-12A,

Sections 8.3 and

13.1 Cycle Time Once, at beginning of

certification test Elemental

mercury ≤ 15 min Same as existing Part 75, App A,
Section 3.5 Relative Accuracy (RA), performed

after certification

checks One set of 12 duplicate test runs, at beginning of Phase 1

evaluation test program, and againduring Phase 2 longterm evaluation Stack Gas ≤ 20%; or for low emitters with avg.

conc. < 5 μ g/m 3

, ≤ 1 μ g/m 3

difference Part 75, App. A, Section 3.3 (FR 5/18/05, 70(95), 28691) and

PS-12A

Section 13.4

a Conducting the 7-day Cal Error test allows for determi nation of the Zero and Upscale Drift specification of PS-12A, which cannot exceed 5% of span (Sections 13.2 and 13.3).

b By collecting linearity check data and system integr ity check data (per Part 75 requirements), the PS-12A Measurement Error and Converter Efficiency tests are al so effectively performed, except that the PS-12A

criterion is ≤ 5% of span with no alternative cr iteria when the stack concentration is ≤ 1 μ g/m 3

.

### 1-3 

## 1.3 Test Site

The facility at which the evaluation testi ng was conducted consists of a coal-fired generating unit referred to as Unit 1. Unit 1 is 14 years old with a capacity of 550 MW. The facility was designed with state-of-the-art pollution c ontrols that include ammonia injection and selective catalytic reduction (SCR) for NO

x 

### control, an electrostatic precipitator for particulate control, a nd a wet limestone slurry scrubber for SO 2 

### control. The facility has been permitted according to EPA criteria for Best Achievable Control Technology (BACT). Fuel for the fac ility is eastern bituminous coal.

The sampling location was at ~ 350 ft up the stack. Section 3 provides further details on the test facility and sampling locations.



## 1.4 Summary of Systems Evaluated

This study was designed to evaluate Hg CE MS that use the latest technology, i.e., dry converter or alternative systems rather than the older wet converter systems. A summary of the Hg CEMS that were eval uated during Phase 1 using the performance

certification test criteria is provided in Table 1-2. A summary of the Hg CEMS that were evaluated during Phase 2 is provided in Table 1-3.

Table 1-2. Phase 1 Summary of Hg CEMS Evaluated

Parameter Forney/Genesis CEM Horiba/Nippon

DM-6D Tekran 3300 Thermo Electron
Gas Conditioning System Glass fiber particulate filter, thermocatalytic converter, chilled KOH impinger, chilled

moisture removal impinger, acid mist

filter. Glass fiber particulate filter, thermocatalytic converter, vapor separator, chilled

dehumidifier tube at probe. Chilled KOH impinger at detector. Inertial filter and dilution system atprobe. Thermocatalytic converter, water wash system at sample conditioner. Inertial filter, dilution system, thermocatalytic converter at probe.

Mercury Detector Cold vapor atomic absorption Cold vapor atomic absorption Cold vapor atomic

fluorescence Cold vapor atomic

fluorescence Measurement Range 0-50 μ g/m 3 0-50 μ g/m 3 Dilution system allows multiple ranges 0-15 μ g/m 3

Resolution 0.1 μ g/m 3 0.1 μ g/m 3 0.001 μ g/m 3 0.01 μ g/m 3

Response Delay Update every 1

second Update every 1

second 2.5 minutes per cycle None. Continuous reading via 4-20 mAoutput, user configurable time averaging on instrument display. Sample Flow Rate 3 LPM 0.5 LPM 0.5 LPM 0.75 LPM Zero Point Adjustment Automatic, once per

hour Automatic, once per

hour None Automatic, daily

Daily Calibration Requirements None. Factory calibrated prior to

installation. None. Factory calibrated prior to

installation. Daily automatic

detector calibration via internal Hg gas generator Daily system calibration via Hg calibration gas generator Output 4-20 mA 4-20 mA System control computer 4-20 mA

Reporting Temperature 25 ° C 0° C 0° C 20 ° C Power Supply 110, 208 VAC 110 VAC 110 VAC 110, 220 VAC Other Utilities Required None DI water at probe. Compressed air, argon gas, DI water,

drain. Compressed air.1-4Table 1-3. Phase 2 Summary of Hg CEMS EvaluatedParameter Durag Forney/Genesis CEM1Horiba/Nippon DM-6D2Opsis Tekran 3300 Thermo ElectronGas ConditioningSystemCeramic filter, heatedsample line, thermocatalytic converterNA1NA2Inertial filter, dilutionsystem, andthermocatalyticconverter at probeInertial filter anddilution system atprobe. Thermocatalyticconverter, water washsystem at sampleconditioner.Inertial filter, dilutionsystem, thermocatalytic converter at probe.Mercury Detector Cold vapor atomicabsorptionNA1NA2Cold vapor atomicabsorptionCold vapor atomicfluorescenceCold vapor atomicfluorescenceMeasurement Range 0-20μg/dscm multiplerangesNA1NA20-15μg/m3Dilution system allowsmultiple ranges0-15μg/m3Resolution 0-1μg/dscm (0.01Bg/dscm if required)NA1NA20.05μg/m30.001μg/m30.01μg/m3Response Delay None. Continuousreading via 4-20 mAoutput, userconfigurable timeaveraging oninstrument display.NA1NA25 minutes per cycle 2.5 minutes per cycle None. Continuousreading via 4-20 mAoutput, userconfigurable timeaveraging oninstrument display.Sample Flow Rate 2 LPM NA1NA21.0 LPM 0.5 LPM 0.75 LPMZero Point Adjustment Automatic, every 2 hup to every 99 hNA1NA2None None Automatic, dailyDaily CalibrationRequirementsDaily systemcalibration via Hgcalibration with gascylinder, if required(automatic dailycalibration module withionic mercury will beavailable in 2006)NA1NA2Daily: NoneMonthly-QuarterlyCalibrationsDaily automaticdetector calibration viainternal Hg gasgeneratorDaily systemcalibration via Hgcalibration gasgeneratorOutput 4-20 mA NA1NA24-20 mA/0-10V/RS232 System controlcomputer4-20 mAReporting Temperature0°CNA1NA20°C/20°C 0°C 20°CPower Supply 110, 220 VAC NA1NA2110 VAC 110 VAC 110, 220 VACOther Utilities Required None NA1NA2Compressedinstrument airCompressed air, argongas, DI water, drain.Compressed air.NOTES:1Forney/Genesis CEM: This instrument was withdrawn from the test program late in Phase 2 testing at the vendor’s request.2Horiba/Nippon DM-6D: This instrument was removed at the vendor’s request prior to the second RA test series.

### 1-5 The Durag Inc., Forney Corporation/Genesi s Laboratory Systems Inc., Opsis Inc., Horiba/Nippon, and ThermoElectron Corporat ion systems were connected to the MRI data logger via their 4 to 20 mA data outputs. The MRI data logger converted each output to a 0 to 10 VDC signal which was then used to calculate the instruments’ readings. The computer display on the MRI da ta logger was verified to match the display on each of

these instruments.

Rather than a 4 to 20 mA output, the Te kran Inc. system provided instrument readings in real-time via its system control computer. The MRI data logger retrieved the

data over a local area network installed between the trailer and the st ack Hg CEM shelter.

The Horiba International Corporation/Ni ppon Instruments Corporation CEMS tested in the Phase 1 work was inoperative during Ph ase 2, and the vendor elected to have their system removed from further testing. The Fo rney/Genesis CEMS also elected to have their CEMS removed from the test pr ogram late in the Phase 2 testing.



## 1.5 Test Program Organization

The following individuals are the key personne l in the management and execution of this test project:

The EPA Work Assignment Manager (WAM) was:

Mr. Bill Grimley U.S. Environmental Protection Agency Office of Air Quality Planning and Standards Air Quality Assessment Division Measurement Technology Group Research Triangle Park, NC 27711 Telephone: (919) 541-1065

The MRI Work Assignment Leader (W AL) for this test project was:

Mr. John Hosenfeld

Midwest Research Institute

425 Volker Blvd. Kansas City, MO 64110-2299 Telephone: (816) 753-7600, ext. 1336

Figure 1-1 presents the test program or ganization, major lines of communication, names, and phone numbers of responsible i ndividuals. Midwest Research Institute was responsible for the project under contract to EPA’s Office of Air Quality Planning and

Standards.

The companies supplying the Hg CEMS for evaluation during the performance testing were Durag, Forney/Genesis, Horiba /Nippon Instruments Corporation, Opsis, Tekran, and Thermo Electron. The EPA is appreciative of these vendors for their participation in this test program.1-6Figure 1-1. Test Program Organization

### 2-1 

# Section 2. Durability, Availability, and Maintenance of CEMS

The following describes the maintenance re lated to Hg CEMS operation during the commissioning, setup, and ongoing operation of the systems at the test site. Summaries of Phase 1 and 2 maintenance events are prov ided in Tables 2-1 and 2-2, respectively.

There were two types of maintenance perf ormed on the Hg CEMS: preventative and

corrective. Preventative maintenance consiste d of tasks performed to prevent system

failure. Corrective maintenance consisted of tasks performed to br ing the system back into normal operation. Corrective maintenance on the Hg CEMS generally fell onto one of six primary categories related to system components/configurations:

• 

### Calibration

• 

### Temperature Adjustment

• 

### Sample Transfer

• 

### Catalyst/Sample Conditioning

• 

### Filter Replacement

• 

### Analyzer Replacement

Corrective maintenance performed on the systems during the setup phase did not attempt to differentiate between required maintenance caused by a natural instrument failure and maintenance required by operator intervention to system while performing

routine checks and measurements. A few ex amples of maintena nce caused by operator

intervention are:

• 

### Instrument offset required by unint entional over-pressurization or underpressurization of the system while introducing daily audit gases.

• 

### Cleaning a blocked orifice caused by intr oducing contamination to system while making connections for system integrity tests.

• 

### Maintenance caused by accidentally bump ing the probe, transfer lines, or analyzer and dislodging accumulated scale or sludge into downstream

components.

• 

### Maintenance caused by temperature ove rcompensation when opening probe

enclosures to make measurement attachments.2-2Table 2-1. Summary of Phase 1 Maintenance Events for Hg CEMS (Nov 2004-Feb 2005)Forney/Genesis Horiba/Nippon Tekran ThermoElectronSystem leaks: replaced a damagedunion and most Teflon fittingsCritical orifice in probe becameclogged: Added particulates filter.A tear was found in pump diaphragm:pump was replacedThe 450-ft heated line between sampleconditioner and analyzer cabinet wasfound to have severe contamination.Repeated attempts at cleaning failed.The heated line was abandoned andthe analyzer was moved to the stackplatformA crack in the probe moisture sensorallowed leakage: replaced the sampleline with smaller diameter TeflontubingStack thermocouple broke loose fromprobe: remaining parts were removedand the port pluggedData output failed shortly before thestart of Run 11: swapped componentsfrom an unused data output channelShort heated line between sampleconditioner and probe wascontaminated and was replacedData output showed excessiveamounts of electrical noise: installed afiltering circuit to correctA hole in the "stinger" portion of theprobe allowed leakage of acid gasesinto the heater causing failureLow flow through probe's criticalorifice: changed dilution ratiotemporarily until probe was cleanedSeveral analyzers failed over a periodof several months: acid mist filter justprior to the analyzer was installed (alsoprevents condensation from reachingthe analyzer)Repeated condensation in sampletransfer line: replaced with heated linebetween probe and analyzerAbout every 2 months material buildupon probe's main sample loop createdblockage: periodically cleaned sampleloop and replaced motive air heaterImpingers used for SO2removal werefound to cause significant loss ofmercury in sample gas. Impingers weremodified.Calcium deposits were accumulatingat the inlet of the KOH impinger:connected hourly water wash systemProbe blowback system was disabledand used as the sample line after theoriginal sample line became unusableAnalyzer exhaust line was blocked:installed heated exhaust assembly toprevent condensation from freezingProblems with condensation in thesample line between conditioner andanalyzer. Improvements made to chillerefficiencyGas/liquid separator and dehumidifiertube had signs of seleniumcontamination: connected 3X dailywater wash systemCeramic probe filter caused loss ofmercury in sample gas. Replacementwith glass fiber filter did not help.Before and during the RATA, thecatalytic converter suffered frombuildup of calcium: replacement wouldremedy for 2 to 5 daysData output showed excessiveamounts of electrical noise withintermittent output signal. Outputmodule was replaced2-3Table 2-2. Summary of Phase 2 Maintenance Events for Hg CEMS (Mar-Sept 2005)DuragForney/GenesisHoriba/NipponOpsis Tekran ThermoElectronLow airflow; replacedfilter to UV detectorReplaced broken glass tube in analyzer(improper overtightening) to correct leakReplaced probe and analyzercomponentsClosed pressure bypass dump four consecutivetimes.Replaced RTD thermocouple connector ontemperature controller to correct overheatingReplaced eductor module tocorrect plugged orificeCleaned out stinger and return port. Zero andspan check performed afterwardReplaced converterafter attempting to fixby increasingtemperature andrecalibrationReplaced probe filter and acid scrubber toimprove response timeCorrected program controlling testsequence, loop flow, and zerocalibration gas deliveryInstalled new inertial filter, probe draw tube, &probe cabinet doors. Changed draw orifice andadded time-controlled external probe blowbacksystemRotated UV light filterby 90° andrecalibrated tocorrect for nonlinearityMelted Teflon on converter causedoverheating of probe. Temporarily replacedRTD thermocouple with a K-typeReplaced eductor module,repaired melted Teflon gasconnection line to correctmeasurement of zero stack gasconcentrationRemoved thermocouple from temperaturecontroller and serviced Gold trapRepaired heat tape and heatedeductor module to correct for lowmeasurement readingsSpan adjusted to match audit gasReplaced inertial filterIncreased convertertemperature thenreplaced catalystand cleaned probeport to correct forslow response timeChanged system span and offsetReplaced dilution pump due to failed bearingReplaced orifice filter on probeIncreased probetemperature toremove accumulatedHgSystem span adjustedRemoved return loop flow tubeand cleaned venturi lines + stackgas return tube to correct for zeromeasurement readingsStack gas values measure at zero; closedpressure bypass dump port four consecutivetimes which did not help.Unspecified repairsmade over next two days then cleaned outresidual debris from fast loop tubing, cleanedlines from probe to analyzer. Increased probetemperature to burn off potential contamination.Installed redesigned probe front end assembly,added tee to probe to allow injection of systemintegrity gas to be introduced upstream of theinertial filter. Replaced four solenoid valves inanalyzed and cleaned out probe stinger.Replaced probe filterReplaced filter disk at probe (possiblecaused by plant startup)Replaced venturi pressuretransducer to correct high loopflow measurementsSystem did not measure stack gas for 5 daysbecause an operator left the system in "probezero" mode after performing daily reference gasmeasurementMaintenance to verify that orifice gasketorientation is correctNew softwareinstalled to allowsystem to operate athigher probetemperatureReplaced probe filter during July RATACleaned out return probe port tocorrect improper proportional valvemeasurementAnalog output to MRI data logger failedresulting in loss of data for several daysChanged probe filter and blew out orificeports. Also adjusted system spanRemoved and cleaned plug in theeductor orifice.Manually zeroed andincreased probetemperatureCleaned out return probeTightened 3 hinged flange bolts to correctlow measurement valuesChanged analyzer pump, probe filter, andincreased span adjustment to correct lowmeasurement valuesReplaced: sample extractionassembly (including orifice), PMT& power base, Hg conditionerfilter, sample filter on Hg analyzer;installed clean inertial filter, andnew lamp on Hg analyzerAdjusted analyzer pump voltage, analyzertemperature, and system span to correct lowmeasurement valuesReplaced probe filterto correct for lowairflow ratesVendor elected tohave their systemremoved from thetest programReplaced voltage power distribution board inanalyzer. Adjusted span and offsetReset software to correct softwarelockup. Data logger lostsynchronization with output link;lost 6 days of data.

### 2-4 

## 2.1 Durag

The Durag system was installed by manufact urer representatives during the week of May 9. The system was commissioned to st ack measurements on May 11. The system was programmed to provide a probe blowback and zero offset check every 2 hours. This procedure typically takes less than 5 minutes. The system span and zero adjustments were performed manually and verified daily by plant personnel throughout the week, Monday through Friday. The system was removed from the site on August 11. The total operation period was three months.

2.1.1 Preventative Maintenance and Checks

Routine preventative maintenance and checks included recording the system sample flow, system pressure, and the zero offset va lue to verify the parameters were within normal operating ranges. A system leak check was performed periodically to verify the system was leak-free. Also included in the routine preventative maintenance was checking and emptying the fluid level of th e condensation collection container. The container is sized to allow up to 2 months of collection before necessary emptying.

The probe filter change was performed J une after a plant outage. The excessive emissions resulting from fuel oil used duri ng plant start-up had a tendency to plug CEM filters and this filter change was a preventative measure.

2.1.2 Corrective Maintenance

The system operated throughout a 3-month peri od at the site with some downtime for preventative or corrective maintenance. Th e corrective maintenance activities to the Durag system are described below.

The span and offset adjustments were pe rformed several times during the initial system commissioning to confirm proper system measurements. Thereafter, the span and offset were adjusted approximately every month.

The sample conditioning catalyst was ch anged twice during the 3 months of operation. The catalyst was changed the first ti me in June due to damage resulting from increasing the catalyst temperature beyond the recommended temperature limit. The catalyst was changed the second time in July prior to the RATA to improve the degrading response time.

In June the analyzer glass cuvet light f ilter was suspected to be delaminating after 1 1⁄2 months of operation. The glass cuvet was rotated 90 degrees to bring the system back into normal operation.

### 2-5 The probe and catalyst temperatures were increased several times during the 3-month period. The temperature increases were performe d in an effort to overcome the system’s delayed response. The delayed response occu rred 15 minutes after each 2-hour system blowback and zero offset check. The time requi red for system to measure pre-blowback

stack concentration values in creased from a nominal 5 minutes to more than 1 hour. In July, the vendor installed new software to a llow the probe temperatur e to be set above the original high temperature limit. When the probe temperature was increased, the system

stack concentration measurements also incr eased more than 50% above the original

measurements.

The probe filter was changed tw ice to correct system problem s. The first probe filter change was performed in July during the mi ddle of a RATA test due to higher than normal Hg measurements. The second probe f ilter change was performed in August to increase the system flow rate that wa s measuring below the low limit threshold.



## 2.2 Forney/Genesis

The Forney/Genesis system was installe d in early November 2004 by personnel from Forney Corporation and Genesis Laboratory Sy stems. The system seemed functional, but exhibited anomalous responses. Testing th roughout the first three months following installation yielded anomalous responses to both reference gas and zero gas (e.g., reference gases were detected at lower than e xpected concentrations and zero gas read as though it had a high background mercury content).

The Forney/Genesis system, though not operational, remained in the stack throughout the period between the February RATA and the May certification testing. During the week before the May certification te sts, Forney representatives were on-site to perform corrective maintenance. Daily corrective and preventative maintenance was required to keep the system operating. Effo rts to continue corrective and preventative

maintenance were then ceased due to lack of replacement parts, and the system was not operational.

A Forney representative was on-site to perform corrective maintenance during the last day of the June certification tests and during the July RATA. Eventually efforts to continue corrective and preventative maintena nce were completely stopped. No further maintenance was performed on the system after Forney determined that it was discontinuing its efforts at the site. The system was removed during the second week in August.

Because the Forney system was rarely operational between corrective maintenance visits during Phase 2 of the demonstration pr oject, maintenance efforts have not been

included in Table 2-2.

### 2-6 

## 2.3 Horiba/Nippon

The Nippon DM-6D system was installed in early November 2004 by technicians from Horiba Instruments and Nippon Inst ruments Corporation. Though the system performed well immediately after installation, leaks and other problems caused deterioration of the system. Further visi ts were made by Horiba personnel in midNovember and early December, and a Nippon repr esentative was on-site in early January.

Maintenance details for this time period are included in Table 2-1.

No preventative or corrective maintenan ce was performed on the Horiba system between February and July. The system was re moved at the vendor’s request prior to the second RATA test series. When the system wa s removed from the port, the stainless steel probe was discovered to be completely co rroded away, leaving nothing but the Teflon sample line.



## 2.4 Opsis

The Opsis system was installed by manufact urer representatives during the week of May 2. The system was commissioned to stack measurements on May 6. The system was programmed to provide a zero check at the t op of every hour. This procedure typically takes less than 5 minutes. The system span and zero adjustments are performed manually and verified daily by plant personnel thr oughout the week (Monday through Friday).

2.4.1 Preventative Maintenance and Checks

Routine preventative maintenance to th e system included recording the probe temperature, the regulated compressed air pressure, and the dilution pump vacuum to ensure they were within the manufacturer’ s setpoint. Periodic preventative maintenance included replacing the probe filter.

2.4.2 Corrective Maintenance

Maintenance during the first month (May ) was mainly performed to address a temperature control problem and slow res ponse time. A broken glass tube was also replaced to correct a leak caused by impr oper over tightening of a mounting screw.

Much of the maintenance during the third month (August) was performed to address

low measurement values.

During the period of operation, the system had a slow response to known changes in Hg concentrations, i.e., from challenges with the reference gases. Corrective maintenance during this period included multiple changes of the probe filters. The probe filters were

### 2-7 changed six times during the 4-month period. The number of probe filter changes was high compared to other instruments.

The instrument output span was adjust ed routinely by the Opsis maintenance representatives during the 4-month peri od. Eight known span adjustments were performed to bring the instrument output m easurements back into alignment with the external reference gas concentrations.



## 2.5 Tekran

Technicians from Tekran Systems, Inco rporated arrived in mid-November and installed the system. The Tekran system remained operating on stack emissions throughout the period between installation a nd system shutdown for project completion in mid-September. Periodic preventative and corrective maintenance was necessary during this period to keep the system opera ting. The Tekran system has a programmable automatic blow back incorporated into the normal operation that occurs every 2 to 4 hours. The instrument zero and span is also checked automatically daily.

2.5.1 Preventative Maintenance

Preventative maintenance on the system incl uded recording the ai r supply pressures daily, recording the Argon gas cy linder pressure daily and re placing it as needed, adding deionized water to the scrubber reservoir, emptying the wasted water reservoir every week or as needed, and cleaning the air filt er to the probe electr onics cabinet weekly.

The Tekran system has a built-in Hg calibrato r. This feature allows the system to be programmed to introduce a single or multiple kno wn Hg concentrations to the probe, the orifice, or the analyzer. This feature allowed for either self-calibration or diagnostic purposes. However, the stack gas concentrati on could not be monito red while performing the self-calibrations or self-diagnostics. As configured, the system conducted its daily checks and calibrations over a 4-hour peri od during the early morning hours, during which the system did not monitor the stack gas Hg concentration.

2.5.2 Corrective Maintenance

A Tekran representative visited the site in December to make repairs and probe modifications. The primary causes for correc tive maintenance duri ng the period between February and May was due to the loop flow or the dilution educ tor orifice becoming plugged. The most notable failure was when the plant had a scheduled shut down to switch on the SCR system. The Tekran loop flow became plugged immediately after the plant came back online. The Tekran system successfully maintained operation after two unscheduled plant outages and re starts during June and July.

### 2-8 During the months between May and the end of the field evaluation in September the following corrective maintenance issues we re addressed. The loop flow return port became plugged nearly each month and requi red cleaning to dislodge the obstruction.

The dilution eductor orifice also beca me plugged nearly each month and required disassembly and cleaning. The inertial filter was typically cleaned or replaced during the

same time as when the dilution eductor was cleaned. The dilution eductor heat tape also required replacing twice during the period between May and Se ptember primarily due to damage caused by repeated disturbing the heat tape to remove the dilution eductor.

The analyzer portion of the system requi red corrective maintenance every three

months. The corrective maintenance incl uded replacing the UV lamp, replacing the sample and conditioning filters, and flushing out the photo cartridges. Also included in the analyzer corrective maintenance in May was replacing the valve assembly.



## 2.6 Thermo

The Thermo system has remained in th e stack throughout the duration between the February RATA and the May certification testing. Periodic preven tative and corrective maintenance was necessary during this period to keep the system operating. The Thermo, as tested, had no automated method for zero a nd span checks. Blowback was added later

as discussed in the corrective maintenance section below.

2.6.1 Preventative Maintenance

Preventative maintenance included recording the air regulator pressure to the system daily. Frequently, the orifice became plugged an d required closing the ambient bleed port at the probe for thirty seconds to dislodge the orifice obstruction. However, the system remained operating after the plant had a schedul ed 4-day shutdown in late April to bring the SCR system on-line. The Thermo system c ontinued to operate afte r the plant start-up. The system also successfully maintained operation after two unsch eduled plant outages and restarts during June and July. The Ther mo, as tested, had no automated method for zero and span checks, but they could be done manually. Blowback was added later as

discussed in the corrective maintenance section below.

2.6.2 Corrective Maintenance

The corrective maintenance during the months between May and September included cleaning the probe stinger and return port on a monthly basi s. The inertial filter required replacing every 2 months . A probe blowback system was added to the system on June 8. On occasion the orifice became pl ugged and required closing the ambient bleed port at the probe for thirty seconds to dislodge the orifice obstruction.

### 2-9 On July 9, the system failed during the se venth RATA run. The output measurements remained high after a routine system blowback then slowly leveled off to zero

concentrations and remained there. Thermo maintenance personnel were on-site during the week of July 11 to repair the system. Th e probe heater was turned off overnight to allow the system to cool for maintenance. The next morning condensation was found in all of the sample lines up to the analyzer. Se veral attempts were made to clean and repair the system during the following 3 weeks. The repair attempts included cleaning the fast loop assembly, replacing the complete probe sample conditioning assembly with a third generation design sample conditioning assembly, replacing the inertial filter, cleaning the probe stinger and return port, replacing the analyzer UV lenses, and replacing four process control solenoid valves in the anal yzer. The system was back in operation on August 4.

On August 12, the operator left the system in “probe zero” mode which prevented the system from measuring stack gas. The stat us was corrected during the next week visit on August 17. Although the system was not meas uring stack gas duri ng this period, the system was functioning.



## 2.7 Summary

Figure 2-1 shows a summary of the long-term operations for each of the CEMS. This summary is presented to clearly illustrate oper ational gaps due to mechanical or computer

failure encountered to date by the various units. Operationa l periods do not take into account passing/failure of da ily/weekly QA/QC checks and no data are shown past August 20. All of the instruments evaluated during this study required preventative maintenance. The systems also required corrective maintenance. The primary preventative maintenance requirements were probe-related (including probe blockage), loop flow blockage, temperature regulation, sample conditioning-re lated, and routine filter changing.

The analyzer portions of the systems were reliable but required quarterly corrective maintenance to keep them functioning properly.2-10NOTE:Horiba/Nippon and Forney/Genesis data not shown as they elected to remove their systems from the test program.Figure 2-1. Phase 1 and 2 Long-Term Monitoring PeriodsInstrument down fordesign upgrade

### 3-1 

# Section 3. Sampling

3.1 Process Data

Phase 1 and Phase 2 plant CEMS data as run averages are provided in Tables 3-1 and

3-2.



## 3.2 Flue Gas Sampling Location

The Hg CEMS and manual ASTM D6784- 02 (Ontario Hydro) mercury sampling

locations were located on the active stac k, approximately 345 ft above ground level, 180 ft (10 duct diameters) above the neares t flow restriction, and 410 ft (> 22 duct diameters) from the outlet. The layout of ports, Hg CEMS, Appendix K sampling, and manual sampling during Phase 1 testing are shown in Figure 3-1. The layout during Phase 2 testing is shown in Figure 3-2.

The Ontario Hydro Method samples were coll ected isokinetically at a single point approximately 5 ft within the stack. This effective distance was based on traverse information provided by the facility. Note that single point sampli ng is a deviation from the method, but it is appropriate for this te st program where the goal was to verify Hg CEMS accuracy against the reference method. Assessing Hg CEMS probe placement in the stack was not part of this test program.

All of the sampling ports are on the same level, thereby allowing the Hg CEMS and Appendix K probes to sample gases similar to those sampled by the Ontario Hydro Method. Figure 3-3 indicates elevations of ports relative to flow restrictions and top of stack for both phases of testing. The Horiba/Nip pon analyzer was in the trailer with its own reference gas delivery syst em while the Durag, Forney/G enesis, Opsis, Tekran, and Thermo/Electron analyzers were on the stack platform with a separate reference gas delivery system. The Forney/Genesis system initially was operated from the trailer, but the analyzer was moved to the stack platform when problems persisted with the heated sample line. Figure 3-4 indicates the sa mpling configuration during Phase 1 and Figure 3-5 indicates the sampli ng configuration during Phase 2.



## 3.3 Ontario Hydro Method

This section provides information on the reference method for the mercury sampling and analysis used for the project.

### 3-2 Table 3-1. Phase 1 Average Plant CEM Data

Run

No. SO 2 low

range ppm NO X conc.

raw ppm CO 2 conc. raw % Exit opacity % Stack flow

10 6 std.

ft 3 /hr Chim gas

Exit 1 temp. °F

1 115 211 12 9 65.29 127

2 107 206 12 9 64.38 126

3 70 189 12 11 63.98 127

4 106 201 12 11 64.71 127

5 108 201 12 11 65.82 128

6 103 215 12 10 64.60 126

7 89 211 12 10 64.93 125

8 100 211 12 11 64.25 126

9 81 211 12 11 63.97 125

10 93 210 12 11 64.07 127

11 67 226 12 11 63.40 127

12 142 200 12 10 62.61 128



### Table 3-2. Phase 2 Average Plant CEM Data

Run

No. SO 2 low

range ppm NO X conc.

raw ppm CO 2

conc. raw % Exit opacity % Stack flow

10 6 std.

ft 3 /hr Chim gas

Exit 1 temp. °F

1 244 10 12 10 71 131

2 201 20 12 10 71 131

3 173 15 12 11 70 132

4 169 13 12 10 69 131

5 137 16 12 9 70 130

6 142 17 12 9 70 130

7 241 11 12 8 69 131

8 231 10 12 8 69 131

9 148 16 12 9 69 131

10 159 16 12 10 68 132

11 224 14 12 10 71 132

12 179 15 12 10 71 132

### 3-3 Figure 3-1. Layout of Sampling Ports and Hg CEMS and Other Sampling Systems During Phase 1 RATA Test 

# N

INACTIVE ACTIVE
STACK
18'-0"

ELEVATOR ESCAPE LADDERHORIBANIPPON CEM CONDITIONED SPACE 8'x12'

8-9.00 ELEVATED PLATFORM

C TEKRAN 75 APPX. K

9-8.00 3-.00 THERMO

PLANT CEMS ONTARIO HYDROFORNEYG ENESIS

### 3-4 Figure 3-2. Layout of Sampling Ports and Hg CEMS and Other Sampling Systems During Phase 2 RATA Test 

# N

INACTIVE ACTIVE
STACK
18'-0"

ELEVATOR ESCAPE LADDER CEM CONDITIONED SPACE 8'x12'

8-9.00 ELEVATED PLATFORM

75 APPX. K TEKRAN OPSIS

9-8.00 3-.00 THERMO

PLANT CEMS ONTARIO HYDROFORNEYG

ENESIS 75 APPX. K DURAG

### 3-5 Figure 3-3. Sampling Location at th e Unit #1 Stack North Inlet Duct

### 3-6 Figure 3-4. Hg CEMS Sampling Configuration During Phase 1 RATA

### 3-7 Figure 3-5. Hg CEMS Sampling Configuration During Phase 2 RATA

### 3-8 3.3.1 Method Summary

The ASTM D 6784-02 “Standard Test Method for Elemental, Oxidized, ParticleBound, and Total Mercury in Flue Gas Genera ted from Coal-Fired Stationary Sources (Ontario Hydro Method),” was used as th e reference method per Part 75, Appendix A, Section 6.5.10 (FR 5/18/05, 70(95), 2 8691). A sche matic of a sampling train is presented in Figure 3-6. Further clarifications on the use of the Ontario Hydro method for this project were:

• 

### Two 2-hr paired-train samples were colle cted isokinetically from a single point

within the stack for each test run.

• 

### Quartz fiber filters were used, and had the same specifications as those described in the method. Filter supports us ed in the filter holders were 100%

Teflon.

• 

### The HNO 3 

### /H 2 

### O 2 

### and KMnO 4 

### /H 2 

### SO 4 

### samples were stored and shipped at water ice temperature; the rest of the samp les were stored and shipped at room temperature. This was done as directed by EPA representatives in response to the paper, “The Ontario Hydro Method for Speciated Mercury Measurements: Issues and Considerations,” by Jeffery V. Ryan and Robert M. Keeney.

• 

### The sample recovery scheme is presented in Figure 3-7.

3.3.2 Determination of Gas Velocity at Sampling Point

Method 2 in Appendix A of 40 CFR 60 was used to measure the gas velocity with a Type S pitot tube during sampling with the Ontario Hydro Method sampling train. Results of the Method 2 testing were used to determine the isokinetic sampling rate for the single-point sampling.

An aneroid barometer calibrated against a calibrated mercury barometer was used to measure atmospheric pressure at the sampling location.

3.3.3 Determination of Dr y Gas Molecular Weight

Method 3B in Appendix A of 40 CFR 60 was used to collect integrated gas bag samples simultaneously with the Ontario H ydro method point sampling for determination of dry gas molecular weight. The integrated gas sampling apparatus used to collect the samples is a component of the sampling train. An integrated gas sample is extracted at a constant rate from the exhaust of the sampli ng train just upstream from the outlet of the dry gas meter outlet orifice.3-9Figure 3-6. Ontario Hydro Sampling Train2001.429-1Modified Greenburg-Smith, 100 mL 1N KCIModified Greenburg-Smith, 100 mL 1N KCIGreenburg-Smith, 100 mL 1N KCIModified Greenburg-Smith, 100 mL 5% HNO3/10% H2O2Sample BoxCheckValveIce BathThermocouplePyrometerStackWallProbeHeaterThermocoupleQuartz LinerPitot TubeGlassFilterHolderHeatedAreaQuartzNozzleInclinedManometerThermocoupleVacuumLineVacuumGaugeFine ControlValveOrificeMain ValveAirtightPumpDry TestMeterThermocouples132412346578Modified Greenburg-Smith, 100 mL 4% KMnO4/10% H2SO4Modified Greenburg-Smith, 100 mL 4% KMnO4/10% H2SO4Greenburg-Smith, 100 mL 4% KMnO4/10% H2SO4Modified Greenburg-Smith, 200 g Silica Gel5678InclinedManometer3-10Figure 3-7. Ontario Hydro Sample Recovery Scheme5th, 6th, & 7thImpingers(KMnO4/H2SO4)U-connectors D-F8thImpinger(Silica gel)Measure impingercontents - weighimpingers andsubtract weightsfrom initialweights.Measure impingercontents - weighimpingers andsubtract weightsfrom initialweights.Transfer contentsto a tared bottleand weighthe bottle.Save contentsfor regenerationand reuse.Rinse impingersand U-connectorstwice with0.1 N HNO3. Athird rinse mustbe done with0.1 N HNO3withseveral drops of10% hydroxylamine.This rinse musthave enough 10%hydroxylamine suchthat the brownstains are easilyremoved.Rinse impingersand U-connectorsa final time with0.1 N HNO3.2001.429-2Nozzle, ProbeLiner, SampleTransfer line(if used), BypassFilter HolderFrontFilterRemove filter fromfilter holder andtransfer to thepetri dish.Quantitativelyremove all filterfragments andparticulate matterremaining in filterholder and transferto the petri dish.Tape cover topetri with labtape to preventany loss ofcontents.Transfer rinsesto tared bottleand weighthe bottle.Filter Support,Filter HolderBack, 90oConnector1st, 2nd, & 3rdImpingers (KCI)U-connectors A-B4th Impinger(HNO3/H2O2)U-connector CAdd small amountsof 5% KMnO4toeach KCI impingeruntil purple colorremains for15 minutes.Measure impingercontents - weighimpingers andsubtract weightfrom initial weight.Measure impingercontents - weighimpinger andsubtract weightfrom initial weight.Transfer contentsto a tared bottleand weighthe bottle.Rinse the impingertwice with0.1 N HNO3.Transfer rinses to the bottle. If the samplebecomes clear, add a small amount of the5% KMnO4solution until a pink or slightlypurple color remains for 90 minutes.Reweigh sample bottle.Transfer rinsesto the bottleand reweighthe bottle.Transfer contentsto a tared bottleand weigh thebottle.Rinse theimpingers andU-connectorsA-B with 10%HNO3. If brownstains remainrinse again with10% HNO3withseveral dropsof 10%hydroxylamine.Rinse impingersand U-connectorsa final time with0.1 N HNO3.Transfer rinses tothe bottle. If samplebecomes clear, addsmall amounts of the5% KMnO4 solutionuntil a pink or slightlypurple color is obtained.Preserve the sampleby adding 1ml of 5%dichromate solution.Reweigh sample bottle.Rinse withbrushing threetimes or morewith 0.1 N HNO3.Rinse components3 times with0.1 N HNO3.

### 3-11 3.3.4 Determination of Moisture Content

Method 4 in Appendix A of 40 CFR 60 incorporated as part of the Ontario Hydro

method was used to determine the moisture (water vapor) content of the gas stream. Moisture collected during samp ling was determined gravimetrically from the difference between the initial and final weights of all of the impingers in a train.

3.3.5 Mercury Analysis

The sample analysis was performed by Ox ford Laboratories in Wilmington, North Carolina. The sample components recovered fr om the Ontario Hydro trains (i.e., rinses, filter, and impinger contents) were digested and analyzed according to the procedures specified in the method except as explained below. For analysis of the mercury, the Ontario Hydro Method incorpor ates Method 7470A, which is a procedure for cold vapor atomic absorption spectroscopy (CVAAS) for mercury previously published in “Test Methods for Evaluating Solid Waste, Physi cal/Chemical (SW-846).” It was discovered near the end of the test program that the laboratory had not been clarifying the KMnO 4 

### impingers prior to extracting an aliquot for analysis as described in Section 13.3.5 of the Ontario Hydro method. To recover from this omission, ARCADIS G&M, Inc. in Research Triangle Park, North Carolina, performed a reanalysis of the KMnO 4 

### impingers.



## 3.4 Reference Gases

MRI used compressed elemental mercury ga s standards throughout the project to verify instrument response. The gases were also used extensively for troubleshooting problems with individual analyzers and speci fic components within each analyzer. The reference, or span, gas standards were pur chased from Spectra Gases (Branchburg, New Jersey) with a nominal concentration range of 1 to 10 μ g/m 3 

### of elemental mercury in nitrogen. Several gas cylinders were used ove r the course of the project, and Table 3-3 summarizes the concentrations of each gas cy linder used. Three lin earity standards were also used during the precertification tests. All gases were certified by Spectra Gases based on a cylinder supplied by NIST (seconda ry certification). Gases have not been characterized to the point th at the delivered concentra tion is accurate to a known uncertainty.

### 3-12 Table 3-3. Elemental Mercury Cylinders
Cylinder

No. Certified conc ( μ g/m 3 ) Approx dates of use CC19870 1.9 Dec. 04 - End of test program CC133357 2.1 Nov. 04 - End of test program CC191724 2.2 July - August 05 CC84954 2.3 Replacement - not used CC134442 5.1 July - August 05 CC191854 5.8 June - July 05 CC173117 9.03 Nov. 04 - End of test program



### 3.4.1 HovaCal Gas

The Hovacal is a calibration gas generato r used to introduce a known concentration of oxidized mercury gas (Hg 2+ 

### ) to the Hg CEMS systems for comparing the Hg CEMS output measurement readings against a known c oncentration. The Hovacal performs this function by regulating the flow rate of a known concentration of oxidized mercury in an aqueous state and by regulating the mass flow ra te of a nitrogen carrier gas to a heated evaporator where the gas-vapor mixture is introduced into the Hg CEM system prior to

the converter.

The Hovacal instrument control parameters were certified by the factory prior to operation on November 02, 2004. The instrument mass flow meter, electronic balance mass, and temperature meter were checked on August 15, 2005. The check showed all of the control parameters were opera ting within factory tolerances.

3.4.2 Cylinder Gases

The Hg reference gas cylinders were provi ded by Spectra Gases Incorporated. The audit gases were provided with a factory concen tration certification of ±10% of the stated concentration. The reference gases contain a vaporized elemental mercury concentration suspended in a nitrogen carrier gas.

3.4.3 Tekran 3310 Gas

The Tekran 3310 generates a range of elemental mercury concentrations by regulating the heat of an el emental mercury source to create a known vapor. Mass flow controllers are used to regul ate the ratio of elemental mercury vapor and supplemental clean air to provide a known vapor c oncentration at a desired flow rate.

The output of the 3310 Hg calibrator was plum bed to a pressure relief bypass tee to prevent over pressurization of the calibrator. The output port of the tee dumped to atmosphere while the second output port of the tee was attached to input of the calibration gas flow regulator attached to the Hg CEM instrument under investigation.

### 4-1 

# Section 4.

Certification Test Results

The certification test results are presented in two parts—the initial certification test results (Phase 1) are presented in Subsecti on 4.1, and the second certif ication test results (Phase 2) are presented in Subsection 4.2. With in each subsection results are provided as certification testing minus th e RATA, and then the RATA.



## 4.1 Phase 1 Certification Test Results

The certification testing is presented in two parts. Section 4.1.1 presents results from the Phase 1 measurement error test, 7-day calib ration error test, the li nearity test, system integrity test, the upscale/dow nscale drift test, an d cycle time test. Section 4.1.2 presents

results from the Phase 1 RATA test. Additiona l test results are presented in Section 4.1.3.

4.1.1 Phase 1 Certificatio n (excluding RATA) Results

Phase 1 certification tests were condu cted between February 15 and 28, 2005 according to Part 75 and PS-12A requirements. The results for each Hg CEMS are provided below. The initial certification for each CEMS included a 7-day calibration error test, a linearity check, a system integrity test (which checks converter efficiency), a measurement error test, and zero/upscale drif t tests. The reported Hg CEMS values are based on the resolution of the analyzer even though the believed resolution is more likely 0.1 mg/m 3 

### . The Hg CEMS results are reported at 20 ° C. The span was defined at

10 μ g/m 3 

### , and values used to assess CEMS perf ormance are summarized based on that span, as shown in Table 4-1 below.

Table 4-1. Summary of Phase 1 CE MS Certification Criteria and Performance (Excluding RATA)

Criteria Met? (Y/N)
Test Criteria Forney a Horiba Tekran Thermo

7 Day Calibration

Error Test Error must be ≤ 5% of span; or ≤ 1 μ g/m 3
(alternative specification when span is defined at

10 μ g/m 3 ). N Y Y Y

Linearity Test Error must be ≤ 10% of reference gas tag value

or ≤ 1 μ g/m 3 , whichever is least restrictive. N N Y Y

System Integrity

Test Error must be ≤ 5% of span from certified gas value (i.e., within ±0.5 μ g/m 3 of certified gas value). N Y Y Y

Cycle Time Test Cycle times must be ≤ 15 minutes. N N Y Y

Measurement

Error Test Error must be ≤ 5% of span from certified gas value (i.e., within ±0.5 μ g/m 3 of certified gas value). N N Y Y

Zero and Upscale
Drift Test Error must be ≤ 5% of span (i.e., within

±0.5 μ g/m 3 of certified gas value). N Y N N

a System was not functioning for most of the cert ification period.

### 4-2 4.1.1.1 Forney/Genesis

Results for the last two days of the Forney 7-day calibration error test are presented in Table 4-2. The system was not functio ning except for the last 2 days of the certification period (February 25 and 26, 2005) and no data for the linearity check, system integrity test (which checks converter efficiency), measurement error test, and zero/upscale drift tests were obtained. The re maining tests were not performed due to a pending system upgrade being developed. This system as tested was configured to operate at the stack sampling elevation.

Table 4-2. Forney 7-Day Calibration Error Test—Phase 1

Reference Gas Concentration ( μ g/m 3 ): 1.3 CEMS reading ( μ g/m 3 ) Error (difference) ( μ g/m 3 ) Result

Date Time Zero Reference Zero Reference Zero Reference

02/25/05 7:55:00 0.3 1. 5 0.3 0.2 Pass Pass

02/26/05 8:40:00 0.2 1. 5 0.2 0.2 Pass Pass 7 Day Cal Error Result: Test not completed (system failure).



### 4.1.1.2 Horiba/Nippon

The Horiba 7-day calibration error, and linea rity check, system integrity test (which checks converter efficiency), and measurem ent error test results are presented in Tables 4-3 through 4-7. The 7-day calibra tion test was performed February 22 through 28, 2005. The linearity test was perf ormed on February 28, 2005. The system integrity test was performed on February 15, 2005. The measurement error test was performed on February 27, 2005. The zero/upscal e test was performed from February 22 through 28, 2005. The data table for the cycle tim e test is not provi ded because it could not be completed. The sample conditioning sy stem (converter) was lo cated at the stack sampling location and the converted sample was transported through a 450-ft heated line (100°F) to the analyzer in the on-site test tr ailer. All reported concen trations are corrected

to 20°C. The Horiba met the criteria for the 7-day calibration error, system integrity, and zero/upscale drift tests, with the catalyst being repl aced twice during this period. The Horiba system did not meet the criteria for the measuremen t error, linearity, and cycle

time tests.

### 4-3 Table 4-3. Horiba/Nippon 7-Day Calibration Error Test—Phase 1

Reference Gas Concentration ( μ g/m 3 ): 1.3 CEMS reading ( μ g/m 3 ) Error (difference) ( μ g/m 3 ) Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

02/22/05 9:50:00 0.09 0. 9 0.1 0.4 Yes Yes

02/23/05 10:10:00 –0.09 1. 0 0.1 0.3 Yes Yes

02/23/05 9:35:00 0.0 0. 8 0.0 0.5 Yes Yes

02/24/05 9:50:00 0.0 0. 8 0.0 0.5 Yes Yes

02/24/05 15:12:00 –0.2 0. 8 0.2 0.5 Yes Yes

02/25/05 15:52:00 0.5 1. 5 0.5 0.2 Yes Yes

02/25/05 10:05:00 0.00 1. 1 0.0 0.2 Yes Yes

02/26/05 10:05:00 –0.09 1. 2 0.1 0.1 Yes Yes

02/26/05 10:17:00 –0.2 1. 0 0.2 0.3 Yes Yes

02/27/05 10:27:00 –0.2 0. 7 0.2 0.6 Yes Yes

02/27/05 10:27:00 0.0 1. 2 0.0 0.1 Yes Yes

02/28/05 10:09:00 0.0 1. 2 0.0 0.1 Yes Yes

7 Day Cal Error Result: Met criteria.

N OTE : 2/24/05 at 18:37, longer re sponse time observed. 2/25/05 at 08:00 replaced Horiba catalyst. 2/27/05 at 08:40, replaced Horiba catalyst.

### 4-4 Table 4-4. Horiba/Nippon Linearity Test—Phase 1

Low-Level Reference Gas Conc. ( μ g/m 3 ): 1.3 Mid-Level Reference Gas Conc. ( μ g/m 3 ): 5.1 High-Level Reference Gas Conc. ( μ g/m 3 ): 10.4

Test Date: 2/28/05

Cycle Time Gas type CEMS reading ( μ g/m 3 )

1 11:03:00 Low 1.2

1 11:27:00 Mid 3.4 1 11:40:00 High 5.9

Gas Low Mid High Average 1.2 3.4 5.9

% Rel. Diff. 3.9% 34% 44%

Linear Error (Diff, μ g/m 3 ) 0.0 1.7 4.5

Criteria met? Yes No No Linearity

Result: Criteria not met. Only the first cycle was performed.



### Table 4-5. Horiba/Nippon System Integrity Test—Phase 1

Mid-Level Oxidized Mercury Reference Gas Conc. ( μ g/m 3 ): 3.5 High-Level Oxidized Mercury Reference Gas Conc. ( μ g/m 3 ): 5.7

Test Date: 02/15/05

Criteria

Time Gas type CEMS reading ( μ g/m 3 ) Error ( μ g/m3) met?

12:01:00 Zero 0.0 0.0 Yes

12:14:00 Mid 3.3 0.2 Yes 12:34:00 High 5.2 0.5 Yes

Test Result: Criteria met.

### 4-5 Table 4-6. Horiba/Nippon Measurement Error Test—Phase 1

Mid-Level Reference Gas, Elemental Mercury Conc. ( μ g/m 3 ): 5.1 High-Level Reference Gas, Elemental Mercury Conc. ( μ g/m 3 ):

– Mid-Level Reference Gas, Oxidized Mercury Conc. ( μ g/m 3 ):

– High-Level Reference Gas, Oxidized Mercury Conc. ( μ g/m 3 ):

– Test Date: 2/27/2005

Gas type Time CEMS reading ( μ g/m 3 ) Error (difference)

( μ g/m 3 ) Criteria

met?

Zero 12:52 0.0 0.0 Yes Hg Mid 13:27 3.3 1.8 No Hg High NC NC NC NC Oxidized Mercury Mid NC NC NC NC Oxidized Mercury High NC NC NC NC Measurement Error Result: Test not completed;NC indicates check not completed.



### Table 4-7. Horiba/Nippon Zero/Upscale Drift Tests—Phase 1

Reference Gas Conc. ( μ g/m 3 ): 1.3 CEMS Reading ( μ g/m 3 ) Drift ( μ g/m 3 ) Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

02/22/05 17:29:00 0.09 0.9 0.1 0.4 Yes Yes

02/23/05 7:19:00 –0.09 1. 0 0.1 0.3 Yes Yes

02/24/05 7:29:00 0.0 0. 8 0.0 0.5 Yes Yes

02/25/05 17:35:00 0.0 1.1 0.0 0.2 Yes Yes

02/26/05 8:19:00 –0.09 1. 2 0.1 0.1 Yes Yes

02/27/05 13:30:00 0.0 1.2 0.0 0.1 Yes Yes

02/28/05 11:03:00 0.0 1.2 0.0 0.1 Yes Yes

N OTE : 2/25/05 at 08:00 catalyst replaced . 2/27/05 at 08:40 catalyst replaced

Zero Drift Result: Criteria met Upscale Drift Result: Criteria met



### 4.1.1.3 Tekran

The Tekran 7-day calibration error test, line arity check, system integrity test (which checks converter efficiency), cycle time, m easurement error test, and zero/upscale drift test results are presented in Tables 4-8 through 4-13. The 7-da y calibration error test was performed between February 15 and 21, 2005. The linearity check and the system integrity and measurement error tests were performed on February 15, 2005. The cycle time and zero/upscale drift tests were pe rformed on February 21, 2005. The system was located at the stack sampling platform and conf igured with a 50-ft heated line (190°C) to the analysis system in the CEM shelter on th e platform. All reporte d concentrations are

corrected to 20°C. The Tekran met the crit eria for the 7-day calibration error, system integrity, measurement error, linearity, and cycle time tests. It did not meet the criteria for

### 4-6 the zero/upscale drift tests of PS 12A whic h does not have the a lternative criteria allowance when the span is defined at 10 ug/m 3



### .

Table 4-8. Tekran 7-Day Calibration Error Test—Phase 1

Reference Gas Concentration (mid, μ g/m 3 ): 5.1 CEMS reading ( μ g/m 3 ) Error (difference) ( μ g/m 3 ) Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

02/15/05 9:50:00 0.000 4. 703 0.000 0.347 Yes Yes
02/16/05 10:10:00 0.000 4.675 0.000 0.375 Yes Yes

02/17/05 9:35:00 0.000 4. 409 0.000 0.641 Yes Yes

02/18/05 15:52:00 0.096 4.640 0.096 0.410 Yes Yes
02/19/05 10:05:00 0.075 4.602 0.075 0.448 Yes Yes

02/20/05 10:27:00 0.122 4.756 0.122 0.294 Yes Yes

02/21/05 10:09:00 0.000 4.613 0.000 0.437 Yes Yes 7-Day Cal Error Result: Criteria met.



### Table 4-9. Tekran Linearity Test—Phase 1

Low-Level Reference Gas Conc. ( μ g/m 3 ): * 2.5 Mid-Level Reference Gas Conc. ( μ g/m 3 ): * 6.1 High-Level Reference Gas Conc. ( μ g/m 3 ): * 9.8

Test Date: 2/21/05

Cycle Time Gas type CEMS reading ( μ g/m 3 )

1 2:12:00 Low 2.707

1 2:22:00 Mid 6.574 1 2:40:00 High 10.191

2 2:55:00 Low 3.002

2 3:02:00 Mid 6.743 2 3:25:00 High 10.356

3 3:40:00 Low 3.104

3 3:55:00 Mid 6.818 3 4:05:00 High 10.357

Gas Low Mid High Average 2.937 6.712 10.302

% Rel. Diff. 19.65% 9.345% 4.859%

Linear Error (Diff, μ g/m 3 ) 0.302 0.124 0.242

Criteria met? Yes Yes Yes * Reference gas produced by Tekran 3310 generator Linearity Result: Criteria met.

### 4-7 Table 4-10. Tekran System Integrity Test—Phase 1

Mid-Level Oxidized Mercury Reference Gas Conc. ( μ g/m 3 ): 3.5 High-Level Oxidized Mercury Reference Gas Conc. ( μ g/m 3 ): 5.7

Test Date: 02/15/05

Time Gas type CEMS reading ( μ g/m 3 ) Error ( μ g/m 3 ) Criteria

met?

12:01:00 Zero 0.000 0.000 Yes

12:14:00 Mid 3.299 0.231 Yes
12:34:00 High 5.185 0.465 Yes

Test Result: Criteria met.



### Table 4-11. Tekran Cycle Time—Phase 1

Upscale Cycle Time Test

Date: 2/21/2005

Start Time: 4:15:00

Stable Time: 4:30:00 Step Change ( μ g/m 3 ): 8.834 95% of Step Change: 8.392 Time of 95% Change: 4:20:00 Upscale Cycle Time: 0:05:00

Downscale Cycle Time Test

Date: 2/21/2005

Start Time: 9:22:30

Stable Time: 9:37:30 Step Change ( μ g/m 3 ): 2.165 95% of Step Change: 2.057 Time of 95% Change:* 9:22:30 Downscale Cycle Time: 0:00:00 Cycle Time: Criteria met * This is a semicontinuous reading instrument, so the step change occurred at the time the next reading was available, which was 2 min and

30 sec.

### 4-8 Table 4-12. Tekran Measurement Error Test—Phase 1

Mid-Level Reference Gas, Elemental Mercury Conc. ( μ g/m 3 ): 1 6.1 High-Level Reference Gas, Elemental Mercury Conc. ( μ g/m 3 ): 1 9.8 Mid-Level Reference Gas, Oxidized Mercury Conc. ( μ g/m 3 ): 2 3.5 High-Level Reference Gas, Oxidized Mercury Conc. ( μ g/m 3 ): 2 5.7
Test Date: 2/15/2005

Gas Type Time CEMS reading ( μ g/m 3 ) Error (difference)

( μ g/m 3 ) Criteria met?

Zero 1:56 0.176 0.176 Yes Elemental Hg Mid 2:26 6.574 0.464 Yes Elemental Hg High 2:44 10.191 0.367 Yes

Oxidized Hg Mid 12:14 3.299 0.010 Yes Oxidized Hg High 12:34 5.185 0.079 Yes

1 Reference gas produced by Tekran 3310 generator, concentration at 20°C.

2 Oxidized mercury gas produced by HovaCal unit.

Measurement Error Result: Criteria met.



### Table 4-13. Tekran Zero/Upscale Drift Tests—Phase 1

Mid-Level Reference Gas Conc. ( μ g/m 3 ): 5.05 CEMS reading ( μ g/m 3 ) Drift ( μ g/m 3 ) Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

02/15/05 9:50:00 0.000 4.703 0. 000 0.347 Yes Yes
02/16/05 9:42:00 0.000 4. 675 0.000 0.375 Yes Yes

02/17/05 9:35:00 0.000 4. 409 0.000 0.641 Yes No

02/18/05 15:52:00 0.096 4.640 0.096 0.410 Yes Yes
02/19/05 10:05:00 0.075 4.602 0.075 0.448 Yes Yes

02/20/05 10:27:00 0.122 4.756 0.122 0.294 Yes Yes

02/21/05 10:09:00 0.000 4.613 0.000 0.437 Yes Yes

Zero Drift Result: Criteria met.

Upscale Drift Result: Criteria not met on

2/17/05.



### 4.1.1.4 ThermoElectron

The ThermoElectron 7-day calibration error test, linearity check, system integrity (which checks converter efficiency), cy cle time test, measurement error test, and zero/upscale drift test results are presented in Tables 4-14 through 4-19. The system was located at the stack sampling platform and was configured with a 50-ft heated line (165°C) to the analysis system in the CEMS shelter on this platform. The 7-day calibration error test was performed Februa ry 18 through 24, 2005. The linearity test was performed on February 26. The system inte grity test was performed February 18, 2005. The cycle time test was performed on Fe bruary 20 (downscale) and February 26 (upscale). The measurement error test was performed on February 18 and 26 and the zero/upscale drift test was perf ormed on February 20. The Thermo met the criteria for the 7-day calibration error, system integrity, measurement error, linearity, and cycle time

tests. It did not meet the criteria for the zer o/upscale drift tests of PS 12A which does not

have the alternative criteria allowance when the span is defined at 10 ug/m 3



### .

### 4-9 Table 4-14. Thermo 7-Day Calibration Error Test—Phase 1

Reference Gas Concentration ( μ g/m 3 ): 1.9 CEMS reading ( μ g/m 3 ) Error (difference) ( μ g/m 3 ) Result

Date Time Zero Reference Zero Reference Zero

criteria

met Span

criteria

met

02/18/05 9:50:00 –0.07 1. 84 0.07 0.06 Yes Yes

02/19/05 10:10:00 0.04 1.93 0.04 0.03 Yes Yes

02/20/05 9:35:00 0.09 2. 32 0.09 0.42 Yes Yes

02/21/05 9:50:00 0.00 2. 74 0.00 0.84 Yes Yes

02/22/05 15:12:00 0.00 2.31 0.00 0.41 Yes Yes

02/23/05 15:52:00 0.00 1.95 0.00 0.05 Yes Yes

02/24/05 10:09:00 –0.09 1.83 0.09 0.07 Yes Yes

7 Day Cal Error Result: Criteria met.



### Table 4-15. Thermo Linearity Test—Phase 1

Low-Level Reference Gas Conc. ( μ g/m 3 ): 1.9 Mid-Level Reference Gas Conc. ( μ g/m 3 ): 5.6 High-Level Reference Gas Conc. ( μ g/m 3 ): 10.4

Test Date: 2/26/05 and

2/27/05 a

Cycle Time Gas type CEMS reading ( μ g/m 3 )

1 12:28:00 Low 1.68

1 12:32:00 Mid 5.27

1 8:58:00 High 10.23

2 14:24:00 Low 1.77

2 14:28:00 Mid 5.38

2 9:14:00 High 10.68

3 14:42:00 Low 2.20

3 14:47:00 Mid 5.44

3 9:27:00 High 10.72

Gas Low Mid High

Average 1.88 5.36 10.54

% Rel. Diff. 0.88% 4.23% 1.38%

Linear Error (Diff, μ g/m 3 ) 0.02 0.24 0.14

Criteria met? Yes Yes Yes

Linearity Result: Criteria met.

a High conc. 9.03 μ g/m 3 cylinder was found to be defective;

10.4 μ g/m 3 was substituted and was run on 2/27/05.

### 4-10 Table 4-16. Thermo System Integrity Test—Phase 1

Mid-Level Oxidized Mercury Reference Gas Conc. ( μ g/m 3 ): 3.5 High-Level Oxidized Mercury Reference Gas Conc. ( μ g/m 3 ): 5.7
Test Date: 02/18/05

Time Gas Type CEMS reading ( μ g/m 3 ) Error ( μ g/m 3 ) Criteria

met?

14:45:00 Zero 0.06 0.06 Yes

16:41:00 Mid 3.43 0.10 Yes

17:08:00 High 5.80 0.15 Yes

Test Result: Criteria met.



### Table 4-17. Thermo Cycle Time—Phase 1
Upscale Cycle Time Test

Date: 2/26/2005

Start Time: 14:55:04

Stable Time: 15:08:04 Step Change ( μ g/m 3 ): 4.00 95% of Step Change: 3.80 Time of 95% Change: 15:04:44 Upscale Cycle Time: 0:09:40 Downscale Cycle Time Test

Date: 2/20/2005

Start Time: 9:21:04

Stable Time: 9:29:54 Step Change ( μ g/m 3 ): 2.74 95% of Step Change: 2.60 Time of 95% Change: 9:23:44 Downscale Cycle Time: 0:02:40 Cycle Time Test: Criteria met.



### Table 4-18. Thermo Measurement Error Test—Phase 1

Mid-Level Reference Gas, Elemental Hg Conc. ( μ g/m 3 ): 5.6 High-Level Reference Gas, Elemental Hg Conc. ( μ g/m 3 ): 10.4 Mid-Level Reference Gas, Oxidized Hg Conc. ( μ g/m 3 ): 1 3.5 High-Level Reference Gas, Oxidized Hg Conc. ( μ g/m 3 ): 1 5.7
Test Dates: 2/18/2005 2 and 2/26/2005

Gas type Time CEMS reading ( μ g/m 3 ) Error (difference)

( μ g/m 3 ) Criteria

met?

Zero 8:26 –0.26 0.26 Yes

Hg Mid 12:32 5.27 0.33 Yes

Hg High 8:58 10.23 0.17 Yes

Oxidized Hg Mid 16:41 3.43 0.1 Yes

Oxidized Hg High 17:08 5.8 0.15 Yes

1 Oxidized Hg gas produced by HovaCal unit.

2 Oxidized Hg tests.

Measurement Error Result: Criteria met.

### 4-11 Table 4-19. Thermo Zero/Upscale Drift Tests—Phase 1

Mid-Level Reference Gas Conc. ( μ g/m 3 ): 1.9 CEMS reading ( μ g/m 3 ) Drift ( μ g/m 3 ) Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Reference

criteria

met?

02/18/05 9:50:00 –0.07 1.84 0.07 0.06 Yes Yes

02/19/05 9:42:00 0.04 1. 93 0.04 0.03 Yes Yes

02/20/05 9:35:00 0.09 2. 32 0.09 0.42 Yes Yes

02/21/05 15:52:00 0.00 2.74 0.00 0.84 Yes No
02/22/05 10:05:00 0.00 2.31 0.00 0.41 Yes Yes

02/23/05 10:27:00 0.00 1.95 0.00 0.05 Yes Yes

02/24/05 10:09:00 –0.09 1.83 0.09 0.07 Yes Yes

Zero Drift Result: Criteria met. Upscale Drift Result: Criteria not met on 2/21/05.



### 4.1.2 Phase 1 RATA Test Results

The data presented in this section are from the Initial RA test conducted during February 22-26, 2005. The testing consisted of 12 test runs comparing four mercury CEMS to the Ontario Hydro (OH) reference method. Overall, emissions as measured by OH appeared to remain fairly constant between 2 and 4 μ g/m 3



### .

The Horiba/Nippon, Tekran, and Thermo instru ments collected data for all 12 of the RA test runs and Forney/Genesis collected data for 7 RA tests runs. Duplicate OH sampling trains were used during all 12 RA test runs. Further details of the Ontario Hydro results and results for each mercury measurem ent system are presented in the sections

that follow.

Mercury analysis results are provided in Appendix E of Volume 2 of this report. Mercury CEMS data collected during the RA test are provided in Appendix F of Volume 2 of this report.

4.1.2.1 Ontario Hy dro Sample Results

Sampling times for the Ontario Hydro sa mpling method are provided in Table 4-20. All runs had the minimum sample collec tion time of 2 hr according to the method. Samples were collected over a period of severa l days in order to obs erve any variation in

emission data that would be useful in evaluating CEMS response.

### 4-12 Table 4-20. Phase 1 RA Test Run Times

Run

number Date Stack sampling intervals (in minutes per 24-hour clock) Sampling time (min)

1 2/22/2005 10:30 - 12:30 120

2 2/22/2005 14:40 - 16:40 120

3 2/23/2005 09:20 - 11:20 120

4 2/23/2005 12:40 - 14:40 120

5 2/23/2005 15:50 - 17:50 120

6 2/24/2005 09:00 - 11:00 120

7 2/24/2005 12:05 - 14:05 120

8 2/24/2005 15:15 - 17:15 120

9 2/25/2005 08:40 - 10:40 120

10 2/25/2005 11:45 - 13:45 120

11 2/25/2005 14:50 - 16:50 120

12 2/26/2005 09:30 - 11:30 120



### Table 4-21 summarizes the sampling condi tions of the reference method train. Ontario Hydro sampling and recovery data ar e provided in Appendix C of Volume 2 of this report. Method 3B sample collection data and the Orsat analysis results for each sample are included in Appendix C of Volume 2. Sample traceability data sheets are provided in Appendix B and sampling equipment calibration results are provided in Appendix D of Volume 2.

Mercury analysis results are presented in Table 4-22 and were obtained by partially following the Ontario Hydro (OH) method analytical procedures. Because it was discovered very late in the test program that the analytical laboratory was not performing a critical step in the Ontario Hydro me thod (they had not been clarifying the

KMnO 4 

### /H 2 

### SO 4 

### impinger sample prior to extracting an aliquot for analysis), the elemental mercury results for the KMnO 4 

### /H 2 

### SO 4 

### impingers are suspect. This omission affects both accuracy and precision.

Data are presented separately for each sa mple train component. Tables 4-23 and 4-24 combine the mercury analysis results with the stack sampling results and provide the mercury emissions on a concentration basis. All test runs used duplicate trains, and precision information is summarized in Tabl e 4-25. Figure 4-1 shows concentrations of the total gaseous and oxidized fraction of me rcury along with scatter points from each

train. The estimated maximum amount of mercur y that could be expected to have been

introduced from the solution blanks is also shown for comparison purposes.

### 4-13 Table 4-21. Phase 1 RA Test Stack Sampling Data
Sampling Gas Avg. stack Iso- time volume Water temp. kinetic (min) (dscm) (%) ( ° F) (%)

Run 1 120 3.127 13.6 125.3 101.3

Run 1 dup 120 3.023 13.5 125.0 101.1

Run 2 120 2.529 13.3 124.4 101.3

Run 2 dup 120 2.412 13.3 123.7 102.1

Run 3 120 2.343 13.6 125.5 98.8

Run 3 dup 120 2.298 13.0 123.8 98.8

Run 4 120 2.559 13.5 125.2 101.6

Run 4 dup 120 2.433 12.8 123.4 100.9

Run 5 120 2.514 14.2 127.0 102.4

Run 5 dup 120 2.445 13.6 125.2 99.4

Run 6 120 2.519 13.4 124.7 100.0

Run 6 dup 120 2.386 13.0 123.6 100.0

Run 7 120 2.467 13.1 123.7 97.3

Run 7 dup 120 2.451 12.5 122.1 100.0

Run 8 120 2.504 13.3 124.2 100.1

Run 8 dup 120 2.379 12.7 122.8 100.0

Run 9 120 2.461 12.8 123.0 100.0

Run 9 dup 120 2.441 12.3 121.8 99.9

Run 10 120 2.510 13.4 124.9 100.0

Run 10 dup 120 2.423 12.8 123.3 100.0

Run 11 120 2.406 13.7 125.5 100.0

Run 11 dup 120 2.356 13.2 124.1 100.1

Run 12 120 2.432 14.1 126.7 100.6

Run 12 dup 120 2.307 13.4 124.9 100.14-14Table 4-22. Phase 1 RA Test Ontario Hydro Mercury Analysis Results (μg)Gaseous PhaseParticle Bound PhaseIonicaElementalField IDFilterProberinsePart.boundsubtotalKClimpingersKCl blankcorrectedamt.bHNO3/H2O2ImpingerHNO3/H2O2imp. blankcorrected amt.bKMnO4/H2SO4impingers(see Note)ElementalsubtotalGasphasesubtotalTotal(μg)Run 1 < 0.005 < 0.012 < 0.017 0.165e0.148 0.037c,e0.033 9.32 9.35 9.50 9.50Run 1 dup < 0.005 < 0.011 < 0.016 0.712 0.641 0.038c0.034 9.99 10.02 10.66 10.66Run 2 < 0.005 < 0.013 < 0.018 0.705 0.635 0.059 0.053 7.04 7.09 7.73 7.73Run 2 dup < 0.005 0.031 0.031 0.556 0.500 0.028c0.025 7.62 7.64 8.14 8.18Run 3 < 0.005 0.029 0.029 0.771 0.693 0.031c0.027 8.42 8.44 9.14 9.16Run 3 dup < 0.005 0.019 0.019 0.727 0.654 0.015c0.014 6.26 6.27 6.92 6.94Run 4 < 0.005 < 0.011 < 0.016 0.871 0.784 0.036c0.032 6.71 6.74 7.53 7.53Run 4 dup < 0.005 < 0.010 < 0.015 1.006 0.905 0.035c0.032 8.20 8.23 9.14 9.14Run 5 < 0.005 < 0.012 < 0.017 1.040 0.936 0.026c,e0.024 8.81 8.83 9.77 9.77Run 5 dup < 0.005 0.016 0.016 1.075 0.968 0.032c0.028 7.95 7.97 8.94 8.96Run 6 < 0.006e< 0.011 < 0.017 0.890 0.801 0.028c,e0.025 11.75 11.77 12.58 12.58Run 6 dup < 0.005 < 0.012e< 0.017 0.938 0.844 0.026c0.024 8.22 8.25 9.09 9.09Run 7 < 0.005 0.020 0.020 0.767 0.690 0.031c,e0.028 7.94 7.97 8.66 8.68Run 7 dup 0.011a0.020e0.030a0.972 0.874 0.030c0.027 8.13 8.15 9.03 9.06Run 8 0.016a< 0.017 0.016a0.906 0.815 0.033c0.030 7.09 7.12 7.93 7.95Run 8 dup 0.006a< 0.010 0.006a0.992 0.893 0.020c,e0.018 6.28 6.29 7.19 7.19Run 9 < 0.005 0.012e0.012 1.190 1.071 0.028c0.025 7.78 7.80 8.87 8.88Run 9 dup < 0.005 0.026 0.026 1.125 1.013 0.029c0.026 7.31 7.34 8.35 8.37Run 10 < 0.005 0.025 0.025 0.980 0.882 0.031c0.027 8.07 8.09 8.97 9.00Run 10 dup < 0.005 < 0.012e< 0.017 1.020 0.918 0.029c0.026 8.43 8.45 9.37 9.37Run 11 0.006a< 0.014 0.006a0.943 0.848 0.027c0.024 7.65 7.67 8.52 8.52Run 11 dup < 0.005 0.033 0.033 0.935 0.842 0.068 0.062 7.58 7.64 8.48 8.51Run 12 < 0.005 0.016e0.016 0.949 0.854 0.038c0.034 6.25 6.28 7.13 7.15Run 12 dup < 0.005 0.022 0.022 0.944 0.849 0.023c0.021 8.37 8.39 9.23 9.26FB 0.016e< 0.006 0.475 0.008c,e0.014SB < 0.005 < 0.005 0.002 0.004 < 0.001Est'd. Max. Contribution from hydroxylamined: 0.002 0.008FB = Field Blank Train; SB = Solution Blank plus Filter BlankaThe Field Blank Train result exceeded 30% of the measured value; however, the contribution doesnot significantly impact total results.bBlank corrections performed per OH method.cThe Solution Blank exceeded 10% of the measured value; however,the contribution does not significantly impact total results.dA maximum of approximately 0.2 mL (1-2 drops) in KCl impingers and 0.5 mL in KMnO4/H2SO4impingers was used during recovery; amount in blank was 0.01565μg/mL.eReanalysis result; original results did notmeet < 10% difference for duplicate analyses.NOTE:KMnO4/H2SO4impinger results are suspect due to impropersample preparation. See Section 5 for details.

### 4-15 Table 4-23. Phase 1 RA Total OH Mercury Concentrations

Particle-bound subtotal Gaseous-phase subtotal b

Mass Concentration Mass Concentration ( μ g) ( μ g/dscm) ( μ g) ( μ g/dscm)

Run 1 < 0.017 N/D 9.50 3.04 Run 1 dup < 0.016 N/D 10.66 3.53 Avg. 3.28

Run 2 < 0.018 N/D 7.73 3.06 Run 2 dup 0.031 0.013 8.14 3.38 Avg. 3.22

Run 3 0.029 0.012 9.14 3.90 Run 3 dup 0.019 0.008 6.92 3.01 Avg. 3.46

Run 4 < 0.016 N/D 7.53 2.94 Run 4 dup < 0.015 N/D 9.14 3.76 Avg. 3.35

Run 5 < 0.017 N/D 9.77 3.89 Run 5 dup 0.016 0.006 8.94 3.66 Avg. 3.77

Run 6 < 0.017 a N/D a 12.58 4.99 Run 6 dup < 0.017 N/D 9.09 3.81 Avg. 4.40

Run 7 0.020 0.008 8.66 3.51 Run 7 dup 0.030 a 0.012 a 9.03 3.68 Avg. 3.60

Run 8 0.016 a 0.006 a 7.93 3.17 Run 8 dup 0.006 a 0.003 a 7.19 3.02 Avg. 3.09

Run 9 0.012 0.005 8.87 3.61 Run 9 dup 0.026 0.010 8.35 3.42 Avg. 3.51

Run 10 0.025 0.010 8.97 3.58 Run 10 dup < 0.017 N/D 9.37 3.87 Avg. 3.72

Run 11 0.006 a 0.002 a 8.52 3.54 Run 11 dup 0.033 0.014 8.48 3.60
Avg. 3.57

Run 12 0.016 0.007 7.13 2.93 Run 12 dup 0.022 0.009 9.23 4.00 Avg. 3.47

a The field blank train result exceeded 30% of the measured value; these re sults are not used in the gaseous-phase mercury concentration calculations.

b Results for the elemental mercury portion (KM n O 4 /H 2 SO 4 impinger samples) of the gaseous-phase are considered suspect due to improper sample preparation. See Section 5 for details.

### 4-16 Table 4-24. Phase 1 Gaseous-Phase OH Mercury

Elemental portion a Oxidized portion Total

gaseous Mass Concentration Mass b Concentration Concentration ( μ g) ( μ g/dscm) ( μ g) ( μ g/dscm) ( μ g/dscm) % Oxidized c (Ionic)

Run 1 9.35 2.99 0.15 0.05 3.04 1.6 Run 1 dup 10.02 3.316 0.64 0.21 3.53 6.0 Avg. 3.15 0.13 3.28 3.9

Run 2 7.09 2.80 0.63 0.25 3.06 8.2 Run 2 dup 7.64 3.17 0.50 0.21 3.38 6.1 Avg. 2.99 0.23 3.22 7.1

Run 3 8.44 3.60 0.69 0.30 3.90 7.6 Run 3 dup 6.27 2.73 0.65 0.28 3.01 9.4 Avg. 3.17 0.29 3.46 8.4

Run 4 6.74 2.63 0.78 0.31 2.94 10.4 Run 4 dup 8.23 3.38 0.91 0.37 3.76 9.9 Avg. 3.01 0.34 3.35 10.1

Run 5 8.83 3.51 0.94 0.37 3.89 9.6 Run 5 dup 7.97 3.26 0.97 0.40 3.66 10.8 Avg. 3.39 0.38 3.77 10.2

Run 6 11.77 4.675 0.801 0.318 4.99 6.4 Run 6 dup 8.25 3.46 0.84 0.35 3.81 9.3 Avg. 4.07 0.34 4.40 7.6

Run 7 7.97 3.23 0.69 0.28 3.51 8.0 Run 7 dup 8.15 3.33 0.87 0.36 3.68 9.7 Avg. 3.28 0.32 3.60 8.9

Run 8 7.12 2.84 0.81 0.33 3.17 10.3 Run 8 dup 6.29 2.64 0.89 0.38 3.02 12.4 Avg. 2.74 0.35 3.09 11.3

Run 9 7.80 3.17 1.07 0.44 3.61 12.1 Run 9 dup 7.34 3.01 1.01 0.41 3.42 12.1 Avg. 3.09 0.43 3.51 12.1

Run 10 8.09 3.22 0.88 0.35 3.58 9.8 Run 10 dup 8.45 3.49 0.92 0.38 3.87 9.8 Avg. 3.36 0.37 3.72 9.8

Run 11 7.67 3.19 0.85 0.35 3.54 10.0 Run 11 dup 7.64 3.24 0.84 0.36 3.60 9.9 Avg. 3.21 0.35 3.57 9.9

Run 12 6.28 2.58 0.85 0.35 2.93 12.0 Run 12 dup 8.39 3.64 0.85 0.37 4.00 9.2 Avg. 3.11 0.36 3.47 10.4

a The KMnO 4 /H 2 SO 4 impinger data are considered suspect due to improper sample preparation. See

Section 5 for details.

b The field blank train result exceeded 30% of the measured value; however, t he contribution does not significantly impact total results.

c % Oxidized = (Oxidized Concentration / Total Concentration) * 100.

### 4-17 Table 4-25. Phase 1 Duplicate OH Train Relative Deviation
Concentration RD (%)

Run avg. Oxidized (KCl) Elemental a Gaseous phase a

Run 1 63% 5% 7%

Run 2 10% 6% 5%

Run 3 2% 14% 13%

Run 4 10% 12% 12%

Run 5 3% 4% 3%

Run 6 5% 15% 13%

Run 7 12% 1% 2%

Run 8 7% 4% 2%

Run 9 2% 3% 3%

Run 10 4% 4% 4%

Run 11 1% 1% 1%

Run 12 2% 17% 15%

The PS-12A objective is ≤ 10% RD for gaseous phase mercury, where % RD = 100 * (Abs(a-b)) / (a+b).
Values shown in bold for Gaseous Phase have a RD > 10%.

a Results for the elemental mercury portion (KMnO 4 /H 2 SO 4 impinger samples) are considered suspect due to improper sample preparation.

See Section 5 for details.

N OTE : Nondetected results in the Particle Bound fraction prevented % RD

calculations.4-18Figure 4-1. Phase 1 OH Gaseous Phase Mercury Concentrations0.01.02.03.04.05.01 2 3 4 5 6 7 8 9 10 11 12Run No.

Hg Conc. (ug/dsm3)OHOH DupAvg Total OHAvg OxidizedOxOx Dup

### 4-19 The OH sampling was performed isokinetically from a single point at a similar effective sampling location as the Hg CEMS a nd sorbent trap. As specified in Part 75 requirements for mercury monitoring a nd PS-12A, only the ionic (oxidized) and

elemental fractions of the OH results are in cluded in the gaseous phase concentration

values used for the RATA calculations. Ther efore, the mercury CEMS and the OH results are on a similar basis (i.e., gaseous phase onl y, concentrations per dry standard volume). The particle-bound fraction, which constituted less than 1% of the total mercury, is reported only for informational purposes.

The field blank train KCl impinger results on Table 4-22 are noteworthy due to the presence of mercury at levels greater than 30% of sample values. The cause is not known. As indicated at the bottom of Table 4-22, th e calculated contribution from hydroxylamine (used in train recovery for the KCl and KMnO 4 

### impingers) could be as high as 0.002 μ g and 0.008 μ g for the KCl and KMnO 4 

### impingers, respectively. The field blank train used glassware from the recovered Run 1 train, whic h remarkably has a low sample result. An

initial concern was that the Run 1 train reco very was incomplete. However, that seems unlikely because no significant increase was observed from recovery of this glassware when used for the next run (the same gla ssware was re-used for even and odd numbered runs). Even though the mercury levels in the field blank train were greater than 30% of the ionic fraction, it should be noted that th e ionic fraction constitutes only about 10% of the total mercury in the train. This ca n be seen in Table 4-24 and Figure 4-1.

In order to verify that the field bla nk KCl impinger sample and the Run 1 KCl impinger sample had not been switched, the laboratory was contacted. The two sample

volumes were rechecked and were verified to be correct for each sample type. These two samples were also reanalyzed with similar re sults. No explanation can be given for the

unusual results obtained from these two samples.

Results from the remaining field blank samp les revealed the presence of mercury in the filter, H 2 

### O 2 

### impinger, and KMnO 4 

### impinger at levels near the detection limit. Also,

two of the six solution blanks indicated the presence of mercury n ear the detection limit (the hydroxylamine solution result was highe r). The laboratory method blanks showed no levels of mercury above detection limits.

The estimated contribution from solution blanks was between 0.5% and 0.7% of the total amount of mercury found in the sample s. Thus, even though mercury was found in the solution blank samples, it did not appear to have an appreciable effect on the overall

result. The KCl and HNO 3 

### /H 2 

### O 2 

### samples were blank correc ted using the decision tree shown in Figure 4-2.

The relative deviation (RD) results in Tabl e 4-25 indicate that even though the Run 1 KCl impinger result was anomalous, it did not have an appreciable impact on the overall result (8% RD). Most significantly, the RD for four of the 12 runs ranged between 12% to 15% RD which is greater than the 10% RD criteria in PS-12A. A review of other sampling parameters (O 2 

### , CO 2 

### , and H 2 

### O) indicates that all parameters for all runs were within 10% of each other, w ith the exception of Run 7 O 2 

### with a difference of 11.5%.

### 4-20 Thus sampling variations do not appear to be contributing to the RD variances for those four runs (3, 4, 6, and 12). The RD calcula tion is Equation 12A-1 from the proposed revision to PS-12A, which was previously called RSD.

Figure 4-2. Decision Tree for Blank Corrections

4.1.2.2 CEMS and A ppendix K RA Results

Table 4-26 summarizes the relative accuracy calculations for each of the Hg CEMS tested. Runs 3, 6, and 12 were not used because the RD values were > 10%. The Run 4 results were used (RD of 12%) in order to provide a 9th run for the RA calculation. Calculations followed the proced ures of promulgated Part 75, and are provided in Table 4-27 through 4-31. Results for each Hg CEMS are briefly discussed below. Emissions appeared to remain fairly constant around 3 μ g/m 3 

### . Because mercury was observed in the solution blanks, blank corrections were us ed for the OH results in accordance with Section 13.4.3.1 of the Ontario Hydro Method. S till, Hg levels measured with the OH method were higher than all average Hg CEM values.

The reported values in the RA tables ar e based on the resolution of the analyzer; however, the believed resolu tion is more likely 0.1 ug/m 3 

### . The Hg CEMS results are reported at 20 ° C.

Table 4-26 and Figure 4-2 show the OH results are consistently higher than CEMS results. Three possible reasons for this difference are (1) OH train contamination, (2) CEMS catalyst failure, or (3) other CEMS system component failure. Relative accuracy calculations were performed in th ree ways. First, relative accuracy was calculated using the average of Run 4 OH da ta. A second and third relative accuracy calculation was then performed using either the Run 4 train or the Run 4 duplicate train results. Comparing OH RD values with RA results sometimes helps to identify outliers or

common trends.

### 4-21 Table 4-26. Phase 1 Summary of All RA Results for All CEMS
CEMS ( μ g/dscm) Run

number Use

for

RA? OH

gaseous

mercury Forney Horiba Tekran Thermo Appx. K e

1 Yes 3.284 N/A 1.8 2.844 2.82 2.611

2 Yes 3.216 N/A 1.9 2.805 2.91 2.606

3 No 3.455 N/A 1.7 2.510 2.38 2.485

4 Yes a 3.348 N/A 1.7 b 2.657 2.42 2.457

5 Yes 3.771 N/A 2.1 3.106 3.10 2.789

6 No 4.402 1.9 1.7 3.414 3.11 2.955

7 Yes 3.597 1.7 1.5 b 2.982 2.48 2.743

8 Yes 3.095 4.0 1.3 2.997 2.47 2.865

9 Yes 3.513 2.3 2.1 3.099 2.23 2.698

10 Yes 3.721 1.5 2.3 3.076 2.00 2.633

11 Yes 3.570 1.6 2.3 3.132 2.22 d 2.814

12 No 3.468 2.0 2.2 3.583 3.18 3.127
Relative Accuracy (5 Runs) 81.9% – – – – Relative Accuracy Using Avg R un 4 OH 51.9% 18.4% 37.5% 27.7% Relative Accuracy Using Run 4 OH 51.0% 17.2% 37.2% 27.0% Relative Accuracy Using Run 4 OH Dup 52.9% 21.3% 38.7% 29.9%

a Run 4 OH result was 2.941 μ g/dscm, Run 4 Dup OH result was 3.755 (Avg. of 3.348).

b Data from half of run was lost.

c Data from first 1-1/2 minutes were lost.

d Results provided by Thermo software due to 4-20 mA output failure to data logger.

e From proposed 40 CFR Part 75, Appendix K method.

NA indicates instrument not available to collect data.4-22Figure 4-3. Summary of RA Phase 1 Tests0.00.51.01.52.02.53.03.54.04.51 2 3 4 5 6 7 8 9 10 11 12Run No.

Hg Conc. (ug/dsm3)Gaseous OHForneyHoribaTekranThermoAppx K

### 4-23 Calculations for Forney/Genesis system produced a relative accuracy (RA) of 82%

for the five available test runs. The Horiba /Nippon system relative accuracy was around 52%. The Thermo system and Appendix K syst em RA results were similar at 38% and 28%, respectively. The Tekran system RA re sults were around 18%. Note that the RA

criteria is < 20% RA or, if the average referenc e method concentrati on is less than 5

μ g/m 3 

### , within 1 μ g/m 3 

### . The Hg CEMS with a difference within 1 μ g/m 3 

### were the Tekran, the Thermo, and the Appendix K systems.

Figure 4-2 shows that with the exception of the Forney/Genesis, the CEMS and Appendix K values generally tracked with the OH results even if they were all slightly lower than the OH results. Figures 4-3 through 4-6 show plots of the run-by-run data for each analyzer, and Tables 4-27 through 4-31 show RA results for each analyzer compared with the OH method. The Appendix K RA results were provided by EPA and are reported here for comparison purposes only.

Figure 4-4. Phase 1 RA—OH Versus Forney/Genesis 0 1 2 3 4 5

1 2 3 4 5 6 7 8 9 10 11 12

Run No.Hg Conc. (ug/m3) OH

Genesis

### 4-24 Figure 4-5. Phase 1 RA—OH Versus Horiba

Figure 4-6. Phase 1 RA—OH Versus Tekran 0 1 2 3 4 5

1 2 3 4 5 6 7 8 9 10 11 12

Run No.Hg Conc. (ug/m3) OH

Horiba

0 1 2 3 4 5

1 2 3 4 5 6 7 8 9 10 11 12

Run No.Hg Conc. (ug/m3) OH

Tekran

### 4-25 Figure 4-7. Phase 1 RA—OH Versus Thermo

Table 4-27. Phase 1 RA Results for Forney/Genesis

Run

number Use
for

RA? Date Time CEMS avg.

response ( μ g/dscm) OH gaseous Hg response

( μ g/dscm) Difference ( μ g/dscm)

1 No 2/22/2005 10:30 - 12: 30 N/A 3.284 3.284

2 No 2/22/2005 14:40 - 16: 40 N/A 3.216 3.216

3 No 2/23/2005 09:20 - 11: 20 N/A 3.455 3.455

4 No 2/23/2005 12:40 - 14: 40 N/A 3.348 3.348

5 No 2/23/2005 15:50 - 17: 50 N/A 3.771 3.771

6 No 2/24/2005 09:00 - 11: 00 1.9 4.402 2.402

7 Yes 2/24/2005 12:05 - 14:05 1.7 3.597 1.797

8 Yes 2/24/2005 15:15 - 17:15 4.0 3.095 –1.005

9 Yes 2/25/2005 08:40 - 10:40 2.3 3.513 1.213

10 Yes 2/25/2005 11:45 - 13:45 1.5 3.721 2.121

11 Yes 2/25/2005 14:50 - 16:50 1.6 3.570 1.970

12 No 2/26/2005 09:30 - 11: 30 2.0 3.468 1.368

Arithmetic Mean a ( μ g/dscm) 2.2 3.5 1.3

Bias Adjustment Factor b 1.6

Standard Deviation c 1.3

Confidence Coefficient d 1.6

Relative Accuracy e using 5 runs (% of RM) 81.9%

a Arithmetic Mean = 1/n Σ d i

. b BAF = 1+ |1/n Σ

 di| / Hg CEMS (avg)

c Standard Deviation = [ ( Σ d i 2 – ( Σ d i ) 2 / n) / (n–1) ] 1/2

. d Confidence C oefficient = t 0.975 * Standard Deviation / n 1/2 , where t 0.975 = 2.776.

e Relative Accuracy = ([Difference Ar ithmetic Mean] + [Confidence Coefficient]) / RM Arithmetic Mean * 100.

N/A indicates instrument not available for data collection 0 1 2 3 4 5

1 2 3 4 5 6 7 8 9 10 11 12

Run No.Hg Conc. (ug/m3) OH

Thermo

### 4-26 Table 4-28. Phase 1 RA Results for Horiba (All 12 Runs)

Run

number Use

for

RA? Date Time CEMS avg.

response ( μ g/dscm) OH gaseous

response ( μ g/dscm) Difference ( μ g/dscm)

1 Yes 2/22/2005 10:30 - 12:30 1.8 3.284 1.484

2 Yes 2/22/2005 14:40 - 16:40 1.9 3.216 1.316

3 No 2/23/2005 09:20 - 11:20 1.7 3.455 1.755

4 a, b Yes 2/23/2005 12:40 - 14:40 1.7 3.348 1.648

5 Yes 2/23/2005 15:50 - 17:50 2.1 3.771 1.671

6 No 2/24/2005 09:00 - 11:00 1.7 4.402 2.702

7 b Yes 2/24/2005 12:05 - 14:05 1.5 3.597 2.097

8 Yes 2/24/2005 15:15 - 17:15 1.3 3.095 1.795

9 Yes 2/25/2005 08:40 - 10:40 2.1 3.513 1.413

10 Yes 2/25/2005 11:45 - 13:45 2.3 3.721 1.421

11 Yes 2/25/2005 14:50 - 16:50 2.3 3.570 1.270

12 No 2/26/2005 09:30 - 11:30 2.2 3.468 1.268

Relative Accuracy Using Avg. Run 4 OH

Arithmetic Mean c ( μ g/dscm) 1.9 3.5 1.6

BAF 1.8
Standard Deviation e 0.3

Confidence Coefficient f 0.2 Relative Accuracy g (% of RM) 51.9% Relative Accuracy Using Run 4 OH Arithmetic Mean ( μ g/dscm) 1.9 3.4 1.5

BAF 1.8

Standard Deviation 0.3

Confidence Coefficient 0.2 Relative Accuracy (% of RM) 51.0% Relative Accuracy Using Run 4 OH Dup Arithmetic Mean ( μ g/dscm) 1.9 3.5 1.6

BAF 1.9

Standard Deviation 0.3

Confidence Coefficient 0.2 Relative Accuracy (% of RM) 52.9%

a Run 4 OH result was 2.941 μ g/dscm, Run 4 Dup OH result was 3.755 (Avg. of 3.348).

b Data from half of run was lost.

c Arithmetic Mean = 1/n S d i. d BAF = 1+ |1/n Σ di| / Hg CEMS (avg)

e Standard Deviation = [ (S d i 2 - (S d i ) 2 / n) / (n-1) ] 1/2

f Confidence Coefficient = 

### t 0.975 * Std Dev / n 1/2 , where 

### t 0.975 = 2.306

g Relative Accuracy = ([Difference Arithmetic Mean] + [Confiden ce Coefficient]) / RM Arithmetic Mean * 100

### 4-27 Table 4-29. Phase 1 RA Results for Tekran (All 12 Runs)

Run

number Use

for

RA? Date Time CEMS avg.

response ( μ g/dscm) OH gaseous

response ( μ g/dscm) Difference ( μ g/dscm)

1 Yes 2/22/2005 10:30 - 12:30 2.844 3.284 0.440

2 Yes 2/22/2005 14:40 - 16:40 2.805 3.216 0.411

3 No 2/23/2005 09:20 - 11:20 2.510 3.455 0.945

4 a Yes 2/23/2005 12:40 - 14:40 2.657 3.348 0.691

5 Yes 2/23/2005 15:50 - 17:50 3.106 3.771 0.665

6 No 2/24/2005 09:00 - 11:00 3.414 4.402 0.988

7 Yes 2/24/2005 12:05 - 14:05 2.982 3.597 0.615

8 Yes 2/24/2005 15:15 - 17:15 2.997 3.095 0.098

9 Yes 2/25/2005 08:40 - 10:40 3.099 3.513 0.414

10 Yes 2/25/2005 11:45 - 13:45 3.076 3.721 0.645

11 Yes 2/25/2005 14:50 - 16:50 3.132 3.570 0.438

12 No 2/26/2005 09:30 - 11:30 3.583 3.468 –0.115

Relative Accuracy Using Avg. Run 4 OH

Arithmetic Mean b ( μ g/dscm) 2.97 3.5 0.5

BAF c 1.2
Standard Deviation d 0.2

Confidence Coefficient e 0.1 Relative Accuracy f (% of RM) 18.4% Relative Accuracy Using Run 4 OH Arithmetic Mean ( μ g/dscm) 2.97 3.4 0.4

BAF c 1.2

Standard Deviation 0.2

Confidence Coefficient 0.1 Relative Accuracy (% of RM) 17.2% Relative Accuracy Using Run 4 OH Dup Arithmetic Mean ( μ g/dscm) 2.97 3.5 0.6

BAF c 1.2

Standard Deviation 0.3

Confidence Coefficient 0.2 Relative Accuracy (% of RM) 21.3%

a Run 4 OH result was 2.941 μ g/dscm, Run 4 Dup OH result was 3.755 (Avg. of 3.348).

b Arithmetic Mean = 1/n S d i.

c BAF = 1+ |1/n Σ di| / Hg CEMS (avg)

d Standard Deviation = [ (S d i 2 - (S d i ) 2 / n) / (n-1) ] 1/2

e Confidence Coefficient = 

### t 0.975 * Std Dev / n 1/2 , where 

### t 0.975 = 2.306

f Relative Accuracy = ([Difference Arithmetic Mean] + [Confidence Coefficient]) / RM Arithmetic Mean * 100.

### 4-28 Table 4-30. Phase 1 Initial RA Re sults for Thermo (All 12 Runs)

Run

number Use

for

RA? Date Time CEMS avg.

response ( μ g/dscm) OH gaseous

response ( μ g/dscm) Difference ( μ g/dscm)

1 Yes 2/22/2005 10:30 - 12:30 2.82 3.284 0.464

2 Yes 2/22/2005 14:40 - 16:40 2.91 3.216 0.306

3 No 2/23/2005 09:20 - 11:20 2.38 3.455 1.075

4 a Yes 2/23/2005 12:40 - 14:40 2.42 3.348 0.928

5 Yes 2/23/2005 15:50 - 17:50 3.10 3.771 0.671

6 No 2/24/2005 09:00 - 11:00 3.11 4.402 1.292

7 Yes 2/24/2005 12:05 - 14:05 2.48 3.597 1.117

8 Yes 2/24/2005 15:15 - 17:15 2.47 3.095 0.625

9 Yes 2/25/2005 08:40 - 10:40 2.23 3.513 1.283

10 b Yes 2/25/2005 11:45 - 13:45 2.00 3.721 1.721

11 c Yes 2/25/2005 14:50 - 16:50 2.22 3.570 1.350

12 No 2/26/2005 09:30 - 11:30 3.18 3.468 0.288

Relative Accuracy Using Avg. Run 4 OH

Arithmetic Mean d ( μ g/dscm) 2.52 3.5 1.0

BAF c 1.4

Standard Deviation e 0.5

Confidence Coefficient f 0.4 Relative Accuracy g (% of RM) 37.5% Relative Accuracy Using Run 4 OH Arithmetic Mean ( μ g/dscm) 2.52 3.4 0.9

BAF c 1.4
Standard Deviation 0.5

Confidence Coefficient 0.4 Relative Accuracy (% of RM) 37.2% Relative Accuracy Using Run 4 OH Dup Arithmetic Mean ( μ g/dscm) 2.52 3.5 1.0

BAF c 1.4

Standard Deviation 0.5

Confidence Coefficient 0.4 Relative Accuracy (% of RM) 38.7%

a Run 4 OH result was 2.941 μ g/dscm, Run 4 Dup OH result was 3.755 (Avg. of 3.348)

b Data from first 1-1/2 minutes was lost.*

c Results provided by Thermo software due to 4-20 mA output failure.*

d Arithmetic Mean = 1/n S d i

e BAF = 1+ |1/n Σ di| / Hg CEMS (avg)

f Standard Deviation = [ (S d i 2 - (S d i ) 2 / n) / (n-1) ] 1/2

g Confidence Coefficient = 

### t 0.975 * Std Dev / n 1/2 , where 

### t 0.975 = 2.306

h Relative Accuracy = ([Difference Arithmetic Mean] + [Confid ence Coefficient]) / RM Arithmetic Mean * 100

### 4-29 Table 4-31. Phase 1 RA Results for Appendix K Method

Run

number Use

for

Best 9 Date Time Appx. K

avg. result ( μ g/dscm) OH

gaseous

response ( μ g/dscm) Difference ( μ g/dscm)

1 Yes 2/22/2005 10:30 - 12:30 2.611 3.284 0.673

2 Yes 2/22/2005 14:40 - 16:40 2.606 3.216 0.610

3 No 2/23/2005 09:20 - 11:20 2.485 3.455 0.971

4 a Yes 2/23/2005 12:40 - 14:40 2.457 3.348 0.891

5 Yes 2/23/2005 15:50 - 17:50 2.789 3.771 0.982

6 No 2/24/2005 09:00 - 11:00 2.955 4.402 1.447

7 Yes 2/24/2005 12:05 - 14:05 2.743 3.597 0.854

8 Yes 2/24/2005 15:15 - 17:15 2.865 3.095 0.230

9 No 2/25/2005 08:40 - 10:40 2.698 3.513 0.815

10 Yes 2/25/2005 11:45 - 13:45 2.633 3.721 1.089

11 Yes 2/25/2005 14:50 - 16:50 2.814 3.570 0.755

12 No 2/26/2005 09:30 - 11:30 3.127 3.468 0.341

Relative Accuracy Using Avg. Run 4 OH

Arithmetic Mean b ( μ g/dscm) 2.69 3.5 0.8

BAF c 1.3

Standard Deviation d 0.3
Confidence Coefficient e 0.2 Relative Accuracy f (% of RM) 27.7% Relative Accuracy Using Run 4 OH Arithmetic Mean ( μ g/dscm) 2.69 3.4 0.7

BAF c 1.3

Standard Deviation 0.3

Confidence Coefficient 0.2 Relative Accuracy (% of RM) 27.0% Relative Accuracy Using Run 4 OH Dup Arithmetic Mean ( μ g/dscm) 2.69 3.5 0.8

BAF c 1.3
Standard Deviation 0.3

Confidence Coefficient 0.2 Relative Accuracy (% of RM) 29.9%

a Run 4 OH result was 2.941 μ g/dscm, Run 4 Dup OH result was 3.755 (Avg. of 3.348)

b Arithmetic Mean = 1/n Σ d i

c BAF = 1+ |1/n Σ di| / Hg CEMS (avg)

d Standard Deviation = [ ( Σ d i 2 - ( Σ d i ) 2 / n) / (n-1) ] 1/2

e Confidence Coefficient = 

### t 0.975 * Standard Deviation / n 1/2 , where 

### t 0.975 = 2.306

f Relative Accuracy = ([Difference Arithmetic Mean] + [Confidence Coefficient]) / RM Arithmetic Mean * 100

### 4-30 4.1.3 Additional Testing

4.1.3.1 Initial Scre ening of Sorbent Trap Data With Hg CEMS

EPA Method 324 sorbent trap data from samples collected per Part 75 Section K on 12/16/04 are compared with Hg CEMS results in Table 4-32.

Table 4-32. Comparison of Sorbent Trap and Hg CEMS Data (12/16/04)

Run

No. Sample ID Start

time End

time Sorbent trap Hg conc. ( μ g/m 3 ) Avg.

sorbent

trap Hg conc. ( μ g/m 3 ) Horiba avg. Hg

conc. ( μ g/m 3 ) Tekran avg. Hg

conc. ( μ g/m 3 )

Trap #1 9:24 11:18 3.0 1 Trap #2 9:24 11:18 3.1 3.0 3.0 2.695

Trap #3 11:38 13:31 3.4 2 Trap #4 11:38 13:31 3.4 3.4 3.8 3.325



### 4.1.3.2 Dynamic Spiking Data

Dynamic spiking and data collection were performed on the Tekran Hg CEMS as a preliminary evaluation of the instrumental reference method concept. Elemental Hg spiking was performed at the probe tip at thr ee levels. These data are presented below in Table 4-33 and Figure 4-7.

Table 4-33. Tekran Elemental Mercury Sample Spikes

Pre-test Pre- and post-test Posttest Average Background Hg: 2.523 2.625 2.659

1.32 μ g/m 3 Spike Instrument Reading: 3.803 Recovered Hg: 1.280 1.178 1.144 Recovery %: 97.0% 89.2% 86.6%

2.64 μ g/m 3 Spike Instrument Reading: 5.458 Recovered Hg: 2.935 2.833 2.799 Recovery %: 111.2% 107.3% 106.0%

3.95 μ g/m 3 Spike Instrument Reading: 7.644 Recovered Hg: 5.121 5.019 4.984 Recovery %: 129.6% 127.1% 126.2% % Recovery = (Instrm Rdg – Background/Amount Spiked).

### 4-31 Figure 4-8. Tekran Elemental Mercury Spiking



## 4.2 Phase 2 Certification Test Results

4.2.1 Certificat ion (excluding RATA)

Certification tests for Phase 2 were conduc ted on three different occasions through the late spring and summer of 2005. The firs t set of certification tests was performed during the period between May 13 through 21, 2005, the second set of ce rtification tests was performed between June 22 and July 1, 2005 and the third set of certification tests was performed between July 6 and 15, 2005. Certification tests were conducted as specified in PS-12A and Part 75. Certification tests were performed on the Durag and Opsis in May shortly after th eir installation, and on the four Durag, Opsis, Tekran, and Thermo systems during June and July.

The results for each Hg CEMS are provided in this section. The certification tests for each instrument included a 7-day calibration error test, a linearity check, a system integrity test (which checks converter e fficiency), a measurement error test, and zero/upscale drift tests. The span was defined at 10 μ g/m 3 

### for each CEMS, and values used to assess CEMS performance are summari zed based on that span, as shown in Table

4-34 below. 2 3 4 5 6 7 8

14:35 14:55 15:15 15:35 15:55 16:15 16:35 16:55 17:15 17:35

T im eug/m 3

### 4-32 Table 4-34. Summary of Phase 2 CEMS C ertification Criteria and Performance (Excluding RATA)

Criteria Met? (Y/N) Test Criteria Durag Opsis Tekran Thermo
7 Day Calibration

Error Test Error must be ≤ 5% of span; or ≤ 1

μ g/m 3 (alternative specification when span is defined at 10 μ g/m 3 ). Y Y Y N

Linearity Test Error must be ≤ 10% of reference gas tag value or ≤ 1 μ g/m 3 , whichever is least

restrictive. N N Y a N

System Integrity

Test Error must be ≤ 5% of span from certified gas value (i.e., within ±0.5 μ g/m 3 of certified gas value). Y c Y b Y c N

Cycle Time Test Cycle times must be ≤ 15 minutes. Y Y Y Y

Measurement

Error Test Error must be ≤ 5% of span from certified gas value (i.e., within ±0.5 μ g/m 3 of certified gas value). Y a N Y a N

Zero and Upscale
Drift Test Error must be ≤ 5% of span (i.e., within

±0.5 μ g/m 3 of certified gas value). Y N Y c N

a Passed the first of two tests performed in July.

b Passed the test performed in June.

c Passed the test performed in May.



### 4.2.1.1 Durag

The Durag 7-day calibration error test, lineari ty check, system integrity test (which tests converter efficiency), m easurement error test, and zero/up scale drift test results are presented in Tables 4-35 through 4-40. Tes ting and test dates are discussed below.

4.2.1.1.1 7-Day Calibration Error Test

The Durag system was challenged with thr ee separate 7-day calibration error tests.

Results from the three calibration error tests are summarized in Table 4-35. The instrument met the performance criteria for a ll three separate tests. The first test was conducted between the dates of May 13 and May 20, 2005. The reference gas used during the May 7-day calibration error test was from the Tekran 3310 Hg calibration source. The purpose of using the Tekran 3310 was due to a limited supply of available reference gases during the test period and an effort to conserve the gases for the remaining duration of the study.

The second 7-day calibration error test was conducted between th e dates of June 22 and June 29, 2005. The reference gas used dur ing the June 7-day calibration error test

varied between the Tekran 3310 Hg calibration source and the 5.8 μ g/m 3 

### cylinder gas

source. The difference between sources was due to the availabili ty of the source

concentration at the availabl e time to perform the test.

A third 7-day calibration error test was conducted between the dates of July 6 and July 15, 2005. The reference gas used during the July test was from the 2.2 μ g/m 3


### cylinder gas source. The 7-day calibration e rror test during the month of July was

conducted within the same time frame as the RATA. This test information was collected and provided to make the test data complete . The information may also be useful in determining the instrument integrity.

### 4-33 Table 4-35. Durag 7-Day Calibration Error Test—Phase 2

Gas Source: Tekran 3310

Concentration: 2.5 μ g/m 3

CEMS Reading Error Criteria met?

Date Time Zero Reference Ze ro Reference Zero Reference

05/13/05 16:32 0.0 2. 2 0.00 0.26 Yes Yes

05/14/05 16:36 0.0 2. 4 0.00 0.06 Yes Yes

05/15/05 11:09 0.0 2. 9 0.00 0.44 Yes Yes

05/16/05 10:52 0.0 2. 1 0.00 0.36 Yes Yes

05/17/05 10:44 0.0 2. 4 0.00 0.06 Yes Yes

05/18/05 9:36 0.0 2. 1 0.00 0.36 Yes Yes

05/19/05 9:03 0.0 2. 7 0.00 0.24 Yes Yes

05/20/05 8:40 0.0 2. 5 0.00 0.04 Yes Yes 7-Day Cal Error Result (5/13 - 5/20): Met criteria.
Gas Source: Tekran 3310 and Cylinder

Concentration: 4.9 and 5.8* μ g/m 3

CEMS Reading Error Criteria met?

Date Time Zero Reference Ze ro Reference Zero Reference

* 06/22/05 16:33 0.1 5. 6 0.10 0.20 Yes Yes

* 06/23/05 9:23 0.1 5. 7 0.10 0.10 Yes Yes

06/24/05 15:43 0.0 5. 3 0.00 0.39 Yes Yes

* 06/25/05 10:46 0.1 5. 8 0.10 0.00 Yes Yes

* 06/26/05 10:52 0.1 5. 3 0.10 0.50 Yes Yes

06/27/05 9:07 0.2 4. 8 0.20 0.11 Yes Yes

* 06/28/05 7:17 0.1 5. 9 0.10 0.10 Yes Yes

* 06/29/05 14:17 0.1 5. 6 0.10 0.20 Yes Yes 7-Day Cal Error Result (6/22 - 6/29): Met criteria.
Gas Source: Cylinder

Concentration: 2.2 μ g/m 3

CEMS Reading Error Criteria met?

Date Time Zero Reference Ze ro Reference Zero Reference

07/06/05 16:59 0.0 2. 2 0.00 0.00 Yes Yes

07/07/05 14:06 0.0 2. 2 0.00 0.00 Yes Yes

07/08/05 13:48 0.0 2. 0 0.00 0.20 Yes Yes

07/09/05 11:54 0.0 2. 4 0.00 0.20 Yes Yes

07/10/05 11:41 0.1 2. 5 0.10 0.30 Yes Yes

07/11/05 12:04 0.1 2. 5 0.10 0.30 Yes Yes

07/12/05 12:10 0.1 2. 6 0.10 0.40 Yes Yes

07/13/05 9:10 0.0 1. 7 0.00 0.50 Yes Yes

07/14/05 12:06 0.0 2. 2 0.00 0.00 Yes Yes

07/15/05 10:43 0.0 2. 5 0.00 0.30 Yes Yes 7 Day Cal Error Result (7/06 - 7/15): Met criteria.



### 4.2.1.1.2 Linearity Test

The Durag system was challenged with two separate linearity tests. Results of the linearity tests are summarized in Table 4- 36. The instrument did not meet the Part 75 criteria during either of the two tests. The first test was conducted on May 16, 2005. The reference gas used during the May measurem ent error test was from the Tekran 3310 mercury calibration source. The Tekran 3310 sour ce was used due to a limited supply of available cylinder gases during th e test period and an effort to conserve the cylinder gases for the remaining duration of the study. During the May linearity test, the average of the three high-level gas concentrations measured by the instrument was 0.1 μg/m3 above the

allowable alternative cr iteria of ±1.0 μg/m3.

### 4-34 The second linearity test was conducte d on July 13, 2005. The reference gas concentrations used during the July test were from the gas cylinder sources. The July test was performed after the RATA, primarily due to the limited time available to conduct the test prior to the RATA. The Durag system did not meet the test criteria during the July linearity test since the averag e of the three high-level gas co ncentrations measured by the instrument was 0.3 μg/m3 above the allowabl e alternative criteria of ±1.0 μg/m3.

An observation for both Durag linearity test s was that from cycle to cycle, the instrument showed an upward measurement trend.

Table 4-36. Durag Linearity Test—Phase 2

From Tekran 3310

Low-Level Gas Concentration: 2.5 μ g/m 3

Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8

Test Date: 5/16/2005 Cycle Time Gas type CEMS Reading

1 15:21 Low 2.0

1 15:36 Mid 6.2 1 15:51 High 10.5

2 16:51 Low 2.8

2 17:01 Mid 6.7 2 17:17 High 11.2

3 17:34 Low 2.8

3 17:51 Mid 6.7 3 18:07 High 11.1 Gas Low Mid High Average 2.5 6.5 10.9
% Error 3.19% 6.44% 11.32%

Linear Error 0.1 0.4 1.1

Criteria met? Yes Yes No 5/16/05 Linearity Result : Criteria not met.
From Cylinders

Low-Level Gas Concentration: 2.2 μ g/m 3

Mid-Level Gas Concentration: 5.1 High-Level Gas Concentration: 10.4

Test Date: 07/13/05 Cycle Time Gas type CEMS reading

1 9:18 Low 1.7

1 9:55 Mid 4.8 1 10:10 High 10.9

2 10:26 Low 2.7

2 10:48 Mid 5.4 2 11:01 High 11.9

3 11:27 Low 3.1

3 11:42 Mid 6.0 3 11:52 High 12.3

9:10 Zero 0 Gas Low Mid High Average 2.5 5.4 11.7
% Error 13.6% 5.9% 12.5%

Linear Error 0.3 0.3 1.3

Criteria met? Yes Yes No 7/13/05 Linearity Result: Criteria not met.

### 4-35 4.2.1.1.3 System Integrity Test

During the May and June certification test periods, system integrity tests were performed on the Durag system. Results of th is system integrity testing are summarized in Table 4-37. The Durag system met the performance criteria for the first system integrity test performed on May 20, 2005, but fail ed to meet the criteria for the second system integrity test conducted on June 28, 2005. A likely cause of the June system integrity test results was the degrading cuvet UV light filter in the analyzer that was diagnosed three days earlier.

Throughout the entire duration that the Dura g system was operating on-site, weekly system integrity tests were performed. The results of all of the weekly system integrity tests are provided in Volume 3, Appendix H. The Durag system met the criteria on two of the 16 weekly system integrity tests performed.

Table 4-37. Durag System Integrity Test—Phase 2

From Hovacal Mid-Level Oxidized Hg Concentration: High-Level Oxidized Hg Concentration: 4.7

7.6

Test Date: 05/20/05

Time Gas type CEMS reading (wet) Error Criteria

met?

13:13 Zero 0.5 0.5 Yes

12:42 Mid 4.6 0.1 Yes 12:13 High 8.6 1.0 Yes

5/20/05 Converter Test Result: Criteria not met.

From Hovacal Mid-Level Oxidized Hg Concentration: High-Level Oxidized Hg Concentration:

Test Date: 4.7

7.5
6/28/2005

Time Gas type CEMS reading (wet) Error Criteria

met?

15:14 Zero 0.1 0.1 Yes

15:40 Mid 3.0 1.7 No 16:01 High 4.4 3.1 No

6/28/05 Test Result: Criteria not met.



### 4.2.1.1.4 Cycl e Time Test

The Durag system was challenged with tw o complete cycle time tests which are

summarized in Table 4-38. The instrument me t the performance criteria for both tests. The first test was conducted on May 19, 2005, a nd the second test was conducted on July 14, 2005, after the RATA. Another cycle time te st was attempted on the Durag system on June 26, 2005, but the system-automated 2-hour back-flush event interrupted the test results. Limited time availability prevented th e test being repeated in June prior to the

RATA that followed the next week.

### 4-36 Table 4-38. Durag Cycle Time—Phase 2

Date: 05/19/05

Time CEM reading Comments

16:44 7.7 Pretest stable stack measurement

17:06 0 Zero and stable 17:06:30 Release CEM back to stack gas 17:13:00 5.9 Reach 95% of stable range 17:21:30 6.2 Stack gas measurement stable

6:30 min Tolerance< 00:15:00

17:28 6.1 Pretest stable stack measurement 17:35 9.9 High level (10.4) reference Gas and stable 17:37:00 Release CEM back to stack gas 17:45:02 6.8 Reach 95% of stable range 17:52:00 6.6 Stack gas measurement stable

8:02 min Tolerance< 00:15:00 Cycle time Test Results: Criteria met.

Date: 07/14/05

Time CEM reading Comments

12:19 3.2 Pretest stable stack measurement

12:28 11.0 Zero and stable 12:29:00 Release CEM back to stack gas 12:39:00 3.1 Reach 95% of stable range 12:44:00 3.1 Stack gas measurement stable

10:00 min Tolerance< 00:15:00

12:53 3.0 Pretest stable stack measurement 13:02 0 High level (9.85) reference Gas and stable 13:04:00 Release CEM back to stack gas 13:13:00 2.8 Reach 95% of stable range 13:19:00 2.8 Stack gas measurement stable

9:00 min Tolerance< 00:15:00 Cycle time Test Results: Criteria met.



### 4.2.1.1.5 Measur ement Error Test

The Durag system was challenged with two separate measurement error tests.

Results of measurement error testing are summarized in Ta ble 4-39. The first test was conducted on May 16, 2005. The reference gas used during the May measurement error test was from the Tekran 3310 Hg calibrati on source. The Tekran 3310 source was used due to a limited supply of available cylinder ga ses during the test peri od and an effort to conserve the gases for the remaining duration of the study.

The second measurement test was conduc ted on July 13, 2005. The reference gas concentrations used during the July measurem ent error test were from the reference gas cylinder. The July test was performed after the RATA primarily due limited time

available to conduct the te st prior to the RATA.

### 4-37 The Durag system did not meet the performance criteria for the high level gas for the first test (off by 0.2 μg/m3), but did meet them for the second test.

Table 4-39. Durag Measurement Error Test—Phase 2

From Tekran 3310

Low-Level Gas Concentration: 2.5

Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8

Test Date: 05/16/05

Gas Type Time CEMS Reading Error Criteria

met?

Zero 15:06 0.0 0 Yes

Low 15:21 2.0 0.5 Yes

Mid 15:36 6.2 0.1 Yes High 15:51 10.5 0.7 No

5/17/05 Measurement Error Result: Criteria not met. From Cylinders

Low-Level Gas Concentration:

Mid-Level Gas Concentration: High-Level Gas Concentration: 2.2

5.1

10.4

Test Date: 7/13/2005

Gas Type Time CEMS Reading Error Criteria

met?

Zero 9:10 0.0 0 Yes

Low 9:18 1.7 0.5 Yes

Mid 9:55 4.8 0.3 Yes High 10:10 10.9 0.5 Yes

7/13/05 Measurement Error Result: Met criteria.



### 4.2.1.1.6 Zero/Upscale Drift Test

The Durag system was challenged with three separate zero/upscale drift tests results

of which are summarized in Table 4-40. The in strument met the perf ormance criteria for all three separate tests. The first zero/ups cale drift test was conducted between the dates of May 13 and May 20, 2005. The reference gas us ed during the test period was from the Tekran 3310 Hg calibration source. The purpos e of using the Tekran 3310 was due to a limited supply of available reference cylinder ga ses during the test period and an effort to conserve the gases for the remaining duration of the study.

The second zero/upscale drift test was conducted between the dates of June 22 and June 29, 2005. The reference gas used during th e June zero/upscale drift test varied between the Tekran 3310 Hg calibration source and the 5.8 μ g/m 3 

### concentration gas cylinder. The difference between gas sources was due to the availability of the gas cylinder at the available tim e to perform the test.

### 4-38 Table 4-40. Durag Zero/Upscale Drift Tests—Phase 2

Gas Source: Tekran 3310

Reference Gas Concentration: 2.5 CEMS Reading Drift Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

05/13/05 16:32 0.0 2.2 0. 00 0.26 Yes Yes

05/14/05 16:36 0.0 2. 4 0.00 0.06 Yes Yes

05/15/05 11:09 0.0 2. 9 0.00 0.44 Yes Yes

05/16/05 10:52 0.0 2. 1 0.00 0.36 Yes Yes

05/17/05 10:44 0.0 2. 4 0.00 0.06 Yes Yes

05/18/05 9:36 0.0 2. 1 0.00 0.36 Yes Yes

05/19/05 9:03 0.0 2. 7 0.00 0.24 Yes Yes

05/20/05 8:40 0.0 2. 5 0.00 0.04 Yes Yes

5/13 - 5/20 Zero Drift Result: Criteria met. 5/13 - 5/20 Upscale Drift Result: Criteria met.
Gas Source: Tekran 3310 and Cylinder*

Reference Gas: 4.9 and 5.8* CEMS Reading Drift Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

* 06/22/05 16:33 0.1 5.6 0.10 0.20 Yes Yes

* 06/23/05 9:23 0.1 5. 7 0.10 0.10 Yes Yes

06/24/05 15:43 0.0 5.3 0.00 0.39 Yes Yes

* 06/25/05 10:46 0.1 5. 8 0.10 0.00 Yes Yes

* 06/26/05 10:52 0.1 5. 3 0.10 0.50 Yes Yes

06/27/05 9:07 0.2 4.8 0.20 0.11 Yes Yes

* 06/28/05 7:17 0.1 5.9 0.10 0.10 Yes Yes
* 06/29/05 14:17 0.1 5.6 0.10 0.20 Yes Yes

6/22 - 6/29 Zero Drift Result: Criteria met. 6/22 – 6/29 Upscale Drift Result: Criteria met. Gas Source: Cylinder

Reference Gas Concentration: 2.2 CEMS Reading Drift Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

07/06/05 16:59 0.0 2.2 0.00 0.00 Yes Yes

07/07/05 14:06 0.0 2. 2 0.00 0.00 Yes Yes

07/08/05 13:48 0.0 2. 0 0.00 0.20 Yes Yes

07/09/05 11:54 0.0 2. 4 0.00 0.20 Yes Yes

07/10/05 11:41 0.1 2. 5 0.10 0.30 Yes Yes

07/11/05 12:04 0.1 2. 5 0.10 0.30 Yes Yes

07/12/05 12:10 0.1 2. 6 0.10 0.40 Yes Yes

07/13/05 9:10 0.0 1. 7 0.00 0.50 Yes Yes

7/6 - 7/13 Zero Drift Result: Criteria met. 7/6 - 7/13 Upscale Drift Result: Criteria met.

### 4-39 A third zero/upscale drift test was conducted between the dates of July 6 and July 13, 2005. The reference gas used during the July zero/upscale drift test was from the 2.2 ug/m3 concentration reference gas cylinde r. The July zero/upscale drift test was

conducted within the same time frame as the RATA. This test information was collected and provided to make the test data complete . The information may also be useful in determining the instrument integrity.

4.2.1.2 Opsis

The Opsis 7-day calibration error test, lineari ty check, system integrity test (which checks converter efficiency), measurement erro r test, and zero/upscale drift test results are presented in Tables 4-41 through 4-46. Te sting and test dates are discussed below.

4.2.1.2.1 7-Day Calibration Error Test

The Opsis system was challenged with thr ee separate 7-day calibration error tests.

Results of the calibration erro r testing are summarized in Table 4-41. The instrument met the performance criteria for three 7-day test periods.

The first test was performed between the dates of May 14 and May 21, 2005. The reference gas used during the May 7-da y calibration error test was a 2.46 μg/m3 concentration from the Tekran 3310 Hg calib ration source. The Tekran 3310 was used due to the limited supply of available cylinde r gases during the test period. On the eighth day of the testing, the Opsis system meas ured 0.8 μg/m3 lower than the 1.0 μg/m3 tolerance limit specified by Part 75. This eighth day measurement was conducted after the gold trap was damaged by the trace nitric acid used in the oxidized mercury solution for the system integrity test.

The second 7-day calibration error test wa s conducted between June 23 and July 1, 2005. The reference gas used during this 7-day calibration error test varied between the Tekran 3310 Hg calibration source and the 5.8 μ g/m 3 

### concentration reference cylinder gas source. The difference between sources wa s due to the availability of the source

concentration at the availabl e time to perform the test.

### 4-40 Table 4-41. Opsis 7-Day Calibration Error Test—Phase 2

Gas Source: Tekran 3310

Reference Gas Concentration: 2.5 CEMS Reading Error Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

05/14/05 14:23 0.4 2. 3 0.4 0.2 Yes Yes

05/15/05 10:37 0.0 2. 3 0.0 0.2 Yes Yes

05/16/05 10:25 0.1 2. 0 0.1 0.6 Yes Yes

05/17/05 9:40 0.2 1. 9 0.2 0.7 Yes Yes

05/18/05 8:58 0.0 2. 0 0.0 0.5 Yes Yes

05/19/05 15:38 0.7 2. 2 0.7 0.3 Yes Yes

05/20/05 9:58 0.0 2. 7 0.0 0.5 Yes Yes

05/21/05 5:09 0.3 0. 7 0.3 1.8 Yes No 7-Day Cal Error Result (5/14 - 5/20): Criteria met. Gas Source: Tekran 3310 and Cylinder*

Reference Gas Concentration: 4.9 and 5.8* CEMS Reading Error Result

Date Time Zero Reference Zero Reference Zero

criteria
met? Span

criteria
met?

* 06/22/05 13:32 0.2 7. 5 0.2 1.7 Yes No

* 06/23/05 9:59 0.2 5. 2 0.2 0.6 Yes Yes

* 06/24/05 16:19 0.3 6. 4 0.3 0.6 Yes Yes

* 06/25/05 10:58 0.0 6. 5 0.0 0.7 Yes Yes

* 06/26/05 10:52 0.1 6. 0 0.1 0.2 Yes Yes

06/27/05 8:58 0.1 4. 6 0.1 0.3 Yes Yes

* 06/28/05 7:19 0.3 4. 9 0.3 0.9 Yes Yes

* 06/29/05 14:19 0.1 5. 4 0.1 0.4 Yes Yes

06/30/05 9:26 0.4 5. 5 0.4 0.6 Yes Yes

07/01/05 8:10 0.2 4. 5 0.2 0.4 Yes Yes 7-Day Cal Error Result (6/23 - 7/01): Criteria met. Gas Source: Cylinder

Reference Gas Concentration: 2.2 CEMS Reading Error Result

Date Time Zero Reference Zero Reference Zero

criteria
met? Span

criteria
met?

07/06/05 14:26 0.0 1. 9 0.0 0.3 Yes Yes

07/07/05 10:00 0.1 2. 1 0.1 0.1 Yes Yes

07/08/05 10:24 0.0 1. 8 0.0 0.4 Yes Yes

07/09/05 11:38 0.1 2. 3 0.1 0.1 Yes Yes

07/10/05 11:30 0.0 2. 1 0.0 0.1 Yes Yes

07/11/05 11:44 0.0 2. 0 0.0 0.2 Yes Yes

07/12/05 12:28 0.3 1. 5 0.3 0.7 Yes Yes

07/13/05 12:47 0.2 1. 6 0.2 0.6 Yes Yes

07/14/05 9:01 0.1 1. 8 0.1 0.4 Yes Yes 7 Day Cal Error Result (7/06 - 7/14): Criteria met.



### A third 7-day calibration error test was conducted between the dates of July 6 and July 14, 2005. The reference gas used during the July 7-day calibra tion error test was

from the 2.2 μ g/m 3 

### concentration cylinder gas source. The 7-day calibration error test during the month of July was conducted with in the same time frame as the RATA.

### 4-41 4.2.1.2.2 Linearity Test

The Opsis system was challenged with three separate linearity tests. Linearity test

results are summarized in Table 4-42. The Opsis instrument did not meet the Part 75 performance criteria during any of the three linearity tests conducted. The first test was conducted on May 20, 2005. The reference gas us ed during the May linearity test was from the Tekran 3310 Hg calibration source. The purpose of using the Tekran 3310 was due to a limited supply of available cylinder ga ses during the test peri od and an effort to conserve the gases for the remaining durat ion of the study. The Opsis system did not

meet the criteria for the zero concentra tion or the low-, mid- , or high-level Hg concentrations during the May test. The Ma y linearity test was di scontinued after the

linear error of mid-level concentra tion measured 2.8 μg/m3 below the + 1.0 μg/m3 test

criteria.

An investigation by Opsis representatives in June concluded that the analyzer gold trap was damaged, perhaps by the nitric aci d in the oxidized mercury solution used during the system integrity test conducted immediately prior to the measurement error

test.

A second linearity test was conducted on the Opsis system on June 29, 2005. The reference gas used during the June linearity test was from the Tekran 3310 Hg calibration

source. The linear error measured for the high-level Hg concentration was 0.4 μg/m3 beyond the ±1.0 μg/m3 test criteria.

A third linearity test wa s conducted on the Opsis system on July 14, 2005. The reference gas concentrations used during the Ju ly linearity error test were from the gas cylinder sources. The July test was performed after the RATA to confirm the results of the linearity test performed prior to the RA TA. The linear error from the mid-level and high-level Hg concentration were 0.7 μg/m 3 and 2.4 μg/m3, respectively, beyond the test

criteria.

### 4-42 Table 4-42. Opsis Linearity Test—Phase 2

Low-Level Gas Concentration: 2.5

Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8

Test Date: 05/20/05 Cycle Time Gas type CEMS reading

1 21:51 Low 1.7
1 22:16 Mid * 2.3 Level Average % Error Linear error Criteria met?

Low 1.7 0.32 0.78 Yes

Mid 2.3 0.62 3.81 No 5/20/05 Linearity Result: Incomplete. * Test aborted; inadequate mid level performance.

Low-Level Gas Concentration: 2.455

Mid-Level Gas Concentration: 6.138 High-Level Gas Concentration: 9.821

Test Date: 6/29/2005 Cycle Time Gas type CEMS reading

1 18:31 Low 2.0

1 18:48 Mid 5.0 1 19:03 High 7.9

2 19:18 Low 2.4

2 19:33 Mid 5.4 2 19:48 High 8.7

3 20:00 Low 2.2

3 20:11 Mid 5.2 3 20:23 High 8.8 Level Average % Error Linear error Criteria met?

Low 2.21 10.18% 0.250 Yes
Mid 5.22 15.00% 0.921 Yes High 8.45 13.99% 1.374 No 6/29/05 Linearity Result: Criteria not met. Reference Gas Sources From Cylinders

Low-Level Gas Concentration: 2.2

Mid-Level Gas Concentration: 5.1 High-Level Gas Concentration: 10.4

Test Date: 7/14/2005 Cycle Time Gas type CEMS reading

1 9:01 Low 1.8

1 9:18 Mid 3.2 1 9:33 High 6.5

2 9:48 Low 2.0

2 10:08 Mid 3.4 2 10:26 High 7.2

3 10:47 Low 2.0

3 11:03 Mid 3.6 3 11:23 High 7.3 Level Average % Error Linear error Criteria met?

Low 1.89 13.9% 0.305 Yes
Mid 3.39 33.6% 1.715 No High 6.99 32.8% 3.412 No 7/14/05 Linearity Result: Criteria not met.

### 4-43 4.2.1.2.3 System Integrity Test

System integrity tests were performe d on the Opsis system on two separate occasions. Results of those tests are summarized in Table 4-43. The first system integrity test was performed on the Opsis system on May 20, 2005. The Opsis system did not meet the test criteria during this test, and th e test was discontinued after the mid-level

concentration measurements were record ed. The system consistently measured abnormally low stack gas values after c onducting the system integrity test. All certification tests performed after the system in tegrity test did not meet the test criteria.

MRI was requested by the on-site Opsis re presentative to re frain from conducting further system integrity tests on the Opsis system until an investigation could be performed to determine the cause of the lo w measurements obtained. An investigation by Opsis representatives in June concluded that the analyzer gold trap was damaged and the cause was suspected to be the nitric acid in the oxidized mercury solution used in the system integrity test.

A second system integrity test was pe rformed on June 28, 2005. New zero and oxidized mercury solutions were prepared fo r the HovaCal that did not include nitric acid. The solutions were prepared with 0.001N HCl. The Opsis system met the system integrity test criteria using the modified so lutions. These modified solutions were made up weekly for the Opsis system integrity test s during the remainder of the test program. The results of weekly system integrity test s are provided in Volume 3, Appendix H. The Opsis met the criteria on two of the 11 w eekly system integrity tests performed.

Table 4-43. Opsis System Integrity Test—Phase 2

Mid-Level Oxidized Mercury Concentration: High-Level Oxidized Mercury Concentration: From Hovacal

2.9

*

Test Date: 05/20/05 Time Gas type CEMS reading Error Criteria met?

4:50 Zero 0.47 0.46 Yes

19:19 Mid 1.40 1.70 No High *

5/20/05 Conv. Test Result: Criteria not met.

*Test discontinued.

From Hovacal Mid-Level Oxidized Mercury Concentration: High-Level Oxidized Mercury Concentration: 3.3

5.3

Test Date: 6/28/2005 Time Gas type CEMS reading Error Criteria met?

17:58 Zero 0 0.0 Yes

18:19 Mid 3.7 0.4 Yes 18:41 High 5.8 0.5 Yes

6/28/05 Test Result: Criteria met.

### 4-44 4.2.1.2.4 Cycl e Time Test

The Opsis system was challenged with one complete cycle time test. An effort was made to perform a cycle time test during the month of May, but the Opsis system was not operating properly resulting in cycle times up to 1 hour. The first complete cycle test was conducted on June 27, 2005. The Opsis instrument met the performance criteria during the June cycle time test and the results are shown in Table 4-44.

Table 4-44. Opsis Cycle Time—Phase 2

Note: No test in May due to slow response time.

Date: 06/27/05

Time CEM reading Comments

14:20 1.2 Pretest stable stack measurement

14:28 0 Zero and stable 14:45:08 Release CEM back to stack gas 14:53:08 1.1 Reach 95% of stable range 15:00:00 2.55 Stack gas measurement stable

0:08:00 Tolerance< 00:15:00

2.7 Pretest stable stack measurement 17:23 9.6 High level (9.85) reference Gas and stable 17:25:38 Release CEM back to stack gas 17:38:08 2.7 Reach 95% of stable range 17:40:38 2.6 Stack gas measurement stable

0:12:30 Tolerance< 00:15:00 6/27/05 Cycle time Test Results: Criteria met.



### 4.2.1.2.5 Measur ement Error Test

The Opsis system was challenged with three separate measurement error tests.

Results of measurement e rror testing are summarized in Table 4-45. The Opsis instrument did not meet the performance cr iteria during any of th e three tests conducted. The first test was conducted on May 20, 2005. The reference gas used during the May

measurement error test was from the Tekran 3310 Hg calibration source. The purpose of using the Tekran 3310 was due to a limited s upply of available cylinder gases during the test period and an effort to conserve the cy linder gases for the remaining duration of the study. The Opsis system did not meet the criteria for the zero concentration point nor any of the mercury concentrations attempted during the May test . The test was aborted after the mid-level mercury concentration was 4.3 μg /m3 below the 0.5 μg/m3 tolerance limit.

An investigation by Opsis representatives in June concluded that the analyzer gold trap may have been damaged by the nitric acid in the oxidized mercury solution used during the system integrity test conducte d prior to the measurement error test.

The second Opsis measurement error test was conducted on June 29, 2005. The reference gas used during the June measurem ent error test was from the Tekran 3310 Hg calibration source. The mid-level Hg result was 0.4 μg/m3 beyond and high-level Hg result was 0.6 μg/m3 beyond the 0.5 μg/m3 tolerance limit. No explanation is available as to why

the instrument did not meet the test criteria.

### 4-45 Table 4-45. Opsis Measurement Error Test—Phase 2

From Tekran 3310
Low-Level Gas Concentration: 2.5
Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8
Test Date: 05/20/05 Test aborted; system unable to measure adequate mid-levels

Gas type Time CEMS reading Error Criteria
met?

Zero 20:58 0.6 0.6 No
Low 21:51 1.7 1.0 No
Mid 22:15 2.3 4.3 No High 10.5 No

5/20/05 Measurement Error Result: Criteria not met.

From Tekran 3310
Low-Level Gas Concentration:
Mid-Level Gas Concentration: High-Level Gas Concentration: 2.455
6.138
9.821
Test Date: 6/29/2005

Gas type Time CEMS reading Error Criteria
met?

Zero 20:43 0.2 0.2 Yes
Low 20:00 2.2 0.2 Yes
Mid 20:11 5.2 0.9 No High 20:23 8.8 1.1 No

6/29/05 Measurement Error Result: Criteria not met. From Cylinders
Low-Level Gas Concentration: 2.2
Mid-Level Gas Concentration: 5.1 High-Level Gas Concentration: 10.4
Test Date: 7/14/2005

Gas type Time CEMS reading Error Criteria
met?

Zero 8:43 0.1 0.1 Yes
Low 9:01 1.8 0.4 Yes
Mid 9:18 3.2 1.9 No High 9:33 6.5 3.9 No

7/14/05 Measurement Error Result: Criteria not met.



### A third measurement error test was conduc ted on July 14, 2005. The reference gas concentrations used during the July measurem ent error test were from the gas cylinder sources. The July test was performed after the RATA primarily due limited time available to conduct the test prior to the RATA. The Opsis system did not meet the performance criteria since the mid-level Hg result wa s 1.4 μg/m3 beyond and high-level Hg result was 3.4 μg/m3 beyond the 0.5 μg/m3 test criterion.

4.2.1.2.6 Zero/Upscale Drift Test

The Opsis system was challenged with three separate zero/upscale drift tests. Results

of those tests are summarized in Tabl e 4-46. The instrument did not meet the performance criteria for all three test peri ods. This test does no t have the alternate

≤ 1 μ g/m 3 

### criteria for a 10 μ g/m 3 

### like the 7-day calibrati on error test. The first

### 4-46 zero/upscale drift test was performed between May 14 a nd May 21, 2005. The reference gas used during the May zero/ upscale drift test was a 2.46 μ g/m3 concentration from the Tekran 3310 Hg calibration source. The purpos e of using the Tekran 3310 was due to the limited supply of available cylinder gases dur ing the test period. On the sixth day, the Opsis system measured 0.2 μ g/m3 beyond the 0.5 μ g/m3 test tolerance for the zero gas and on the fourth day, the system did not m eet the upscale gas test criteria both because

PS 12A does not have the alternative criteria allowance when the span is defined at 10 ug/m 3 

### . The eighth day measurement which was made after the gold trap was damaged

also did not meet the criteria.

Table 4-46. Opsis Zero/Upscale Drift Tests—Phase 2

Gas Source: Tekran 3310
Reference Gas Concentration: 2.5 CEMS reading Drift Result

Date Time Zero Reference Zero Reference Zero criteria
met? Span criteria
met?

05/14/05 14:23 0.4 2. 3 0.4 0.2 Yes Yes
05/15/05 10:37 0.0 2. 3 0.0 0.2 Yes Yes
05/16/05 10:25 0.1 2. 0 0.1 0.5 Yes Yes
05/17/05 9:40 0.2 1. 9 0.2 0.6 Yes No
05/18/05 8:58 0.0 2. 0 0.0 0.5 Yes Yes
05/19/05 15:38 0.7 2. 2 0.7 0.3 No Yes
05/20/05 9:58 0.0 2. 7 0.0 0.2 Yes Yes
05/21/05 5:09 0.3 0. 7 0.3 1.8 Yes No

5/14 - 5/21 Zero Drift Resu lt: Criteria not met. 5/14 - 5/21 Upscale Drift Result: Criteria not met. Gas Source: Tekran 3100 and Cylinder*
Reference Gas Concentration: 4.9 (Tekran) and 5.8* CEMS reading Drift Result

Date Time Zero Audit Zero Audit Zero

criteria

met Span

criteria
met?

* 06/23/05 9:59 0.2 5.2 0.2 0.6 Yes No
* 06/24/05 16:19 0.3 6. 4 0.3 0.6 Yes No

* 06/25/05 10:58 0.0 6. 5 0.0 0.7 Yes No
* 06/26/05 10:52 0.1 6. 0 0.1 0.2 Yes Yes
06/27/05 8:58 0.1 4. 6 0.1 0.3 Yes Yes
* 06/28/05 7:19 0.3 4. 9 0.3 0.9 Yes No
* 06/29/05 14:19 0.1 5. 4 0.1 0.4 Yes Yes
06/30/05 9:26 0.4 5. 5 0.4 0.6 Yes No

6/23 - 6/30 Zero Drift Result: Criteria met. 6/23 - 6/30 Upscale Drift Result: Criteria not met.
Gas Source: Cylinder

Reference Gas Concentration: 2.2 CEMS reading Drift Result

Date Time Zero Audit Zero Audit Zero criteria met? Span criteria met?

07/06/05 14:26 0.0 1.9 0.0 0.3 Yes Yes
07/07/05 10:00 0.1 2. 1 0.1 0.1 Yes Yes
07/08/05 10:24 0.0 1. 8 0.0 0.4 Yes Yes
07/09/05 11:38 0.1 2. 3 0.1 0.1 Yes Yes
07/10/05 11:30 0.0 2. 1 0.0 0.1 Yes Yes
07/11/05 11:44 0.0 2. 0 0.0 0.2 Yes Yes
07/12/05 12:28 0.3 1. 5 0.3 0.7 Yes No
07/13/05 12:47 0.2 1.6 0.2 0.6 Yes No

7/06 - 7/13 Zero Drift Result: Criteria met. 7/06 - 7/13 Upscale Drift Result: Criteria not met.

### 4-47 The second 7-day calibration error test was conducted between th e dates of June 23 and June 30, 2005. The reference gas used dur ing the June 7-day calibration error test varied between the Tekran 3310 Hg gas source and the 5.8 μ g/m 3 

### concentration gas cylinder. Two sources were used due to the av ailability of the source concentration at the time available to perform the test. The syst em did not meet the upscale drift criteria

because PS 12A does not have the alternative cr iteria allowance when the span is defined at 10 ug/m 3



### .

A third 7-day calibration error test wa s conducted between July 6 and July 13, 2005. The reference gas used during the July 7-da y calibration error test was from the 2.2 μ g/m 3


### gas cylinder. The 7-day calibration error te st during the month of July was conducted

within the same time frame as the RATA. On the fourth day of the test, the system

measured 0.1 μ g/m3 beyond the 0.5 μ g/m3 tolerance limit (5% of span) specified by

PS 12A.

4.2.1.3 Tekran

The Tekran 7-day calibration error test, line arity check, system integrity test (which checks converter efficiency), measurement erro r test, and zero/upscale drift test results are presented in Tables 4-47 through 4-52. Th e Tekran system was located at the stack sampling platform and was configured with a 50-ft heated line (190°C) to the analysis system in the CEMS shelter on this platform. All reported concentrations are corrected to 20°C. Testing and test da tes are discussed below.

4.2.1.3.1 7-Day Calibration Error Test

The Tekran system was challenged with two complete 7-day calibra tion error tests.

Those test results are summarized in Tabl e 4-47. The instrument met the performance

criteria for both tests. The first test was performed between May 13 and May 20, 2005. The reference gas used during the May 7-day calibration error test varied between the Tekran 3310 Hg calibration source, and two gas cylinders with concentrations of

1.9 μ g/m 3 

### and 2.2 μ g/m 3 

### . The purpose of using the Tekr an 3310 was due to the limited supply of available cylinder gases during th e test period; the purpose of using gas cylinder sources was to provide an external reference gas source.

### 4-48 Table 4-47. Tekran 7-Day Calibration Error Test—Phase 2
Gas Source: Tekran 3310 and Cylinders Reference Gas Concentration: 2.5, 1.9* and 2.1** μ g/m 3

CEMS reading Error Result

Date Time Zero Reference Zero Reference Zero

criteria

met Span

criteria

met?

05/13/05 13:28 0.0 2.2 0.00 0.28 Yes Yes 05/14/05 8:42 0.0 2.3 0.00 0.19 Yes Yes
* 05/15/05 9:49 0.0 1.9 0.00 0.01 Yes Yes

05/15/05 12:11 0.0 2.1 0.00 0.31 Yes Yes
* 05/16/05 11:59 0.0 2.0 0.00 0.11 Yes Yes

05/16/05 13:54 0.0 2.0 0.00 0.44 Yes Yes 05/17/05 11:28 0.0 2.0 0.00 0.44 Yes Yes
* 05/17/05 13:55 0.0 1.9 0.00 0.01 Yes Yes
* 05/18/05 12:15 0.0 2.0 0.00 0.13 Yes Yes

05/18/05 15:42 0.0 1.9 0.00 0.52 Yes Yes
** 05/19/05 10:09 0.0 2.1 0.00 0.01 Yes Yes
** 05/20/05 15:57 0.0 2.1 0.00 0.03 Yes Yes 7-Day Cal Error Result (5/13 - 5/20): Met criteria. Gas Source: Tekran 3310 and Cylinder

Reference Gas Concentration: 2.5 and 2.2* μ g/m 3

CEMS Reading Error Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

* 07/06/05 17:34 0.0 1.957 0.00 0.40 Yes Yes * 07/07/05 9:03 0.0 2.014 0.00 0.35 Yes Yes

07/08/05 9:34 0.0 2.071 0.00 0.56 Yes Yes
07/09/05 8:58 0.0 1.957 0.00 0.68 Yes Yes 07/10/05 8:54 0.0 1.923 0.00 0.71 Yes Yes
07/11/05 8:54 0.0 1.923 0.00 0.71 Yes Yes
07/12/05 8:49 0.0 2.008 0.00 0.63 Yes Yes * 07/13/05 9:15 0.1 2.423 0.09 0.06 Yes Yes
* 07/14/05 9:32 0.0 2.389 0.00 0.03 Yes Yes
* 07/15/05 10:19 0.0 2.454 0.00 0.09 Yes Yes 7-Day Cal Error Result (7/6 - 7/15): Criteria met.



### An effort made to conduct a 7-day calibra tion error test during the month of June was interrupted by a system dilution orifi ce blockage on June 24. The June 25 daily measurement was not made since the system was not back in operation until June 26. The primary purpose of the July 7-day calibration erro r test was to repeat the interrupted June

test.

### 4-49 The second Tekran 7-day calibration erro r test was conducted between July 6 and July 15, 2005 which also overlapped with th e RATA. The reference gas used during the July test varied between the Tekran 3310 Hg calibration source and the 2.2 μ g/m 3


### cylinder gas source. Two different reference gase s were used in an effort to conserve the cylinder gases thereby ensuring that ther e would be enough gases to complete the certification tests on all of the Hg CEMS.

4.2.1.3.2 Linearity Test

The results of the two linear ity tests completed on the Tekran system are shown in

Table 4-48. No effort was made to conduct a linearity test on the Tekran system during the month of May. An automated linearity test using reference gases generated by the Tekran 3310 Hg calibration source was atte mpted on July 1, 2005 but was interrupted when on-site operators unintentionally terminat ed the test to conduc t a daily calibration error test. Another automated linearity test was completed on July 8, 2005 using the Tekran 3310 Hg calibration source and the test criteria were met.

A second linearity test was completed on July 13, 2005. The reference gas concentrations used during the July 13 test were from the gas cylinder sources. The July test was performed after the RATA primarily due to the fact that no low concentration cylinder gas was available in June to conduc t a test independent of the Tekran 3310 Hg calibration source. The Tekran system did not meet the test criteria during the July 13 linearity test since the averag e of the three high-level gas co ncentrations measured by the

instrument was 0.2 μ g/m3 beyond the allowable test criteria of ±1.0 μg/m3.

### 4-50 Table 4-48. Tekran Linearity Test—Phase 2

From Tekran 3310

Low-Level Gas Concentration: 2.5

Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8

Test Date: 07/08/05 Cycle Time Gas type CEMS reading

1 1:43 Low 2.613

1 4:53 Mid 6.655 1 2:10 High 10.507

2 2:25 Low 2.692

2 2:43 Mid 6.63 2 2:57 High 10.147

3 3:12 Low 2.729

3 3:25 Mid 6.636 3 3:42 High 10.531

1:30:00 Zero 0 Gas Low Mid High Average 2.678 6.640 10.395
% Error 1.63% 0.79% 1.39%

Linear Error 0.043 0.052 0.146

Criteria met? Yes Yes Yes 7/8/05 Linearity Result: Met criteria. From Cylinders

Low-Level Gas Concentration: 2.2

Mid-Level Gas Concentration: 5.1 High-Level Gas Concentration: 10.4

Test Date: 07/13/05 Cycle Time Gas type CEMS reading

1 9:30 Low 2.423

1 9:55 Mid 4.42 1 10:19 High 9.198

2 10:31 Low 2.503

2 10:43 Mid 4.539 2 11:01 High 9.152

3 11:20 Low 2.509

3 11:42 Mid 4.585 3 11:57 High 9.17

9:15:00 Zero 0.085 Gas Low Mid High Average 2.478 4.515 9.173
% Error 12.65% 11.48% 11.79%

Linear Error 0.278 0.585 1.227
Criteria met? Yes Yes No 7/13/05 Linearity Result: Criteria not met.

### 4-51 4.2.1.3.3 System Integrity Test

During the May and June certification test pe riods, two system integrity tests were performed on the Tekran system as shown in Table 4-49. The Tekran system met the test criteria during first system integrity test performed on May 19, 2005 but did not meet the test criteria during the sec ond system integrity test conducted on June 28, 2002. On June 28, the result for the mid-level gas was 0.2 μ g/m3 beyond the 0.5 μ g/m3 test criteria and the result for the high -level gas was 0.7 μ g/m3 beyond the 0.5 μ g/m3 test criteria.

The Tekran system not meeting the test cr iteria during the June 28 test could have

been due to a failure of the dilution educto r heater that occurred on the same day. The heater failure likely occurred due to an operato r maintenance error installing the heater on

June 26.

Results of the weekly system integrity te sts are provided in Volume 3, Appendix H.

The Tekran met the criteria fo r 11 of the 22 tests performed.

Table 4-49. Tekran System Integrity Test—Phase 2

From Hovacal Mid-Level Oxidized Mercury Concentration: 3.5 High-Level Oxidized Mercury Concentration: 5.6

Test Date: 05/19/05

Time Gas type CEMS reading Error Criteria

met?

15:09 Zero 0.125 0.13 Yes

16:05 Mid 3.510 0.03 Yes 16:33 High 5.785 0.22 Yes

5/19/05 Test Result: Met criteria.

From Hovacal Mid-Level Oxidized Mercury Concentration: 3.3 High-Level Oxidized Mercury Concentration: 5.3

Test Date: 6/28/2005

Time Gas type CEMS reading Error Criteria

met?

11:28 Zero 0.205 0.19 Yes

11:52 Mid 2.821 0.70 No 12:14 High 4.454 1.19 No

6/28/05 Test Result: Criteria not met.



### 4.2.1.3.4 Cycl e Time Test

The Tekran system was challenged with one complete cycle time test on July 14,

2005 and met the test criteria du ring the test as shown in Table 4-50. Two other cycle time tests were attempted on June 30, 2005 but were aborted. The first attempt was aborted due to an operator e rror while the second was a borted due to unstable stack concentrations during the test period. Limited time availability prev ented another attempt of the cycle time test in June prior to the RATA that followed the next week.

### 4-52 Table 4-50. Tekran Cycle Time Test—Phase 2

Date: 07/14/05

Time CEM reading Comments

12:10 1.97 Pretest stable stack measurement

13:02 0 Zero and stable 13:04:10 Release CEM back to stack gas 13:09:00 2.036 Reach 95% of stable range 13:19:00 2.059 Stack gas measurement stable

0:04:50 Tolerance< 00:15:00

12:10 2.02 Pretest stable stack measurement 12:28 9.073 High level (9.85) cylinder Gas and stable 12:29:10 Release CEM back to stack gas 12:37:00 1.951 Reach 95% of stable range 12:44:00 1.928 Stack gas measurement stable

0:07:50 Tolerance< 00:15:00 7/14/05 Cycle time Test Results: Met criteria.



### 4.2.1.3.5 Measur ement Error Test

No effort was made to conduct a measurement error test on the Tekran system during the month of May. An automated measurement error test using the Tekran 3310 Hg calibration source was attempted on July 1, 2005, but was interrupted by on-site operators unintentionally terminating the test to c onduct a daily calibration error test. Another automated measurement error test was comp leted on July 8, 2005 using the Tekran 3310 Hg calibration source and the instrument met the test criteria.

The second measurement error test was conducted on July 13, 2005. The reference gas concentrations used during the July measurement error test were from the reference gas cylinder sources. The July test was perf ormed after the RATA primarily due to the

lack of available low concentr ation reference gas in June to conduct a test independent of the Tekran 3310 Hg calibration source. The Tekr an system did not meet the test criteria during the July 13 test. The resu lt for the high-level gas was 0.7 μ g/m3 beyond the

0.5 μ g/m3 test criteria limit. The results of al l of the completed measurement error tests

are shown in Table 4-51.

### 4-53 Table 4-51. Tekran Measurement Error Test—Phase 2

From Tekran 3310 From Tekran 3310

Low-Level Gas Concentration: 2.5

Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8

Test Date: 7/8/2005 Gas type Time CEMS reading Error Criteria met?

Zero 1:30 0.0 0.0 Yes

Low 1:43 2.613 0.0 Yes

Mid 4:53 6.655 0.1 Yes High 2:10 10.507 0.0 Yes

7/08/05 Measurement Error Result: Met criteria. From Cylinders

Low-Level Gas Concentration: 2.2

Mid-Level Gas Concentration: 5.1 High-Level Gas Concentration: 10.4

Test Date: 7/13/2005 Gas type Time CEMS reading Error Criteria met?

Zero 9:15 0.1 0.1 Yes

Low 9:30 2.423 0.2 Yes

Mid 9:55 4.420 0.7 No High 10:19 9.198 1.2 No

7/13/05 Measurement Error Result: Criteria not met.



### 4.2.1.3.6 Zero/Upscale Drift Test

Results of the Tekran zero/ upscale drift testing are show n in Table 4-52. The Tekran system was challenged with two separate drif t tests. The instrument met the test method

criteria for the first test. The first zero/ upscale drift test was conducted between May 13 and May 17, 2005. The reference gas used during the May zero/upscale drift test varied between the Tekran 3310 Hg calibration source, and the 1.9 μ g/m3 and the 2.1 μ g/m3 Hg concentration gas cylinder sources. The di fference between Hg sources was due to the availability of the source concentration at the available time to perform the test.

A second zero/upscale drift test was c onducted between July 8 and July 15, 2005. The reference gas used during the July zero/ups cale drift test also varied between the Tekran 3310 Hg calibration source and the 2.2 μ g/m3 Hg concentration gas cylinder. The

difference between sources was due to the avai lability of the source concentration at the available time to perform the test. On the firs t four days of the test , the system measured

less than 0.5 μ g/m3 tolerance limit (5% of span) sp ecified by PS 12A which does not have an alternative criteria for spans at 10 μ g/m3.

### 4-54 Table 4-52. Tekran Zero/Upscale Drift Tests—Phase 2
Reference Gas Source: Tekran 3310 and Cylinder Reference Gas Concentration: 2.5, 1.9*, 2.1** CEMS Reading Drift Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

05/13/05 13:28 0.0 2.2 0.00 0.28 Yes Yes

05/14/05 8:42 0.0 2.3 0.00 0.19 Yes Yes

* 05/15/05 9:49 0.0 1.9 0.00 0.01 Yes Yes

05/15/05 12:11 0.0 2.1 0.00 0.31 Yes Yes

* 05/16/05 11:59 0.0 2.0 0.00 0.11 Yes Yes

05/16/05 13:54 0.0 2.0 0.00 0.44 Yes Yes

05/17/05 11:28 0.0 2.0 0.00 0.44 Yes Yes

* 05/17/05 13:55 0.0 1.9 0.00 0.01 Yes Yes

5/13 - 5/17 Zero Drift Result: Met criteria. 5/13 - 5/17 Upscale Drift Result: Met criteria. Reference Gas Source: Tekran 3310 and Cylinder Low-Level Gas Concentration: 2.5, 2.2* CEMS Reading Drift Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

07/08/05 9:34 0.0 2.071 0.00 0.56 Yes No

07/09/05 8:58 0.0 1.957 0.00 0.68 Yes No

07/10/05 8:54 0.0 1.923 0.00 0.71 Yes No

07/11/05 8:54 0.0 1.923 0.00 0.71 Yes No

07/12/05 8:49 0.0 2.008 0.00 0.63 Yes No

* 07/13/05 9:15 0.1 2.171 0.09 0.06 Yes Yes

* 07/14/05 9:32 0.0 2.389 0.00 0.03 Yes Yes

* 07/15/05 10:19 0.0 2.454 0.00 0.09 Yes Yes

7/8 - 7/15 Zero Drift Result: Met criteria. 7/8 - 7/15 Upscale Drift Result: Criteria not met.



### 4.2.1.4 ThermoElectron

The ThermoElectron 7-day calibration error test, linearity check, system integrity test (which checks converter e fficiency), measurement error test, and zero/upscale drift test results are presented in Tables 4- 53 through 4-58. The Thermo CEMS system was located at the stack sampling platform and conf igured with a 50-ft heated line (165°C) to the analysis system in the CEMS shelter on this platform.

4.2.1.4.1 7-Day Calibration Error Test

The Thermo system was challenged with one partial and one complete 7-day calibration error test. The pa rtial test was performed between May 13 and May 20, 2005. The reference gas used during the May 7-da y calibration error test was from the Tekran 3310 Hg calibration source. Ma intenance to the system by Thermo representatives on the sixth da y prevented an opportunity to obtain the sixth of seven

### 4-55 consecutive days of measurements. Although all of the recorded measurements leading to the sixth day as well as the se venth day were within the 1.0 μ g/m3 test, the test did not

meet the test criteria since 7 c onsecutive days were not completed.

A complete 7-day calibration error test was conducted on the Thermo system between June 23 and June 30, 2005. The referenc e gas used during this 7-day calibration

error test varied between the Tekran 3310 Hg calibration source and the 5.8 μ g/m 3


### reference gas cylinder. The Thermo system did not meet the test criteria during the test performed in June. During the first five days and last day of testing, the Thermo system

measured from 0.2 μ g/m3 to 1.7 μ g/m3 beyond the 1.0 μ g/m3 test criteria limit. The results for both 7-day calibration error te sts are shown in Table 4-53.

Plans to repeat the 7-day ca libration error test during th e period of the RATA were unsuccessful after the Thermo system failed to operate properly and required corrective

maintenance in the middle of the fifth RATA test run.

Table 4-53. Thermo 7-Day Calibration Error Test—Phase 2

Gas Source: Tekran 3310

Reference Gas Concentration: 2.5 CEMS reading Error Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

5/14/05 0.70 –0.12 2.81 0.12 0.35 Yes Yes

5/15/05 0.48 –0.04 2.60 0.04 0.14 Yes Yes

5/16/05 0.48 –0.38 2.63 0.38 0.17 Yes Yes

5/17/05 0.44 –0.34 2.40 0.34 0.06 Yes Yes

5/18/05 0.40 –0.34 2.29 0.34 0.17 Yes Yes 5/19/05 Maintenance to system prev ented daily measurement

5/20/05 0.65 0.03 2.70 0.03 0.24 Yes Yes 7 Day Cal Error Result: Incomplete Gas Source: Tekran 3310 and Cylinder*

Reference Gas Concentration: 4.9 and 5.8* CEMS reading Error Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

* 06/22/05 17:02 0.25 7.76 0.25 1.96 Yes No

* 06/23/05 11:29 0.28 6.99 0.28 1.19 Yes No

* 06/24/05 11:33 0.18 7.44 0.18 1.64 Yes No

* 06/25/05 11:50 0.37 8.32 0.37 2.52 Yes No

* 06/26/05 11:20 0.22 7.63 0.22 1.83 Yes No

06/27/05 9:22 0.26 4.52 0.26 0.39 Yes Yes

* 06/28/05 12:11 0.43 6.59 0.43 0.79 Yes Yes

* 06/29/05 11:51 0.05 5.89 0.05 0.09 Yes Yes

* 06/30/05 11:12 0.46 6.11 0.46 0.31 Yes Yes

* 07/01/05 8:22 0.03 8.48 0.03 2.68 Yes No 7-Day Cal Error Result (6/22 - 7/01): Criteria not met.

### 4-56 4.2.1.4.2 Linearity Test

Results of linearity testing of the Thermo system are summarized in Table 4-54. One linearity test was conducted on the Thermo system on June 29, 2005. The reference gas concentrations used were from the Tekran 3310 Hg calibration source. The Thermo system did not meet the test criteria during this linearity test since the average of the three high-level gas concentrations measured by the instrument was 0.1 μ g/m3 beyond the

allowable tolerance of ±1.0 μ g/m3.

Table 4-54. Thermo Linearity Test—Phase 2

From Tekran 3310
Low-Level Gas Concentration: 2.5

Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8

Test date: 6/29/2005 Cycle Time Gas type CEMS reading

1 18:33 Low 2.19

1 18:47 Mid 5.26 1 18:58 High 8.81

2 19:18 Low 2.53

2 19:24 Mid 5.38 2 19:44 High 8.75

3 19:49 Low 2.47

3 20:09 Mid 5.29 3 20:19 High 8.53

20:34 Zero 0.27 Gas Low Mid High Average 2.40 5.31 8.70
% Error 2.6% 13.5% 11.4%

Linear Error 0.063 0.830 1.12

Criteria met? Yes Yes No 6/29/05 Linearity Result: Criteria not met.



### 4.2.1.4.3 System Integrity Test

The results of the weekly system integrit y tests on the Thermo system are provided in Table 4-55. System integrity tests were performed on the Thermo during both the May and June, 2005 certification test periods. The Th ermo system did not meet the test criteria during either of the two system integrity te sts performed. The results for the high-level gas were 0.4 μ g/m3 beyond the allowable test tolerance of + 0.5 μ g/m3 for both the May and June tests. Results of the weekly syst em integrity tests are provided in Volume 3, Appendix H. The Thermo met the criteria for three of the 22 tests performed.

### 4-57 Table 4-55. Thermo System Integrity Test—Phase 2

From Hovacal Mid-Level Oxidized Mercury Concentration: 3.3 High-Level Oxidized Mercury Concentration: 5.3

Test Date: 05/19/05

Time Gas type CEMS reading Error Criteria met?

12:45 Zero –0.13 0.13 Yes

12:23 Mid 3.64 0.33 Yes 11:59 High 6.21 0.88 No

5/19/05 Converter Test Result: Criteria not met.

From Hovacal Mid-Level Oxidized Mercury Concentration: 3.3 High-Level Oxidized Mercury Concentration: 5.3

Test Date: 6/29/2005

Time Gas Type CEMS Reading Error Criteria met?

14:34 Zero 0.17 0.17 Yes

14:54 Mid 3.72 0.43 Yes 15:09 High 6.18 0.85 No

6/29/05 Test Result: Criteria not met.



### 4.2.1.4.4 Cycl e Time Test

The Thermo system was challenged with one cycle time test on June 26, 2005. The instrument met the test method criteria during the test. The results of the June 26 cycle

time test are shown in Table 4-56.

Table 4-56. Thermo Cycle Time—Phase 2

Date: 06/26/05 Time CEM reading Comments

15:57 2.6 Pretest stable stack measurement

16:12 0.7 Zero and stable 16:14:00 Release CEM back to stack gas 16:19:48 2.45 Reach 95% of stable range 16:24:08 2.55 Stack gas measurement stable

0:05:48 Tolerance< 00:15:00

Pretest stable stack measurement 16:39 11.39 High level (9.85) reference Gas and stable 16:38:00 Release CEM back to stack gas 16:49:08 2.82 Reach 95% of stable range 16:58:58 2.64 Stack gas measurement stable

0:11:08 Tolerance< 00:15:00 6/26/05 Cycle time Test Results: Met criteria.



### 4.2.1.4.5 Measur ement Error Test

A measurement error test was conducted on the Thermo system using the Tekran 3310 Hg calibration source on June 29, 2005. The Thermo system did not meet the test criteria. The results for both the mid- and high-level Hg gases were beyond the 0.5 μ g/m3

test tolerance limit. Results of the measur ement error test are shown in Table 4-57.

### 4-58 Table 4-57. Thermo Measurement Error Test—Phase 2

From Tekran 3310

Low-Level Gas Concentration: 2.5

Mid-Level Gas Concentration: 6.1 High-Level Gas Concentration: 9.8

Test Date: 6/29/2005

Gas type Time CEMS reading Error Criteria

met?

Zero 20:34 0.27 0.27 Yes

Low 19:49 2.47 0.01 Yes

Mid 20:09 5.29 0.85 No High 20:19 8.53 1.29 No

6/29/05 Measurement Error Result: Criteria not met.



### 4.2.1.4.6 Zero/Upscale Drift Test

Zero/upscale drift test results for the Th ermo system are shown in Table 4-58. The Thermo system underwent one partial and one complete zero/upscale drift test. The

Thermo did not meet the test criteria on either of the two tests conducted. The partial test was performed between May 13 and May 20, 2005. The reference gas used during the May zero/upscale drift test was from th e Tekran 3310 Hg calibration source. Maintenance to the system by Thermo repr esentatives on the sixth day prevented an opportunity to obtain the sixt h of seven consecutive days of measurements. All the recorded measurements leading to the sixth day as well as the seventh day were within

the 0.5 μ g/m3 test limitation, due to the missed si xth day of comparative test data, the Thermo system did not meet the test method criteria for the May zero/ upscale drift test.

A second zero/upscale drift test was conducted between June 23 and June 30, 2005. The reference gas used during the June zero/ups cale drift test varied between the Tekran 3310 Hg calibration source and the 5.8 μ g/m3 Hg concentration reference gas cylinder

source. The difference between sources was due to the availab ility of the source

concentration at the available time to perform the test. The Thermo instrument measured

from 0.3 μ g/m3 to 2.0 μ g/m3 beyond the allowable 0.5 μ g/m3 test tolerance on five of eight test dates.

### 4-59 Table 4-58. Thermo Zero/Upscale Drift Tests—Phase 2

Gas Source: Tekran 3310

Reference Gas Concentration: 2.5 CEMS reading Drift Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

05/14/05 16:41 –0.1 2.8 0.12 0.35 Yes Yes

05/15/05 11:34 0.0 2.6 0.04 0.14 Yes Yes

05/16/05 11:28 –0.4 2.6 0.38 0.17 Yes Yes

05/17/05 10:35 –0.3 2.4 0.34 0.06 Yes Yes

05/18/05 9:36 –0.3 2.3 0.34 0.17 Yes Yes 05/19/05 Maintenance to system prev ented daily measurement
05/20/05 15:38 0.0 2.7 0.03 0.24 Yes Yes Zero Drift Result: Incomplete Upscale Drift Result: Incomplete Gas Source: Tekran 3310 and Cylinder

Reference Gas Concentration: 4.9 and 5.8* CEMS reading Drift Result

Date Time Zero Reference Zero Reference Zero

criteria

met? Span

criteria

met?

* 06/23/05 11:29 0.28 6.99 0.28 1.19 Yes No

* 06/24/05 11:33 0.18 7.44 0.18 1.64 Yes No

* 06/25/05 11:50 0.37 8.32 0.37 2.52 Yes No

* 06/26/05 11:20 0.22 7.63 0.22 1.83 Yes No

06/27/05 9:22 0.26 4.52 0.26 0.39 Yes Yes

* 06/28/05 12:11 0.43 6.59 0.43 0.79 Yes No

* 06/29/05 11:51 0.05 5.89 0.05 0.09 Yes Yes

* 06/30/05 11:12 0.46 6.11 0.46 0.31 Yes Yes

6/23 - 6/30 Zero Drift Result: Met criteria. 6/23 - 6/30 Upscale Drift Result: Criteria not met.



### 4.2.2 Phase 2 RATA Test Results

The data presented in this section are fr om the RA test conducted during July 7-12, 2005. The testing consisted of 12 test runs comparing four mercury Hg CEMS to the Ontario Hydro (OH) reference method. Overa ll, emissions as measured by OH displayed a general downward trend from 3 to 1.4 μ g/m 3 

### over the course of 12 runs.

The Durag, Opsis, and Tekran instruments co llected data for all 12 of the RA tests

and the Thermo instrument collected usable da ta for most of the first 5 RA test runs. Duplicate OH sampling trains were used during all 12 RA test runs. Further details of the Ontario Hydro results and results for each mercury CEMS are presented in the sections

that follow.

Mercury analysis results are provided in Appendix E of Volume 3. Mercury CEMS data collected during the RA test are provided in Appendix F of Volume 3.

### 4-60 4.2.2.1 Ontario Hy dro Sample Results

Sampling times for the Ontario Hydro sa mpling method are provided in Table 4-59. All runs had sample collection times of 2 hr according to the method. Samples were collected over a period of several days in or der to observe any vari ation in emission data that would be useful in evaluating CEMS response.

Table 4-59. Phase 2 RA Test Run Times

Run

number Date Stack sampling intervals (in minutes per 24-hour clock) Sampling time (min)

1 7/7/2005 10:45 - 12:45 120

2 7/7/2005 14:35 - 16:35 120

3 7/8/2005 10:00 - 12:00 120

4 7/8/2005 13:55 - 15:55 120

5 7/9/2005 9:25 - 11:25 120

6 7/9/2005 13:10 - 15:10 120

7 7/10/2005 9:25 - 11:25 120

8 7/10/2005 12:40 - 14:40 120

9 7/11/2005 09:15 - 11:15 120

10 7/11/2005 14:00 - 16:00 120

11 7/12/2005 9:45 - 11:45 120

12 7/12/2005 13:00 - 15:00 120



### Table 4-60 summarizes the sampling condi tions of the reference method trains. Ontario Hydro sampling and recovery data ar e provided in Appendix C of Volume 3 of this report. Method 3B sample collection data and the Orsat analysis results for each sample are also included with Appendix C. Sa mple traceability data sheets are presented in Appendix B, and sampling equipment calibra tion results are in Appendix D of Volume

3.

Mercury analysis results are presented in Table 4-61 and were obtained using the Ontario Hydro (OH) method analytical procedur es. Data are presented separately for each sample train component.

The reproducibility between run duplicates for the KMnO 4 

### /H 2 

### SO 4 

### fraction of the OH sampling trains was large (> 10% RD) for 8 of the 12 runs. The analyt ical laboratory was asked to reanalyze this fraction from each of th e trains. This time a di fferent set of 8 runs had large RD (> 10%) values, so the labor atory was contacted. During a conversation with the laboratory, it was discovered that they had did not clear the KMnO 4 

### samples prior to extracting an aliquot for analysis. Reanalysis results are included in Appendix E of Volume 3 of this report.

Because the highest amount of mercury is found in the KMnO 4 

### /H 2 

### SO 4 

### impingers,

with much of it located in the brown residue inside the sample bottle, both the first and

second KMnO 4 

### /H 2 

### SO 4 

### sample results were considered nonrepresentative of the sample.

### 4-61 Table 4-60. Phase 2 RA Test Stack Sampling Data
Sampling Gas Orsat Analysis Avg. stack Iso- time volume Oxygen CO 2 Water temp. kinetic (min) (dscm) (%) (%) (%) ( ° F) (%)

Run 1 120 2.615 5.6 12.4 16.0 131.1 102.7

Run 1 dup 120 2.589 5.0 13.4 15.2 129.3 103.6

Run 2 120 2.084 5.6 12.4 15.9 130.7 102.6

Run 2 dup 120 2.107 5.2 13.4 15.1 128.9 104.2

Run 3 120 2.027 5.6 12.6 16.3 131.8 101.2

Run 3 dup 120 2.042 4.8 13.4 15.6 130.2 102.7

Run 4 120 2.026 5.4 12.8 15.7 130.7 102.5

Run 4 dup 120 2.059 4.8 13.4 14.9 128.6 103.8

Run 5 120 2.015 5.6 12.6 15.6 130.3 99.7

Run 5 dup 120 2.060 6.4 12.2 15.0 128.9 102.4

Run 6 120 2.031 5.8 12.6 15.2 129.5 97.6

Run 6 dup 120 2.090 6.0 12.6 14.5 127.7 102.3

Run 7 120 2.035 5.6 12.8 15.5 130.1 100.6

Run 7 dup 120 2.042 5.6 12.8 14.9 128.7 102.5

Run 8 120 2.068 5.6 12.6 15.8 130.8 102.5

Run 8 dup 120 2.060 5.6 13.0 15.0 129.0 102.3

Run 9 120 2.011 5.4 12.8 16.0 131.1 100.9

Run 9 dup 120 2.031 5.4 12.8 15.3 129.3 102.5

Run 10 120 2.018 5.4 12.8 15.9 131.0 102.7

Run 10 dup 120 2.001 5.0 13.2 15.4 129.6 102.3

Run 11 120 2.070 5.2 13.2 16.0 130.9 102.4

Run 11 dup 120 2.060 5.2 13.2 15.6 130.0 102.6

Run 12 120 2.147 5.6 12.8 15.8 130.5 103.5

Run 12 dup 120 2.082 5.6 12.8 15.4 129.7 102.44-62Table 4-61. Phase 2 RA Test Ontario Hydro Mercury Analysis Results (μg)Gaseous phaseIonic ElementalParticle bound phaseField IDFilterProberinsePart. boundsubtotalKClimpingersHNO3/H2O2impingerHNO3/H2O2imp. blankcorrectedamt.bKMnO4/H2SO4impingerscElementalsubtotalGaseousphasesubtotalTotal(μg)Run 1 0.011a0.020 0.031 0.980 0.170 0.160 5.76 5.93 6.90 6.94Run 1 dup 0.021a0.030 0.052 1.013 0.164 0.154 6.30 6.46 7.47 7.53Run 2 < 0.005 < 0.015 < 0.020 0.486 0.072a0.062 3.91 3.98 4.46 4.47Run 2 dup < 0.005 < 0.011 < 0.016 0.636 0.082a0.0722.43 2.51 3.13 3.14Run 3 < 0.005 < 0.018 < 0.023 0.509 0.087a0.077 3.99 4.08 4.58 4.59Run 3 dup < 0.005 < 0.016 < 0.021 0.579 0.106a0.096 4.05 4.16 4.73 4.74Run 4 0.013a0.064 0.077 0.487 0.095a0.085 3.21 3.31 3.78 3.87Run 4 dup < 0.005 0.061 0.061 0.531 0.078a0.068 3.19 3.27 3.79 3.86Run 5 < 0.005 0.029 0.029 0.455 0.076a0.066 3.14 3.22 3.66 3.70Run 5 dup < 0.005 0.029 0.029 0.456 0.100a0.090 3.01 3.11 3.56 3.60Run 6 < 0.005 0.024 0.024 0.306 0.101a0.091 3.08 3.18 3.47 3.51Run 6 dup < 0.005 0.036 0.036 0.385 0.060a0.050 2.96 3.02 3.39 3.44Run 7 < 0.005 0.046 0.046 0.441 0.133a0.123 3.09 3.22 3.65 3.71Run 7 dup < 0.005 < 0.019 < 0.024 0.499 0.120a0.1102.23 2.35 2.83 2.84Run 8 < 0.005 0.023 0.023 0.458 0.123a0.113 3.12 3.25 3.69 3.73Run 8 dup < 0.005 < 0.022 < 0.027 0.637 0.099a0.089 3.30 3.39 4.02 4.03Run 9 < 0.005 < 0.021 < 0.026 0.550 0.096a0.086 4.27 4.37 4.91 4.92Run 9 dup < 0.005 < 0.019 < 0.024 0.771 0.071a0.061 4.15 4.22 4.98 4.99Run 10 0.006a0.055 0.061 0.897 0.058a0.048 4.42 4.48 5.37 5.44Run 10 dup < 0.005 0.033 0.033 0.769 0.052ad0.0423.18 3.23 3.99 4.03Run 11 0.007a< 0.016 0.007 0.370 0.113a0.103 3.40 3.52 3.88 3.89Run 11 dup < 0.005 0.019 0.019 0.357 0.081a0.071 3.69 3.77 4.12 4.15Run 12 < 0.005 < 0.020 < 0.025 0.337 0.096a0.086 2.84 2.94 3.27 3.28Run 12 dup < 0.005< 0.020 < 0.025 0.341 0.080a0.0702.05 2.13 2.46 2.47FB-20.006 < 0.007 < 0.012 0.032 < 0.016FB-40.010 < 0.008 < 0.014 0.057 0.019SB< 0.005 < 0.006 < 0.001 0.006 0.003Hydroxylaminee0.00004 0.00004FB = Field Blank Train; SB = Solution Blank plus Filter Blank.aThe Field Blank Train result exceeded 30% of the measured value, however the contribution doesnot significantly impact totalresults.bBlank corrections performed per OH method.cResults were reanalyzed with no way to correct for solution blank; however, the estimated blankcontribution is less than 1% of the mercury total.dThe Solution Blank exceeded 10% of the measured value; howeverthe contribution does not significantly impact total results.eA maximum of approximately 0.2 mL (1-2 drops) in KCl impingers and 0.2 mL in KMnO4/H2SO4impingers was used during recovery; amount in blank was 0.0002μg/mL.NOTE:Bolded sample results are biased low.

### 4-63 A second laboratory (ARCADIS G&M, Inc. in Research Triangle Park, NC) was asked to reanalyze the remaining portion of the original KMnO 4 

### /H 2 

### SO 4 

### samples. Upon receipt at ARCADIS, the remaining sample vol ume in the bottles did not add up correctly. Subsequent conversations with Oxford Labor atory revealed that one 50-mL aliquot was extracted from each sample for preparation and duplicate analysis (i.e., one sample aliquot processed, then analyzed tw ice). Also, the four KMnO 4 

### /H 2 

### SO 4 

### samples which had been spiked were missing an additional 100-mL to 200-mL volume with no corresponding analytical data.

In order to determine the fraction of mercury contained in the KMnO 4 

### fraction of each train, analytical results from each Oxford a liquot times the aliquot volume was added to the ARACADIS analytical resu lt times the remaining sample volume to obtain a sum total mass. Because the four spiked samples from Oxford were missing an additional 100-mL to 200-mL of sample, the results on those sa mples are biased low since those missing

amounts cannot be added into the total.

Tables 4-62 and 4-63 combine the mercury an alysis results with the stack sampling results and provide the mercur y emissions on a concentration basis. All test runs used duplicate trains, and precision information is summarized in Table 4-64. The relatively large RD for the elemental fraction on Runs 2, 7, 10, and 12 is most lik ely the result of not having the complete samples for analysis for those runs. Figure 4-9 shows concentrations of the total gaseous and oxidized fraction of mercury along with scatter points from each

train.

The OH sampling was performed isokinetically from a single point at a similar effective sampling location as the Hg CEMS and sorbent trap monitoring system. As specified in Part 75 requirements for me rcury monitoring and PS-12A, only the ionic (oxidized) and elemental fractions of the OH results are included in the gaseous phase

concentration values used for the RATA cal culations. Therefore, the mercury CEMS and the OH results are on a similar basis (i.e., gaseous phase only, concentrations per dry standard volume). The particle-bound fraction, which constituted 1% (o r less) of the total mercury, is reported only fo r informational purposes.

The field blank train HNO 3 

### /H 2 

### O 2 

### impinger results previous ly shown on Table 4-61 are noteworthy due to the presence of mercury at levels greater th an 30% of the field sample values. The cause is not known. Even though the mercury levels in th e field blank trains were greater than 30% of the stack samples, it should be noted that th is fraction constitutes only about 5% of the total mercury in the train.

### 4-64 Table 4-62. RA Total OH Mercury Concentrations

Particle-bound subtotal Gaseous-phase subtotal

Mass ( μ g) Concentration ( μ g/dscm) Mass ( μ g) Concentration ( μ g/dscm)

Run 1 0.031 a 0.012 6.90 2.64
Run 1 rep 0.052 a 0.020 7.47 2.89
Avg. 2.77

Run 2 <0.020 N/D 4.46 b 2.14
Run 2 rep <0.016 N/D 3.13 b 1.49
Avg. 1.82

Run 3 <0.023 N/D 4.58 b 2.26
Run 3 rep <0.021 N/D 4.73 b 2.32
Avg. 2.29

Run 4 0.077 a 0.038 3.78 b 1.87
Run 4 rep 0.061 0.030 3.79 b 1.84
Avg. 1.86

Run 5 0.029 0.014 3.66 b 1.82
Run 5 rep 0.029 0.014 3.56 b 1.73
Avg. 1.78

Run 6 0.024 0.012 3.47 b 1.71
Run 6 rep 0.036 0.017 3.39 b 1.62
Avg. 1.67

Run 7 0.046 0.023 3.65 b 1.79
Run 7 rep <0.024 N/D 2.83 b 1.39
Avg. 1.60

Run 8 0.023 0.011 3.69 b 1.79
Run 8 rep <0.027 N/D 4.02 b 1.95
Avg. 1.87

Run 9 <0.026 N/D 4.91 b 2.44
Run 9 rep <0.024 N/D 4.98 b 2.45
Avg. 2.45

Run 10 0.061 a 0.030 5.37 b 2.66
Run 10 rep 0.033 0.016 3.99 b d 1.99
Avg. 2.33

Run 11 0.007 a 0.003 3.88 b 1.87
Run 11 rep 0.019 0.009 4.12 b 2.00
Avg. 1.94

Run 12 <0.025 N/D 3.27 b 1.52
Run 12 rep <0.025 N/D 2.46 b 1.18
Avg. 1.36

a The field blank train result exceeded 30% of the measured value; these re sults are not used in the gaseous-phase mercury concentration calculations.

b The Field Blank Train result exceeded 30% of t he measured value, however the contribution does not significantly impact total results.

c The Solution Blank exceeded 10% of the measur ed value; however, the contribution does not significantly impact total results.

N OTE : Shaded sample results are biased low.

### 4-65 Table 4-63. Phase 2 RA Gaseous-Phase Mercury From OH Testing

Elemental portion Oxidized portion Total

gaseous
Mass ( μ g) Concentration ( μ g/dscm) Mass ( μ g) Concentration ( μ g/dscm) Concentration ( μ g/dscm) % Oxidized a (Ionic)

Run 1 5.93 2.27 0.980 0.375 2.64 14.2 Run 1 rep 6.46 2.50 1.013 0.391 2.89 13.6 Avg. 2.38 0.383 2.77 13.9

Run 2 3.98 1.91 0.486 0.233 2.14 10.88 Run 2 rep 2.51 1.19 0.636 0.302 1.49 20.2 Avg. 1.55 0.268 1.82 14.72

Run 3 4.08 2.01 0.509 0.251 2.26 11.1 Run 3 rep 4.16 2.04 0.579 0.284 2.32 12.2 Avg. 2.03 0.267 2.29 11.7

Run 4 3.31 1.63 0.487 0.240 1.87 12.8 Run 4 rep 3.27 1.59 0.531 0.258 1.84 14.0 Avg. 1.61 0.249 1.86 13.4

Run 5 3.22 1.60 0.455 0.226 1.82 12.4 Run 5 rep 3.11 1.51 0.456 0.221 1.73 12.8 Avg. 1.55 0.223 1.78 12.6

Run 6 3.18 1.56 0.306 0.150 1.72 8.77 Run 6 rep 3.02 1.443 0.385 0.184 1.62 11.3 Avg. 1.50 0.167 1.67 10.0

Run 7 3.22 1.58 0.441 0.216 1.79 12.04 Run 7 rep 2.35 1.15 0.499 0.244 1.39 17.5 Avg. 1.37 0.230 1.60 14.4

Run 8 3.25 1.57 0.458 0.221 1.79 12.4 Run 8 rep 3.39 1.65 0.637 0.309 1.96 15.8 Avg. 1.61 0.265 1.87 14.2

Run 9 4.37 2.17 0.550 0.274 2.44 11.2 Run 9 rep 4.22 2.08 0.771 0.380 2.45 15.5 Avg. 2.12 0.327 2.45 13.3

Run 10 4.48 2.22 0.897 0.445 2.66 16.7 Run 10 rep 3.23 1.614 0.769 0.38 2.00 19.2 Avg. 1.92 0.414 2.33 17.8

Run 11 3.52 1.70 0.370 0.179 1.87 9.5 Run 11 rep 3.77 1.83 0.357 0.173 2.00 8.6 Avg. 1.77 0.176 1.94 9.1

Run 12 2.94 1.37 0.337 0.157 1.52 10.3 Run 12 rep 2.130 1.02 0.341 0.164 1.18 13.8 Avg. 1.20 0.160 1.36 11.8

a % Oxidized = (Oxidized Concentration / Total Concentration) * 100.

N OTE : Runs 2Rep, 7Rep, 10Rep, and 12Rep (shaded) are biased low.

### 4-66 Table 4-64. Phase 2 Paired OH Tr ain Relative De viation (RD)

Concentration %RD Run Avg Oxidized (KCl) Elemental Gaseous subtotal

Run 1 2% 5% 5%

Run 2 13% 23% 18%

Run 3 6% 1% 1%

Run 4 4% 1% 1%

Run 5 1% 3% 3%

Run 6 10% 4% 3%

Run 7 6% 16% 13%

Run 8 17% 2% 4%

Run 9 16% 2% 0.2%

Run 10 7% 16% 14%

Run 11 2% 4% 3%

Run 12 2% 14% 13%

The PS-12A objective is <10% RD, wh ere %RD = 100 * (Abs(a-b)) / (a+b).

Values shown in bold for Gaseous Subtotal have a RD > 10%. Shaded values have RD calculated from samples with low biased results.4-67Figure 4-9. Phase 2 OH Gaseous Phase Mercury Concentrations0123451 2 3 4 5 6 7 8 9 10 11 12Run No.

Hg Conc. (ug/dsm3)OHOH RepAvg Total OHAvg OxidizedOxOx Rep

### 4-68 Results from the remaining field blank samp les revealed the presence of mercury in

the filter and KMnO 4 

### impingers at levels near the de tection limit. Also, two of the six solution blanks indicated the pr esence of mercury near the dete ction limit. As previously

indicated at the bottom of Ta ble 4-67, the calculated contribution from hydroxylamine (used in train recovery for the KCl and KMnO 4 

### impingers) is not expected to have contributed significantly to the remaining impingers. The laboratory method blanks showed no levels of mercury above detection limits.

The estimated contribution from solution blanks was less than 1% of the total amount of mercury found in the samples. Thus, even though mercury was found in the

HNO 3 

### /H 2 

### O 2 

### and KMnO 4 

### /H 2 

### SO 4 

### solution blank samples, it did not appear to have an appreciable effect on the overall result. The HNO 3 

### /H 2 

### O 2 

### samples were blank-corrected using the decision tree shown below in Fi gure 4-10, as described in Section 13.4.3.1 of the Ontario Hydro Method. The KMnO 4 

### /H 2 

### SO 4 

### samples could not be blank corrected since the results are a combination of more than one analysis.

Figure 4-10. Decision Tree for Blank Corrections

Most significantly, the Relative Deviati on (RD) for seven of the 12 runs exceeded the 10% RD criteria in PS-12A. The great est deviation is attributed to the KMnO 4 

### /H 2 

### SO 4 

### impingers. These impingers were reanalyzed, but since the H 2 

### O 2 

### impinger results

contributed < 5% of the total and were c onsistent over a narrow concentration range, those impingers were not reanalyzed. A review of other sampling parameters (O 2 

### , CO 2 

### , and H 2 

### O) indicates that all parameters for all ru ns were within 8% of each other. Thus sampling variations do not appear to be cont ributing to the RD variances for those four runs (3, 4, 6, and 12). The RD calculation (p reviously called RSD) is Equation K-7 from Part 75 Appendix K (per 75.22) a nd Equation 12A-1 from PS-12A.

4.2.2.2 CEMS RA Results

Table 4-65 summarizes the relative accur acy calculations for each of the CEMS

evaluated. Because four of the runs had a RD > 10%, and only three could be eliminated

### 4-69 the two runs with the largest RD (Runs 2 a nd 10) were eliminated first. The remaining two runs had a RD of 13% (Runs 7 and 12). The RA was calculated using first one then the other of these remaining two runs. The run which produced the lowest RA value was included for reporting. Calculations followed th e procedures of Part 75, and are provided in Table 4-66 through 4-69. Hg CEMS data ar e included in Appendix F, and results for each analyzer are briefly discussed below. Emissions appeared to follow a generally decreasing trend from around 3 μ g/m 3 

### to 1.4 μ g/m 3 

### throughout the course of the test. Because mercury was observed in the solution blanks, blank corrections were applied to the OH results. Hg levels measured with th e OH method were fairly consistent with all average Hg CEM values.

The reported values in the RA tables ar e based on the resolution of the analyzer; however the believed resolution is more likely 0.1 ug/m 3



### .

Table 4-65 and Figure 4-11 show that despit e the large RD numbers seen in Runs 2, 7, 10, and 12, the average OH results are consiste nt with much of the CEMS results.

Table 4-65. Phase 2 Summary of All RA Results for All CEMS
CEMS ( μ g/dscm) Run

number OH gaseous

mercury Durag Opsis Tekran Thermo

1 2.77 6.07 2.19 2.41 2.19

2 1.82 3.88 2.01 1.93 1.79

3 2.29 3.67 1.77 2.08 1.94

4 1.86 2.59 1.69 1.40 1.47

5 1.78 2.51 1.34 1.37 2.19

6 1.67 1.53 1.50 1.44 –0.32

7 1.60 2.15 1.24 1.55 –0.26

8 1.87 1.79 1.70 1.57 –0.21

9 2.45 2.69 1.28 2.16 –0.20

10 2.33 2.65 1.45 1.92 –0.11

11 1.94 1.56 1.19 1.65 0.38

12 1.36 1.29 1.05 1.31 3.03 Relative Accuracy using

best 9 runs 75.7% 36.2% 18.8% 94.5%

N OTE : Data in bold indicates that run was not used to calculate Relative Accuracy.



### Note that the RA crite ria can be either < 20% RA or + 1 μ g/m 3 

### . All four CEMS met

the mean difference criteria of < 1 μ g/m 3 

### (though the Thermo system quit operating accurately during Run 5.) Calculations for Du rag produced a relative accuracy of 76% for the best 9 test runs. Opsis relative accuracy was around 36% . Tekran RA results were

around 19%. The Thermo RA results were about 95% .

Figures 4-12 through 4-15 show plots of the run-by-run data for each analyzer, and Tables 4-66 through 4-69 show RA results for each analyzer compared with the OH

method.4-70Figure 4-11. Phase 2 Summary of RA Tests-0.50.00.51.01.52.02.53.03.54.04.51 2 3 4 5 6 7 8 9 10 11 12Run No.

Hg Conc. (ug/dsm3)Gaseous OHDuragOpsisTekranThermo

### 4-71 Figure 4-12. Phase 2 RA—OH Versus Durag

Figure 4-13. Phase 2 RA—OH Versus Opsis 0 1 2 3 4 5 6 7

1 2 3 4 5 6 7 8 9 10 11 12

Run No.HgC o n c .(ug/m 3) O H M e th o d

Durag

0 1 2 3

1 2 3 4 5 6 7 8 9 10 11 12

Run No.HgC o n c .(ug/m 3) O H M e th o d

O p s is

### 4-72 Figure 4-14. Phase 2 RA—OH Versus Tekran

Figure 4-15. Phase 2 RA—OH Versus Thermo -0 .5 0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 3 .0 3 .5

1 2 3 4 5 6 7 8 9 10 11 12

Run No.HgC o n c .(ug/m 3) O H M e th o d

Thermo 0 1 2 3

1 2 3 4 5 6 7 8 9 10 11 12

Run No.HgC o n c .(ug/m 3) O H M e th o d

Tekran

### 4-73 Table 4-66. Phase 2 RA Results for Durag

CEMS Avg. OH Total Hg Difference

Run Response Response (d)

Number Use Date Time (ug/dscm) (ug/dscm) (ug/dscm)

1 Yes 7/7/2005 10:45 - 12:45 6.07 2.77 -3.30

2 No 7/7/2005 14:35 - 16:35 3.881 1.82 -2.061

3 Yes 7/8/2005 10:00 - 12:00 3.67 2.29 -1.38

4 Yes 7/8/2005 13:55 - 15:55 2.59 1.86 -0.73

5 Yes 7/9/2005 9:25 - 11:25 2.51 1.78 -0.73

6 Yes 7/9/2005 13:10 - 15:10 1.53 1.67 0.14

7 No 7/10/2005 9:25 - 11:25 2.15 1.6 -0.55

8 Yes 7/10/2005 12:40 - 14:40 1.79 1.87 0.08

9 Yes 7/11/2005 09:15 - 11:15 2.69 2.45 -0.24

10 No 7/11/2005 14:00 - 16:00 2.654 2.33 -0.324

11 Yes 7/12/2005 9:45 - 111:45 1.56 1.94 0.38

12 Yes 7/12/2005 13:00 - 15:00 1.29 1.36 0.07

Arithmetic Mean a (ug/dscm): 2.63 2.00 -0.63

BAF b 1.24

Standard Deviation 1.14

Confidence Coefficient d 0.88

Relative Accuracy e (% of RM) 75.7%

a Arithmetic Mean = 1/n S d i

b BAF = 1 + I 1/n S d i I / HgCEMS(avg)

c Standard Deviation = [ (S d i 2 - (S d i ) 2 / n) / (n-1) ] 1/2

d Confidence Corfficient = t 0.975 * Standard Deviation / n 1/2 , where t 0.975 = 2.306

e Relative Accuracy = ([Difference Arithmetic Mean] + [Confidence Coefficient]) / RM Arithmetic Mean *

100

### 4-74 Table 4-67. Phase 2 RA Results for Opsis

CEMS Avg. OH Total Hg Difference

Run Response Response (d)

Number Use Date Time (ug/dscm) (ug/dscm) (ug/dscm)

1 Yes 7/7/2005 10:45 - 12:45 2.19 2.77 0.58

2 No 7/7/2005 14:35 - 16:35 2.007 1.82 -0.187

3 Yes 7/8/2005 10:00 - 12:00 1.77 2.29 0.52

4 Yes 7/8/2005 13:55 - 15:55 1.69 1.86 0.17

5 Yes 7/9/2005 9:25 - 11:25 1.34 1.78 0.44

6 Yes 7/9/2005 13:10 - 15:10 1.50 1.67 0.17

7 Yes 7/10/2005 9:25 - 11:25 1.24 1.60 0.36

8 Yes 7/10/2005 12:40 - 14:40 1.70 1.87 0.17

9 Yes 7/11/2005 09:15 - 11:15 1.28 2.45 1.17

10 No 7/11/2005 14:00 - 16:00 1.449 2.33 0.881

11 Yes 7/12/2005 9:45 - 111:45 1.19 1.94 0.75

12 No 7/12/2005 13:00 - 15:00 1.053 1.36 0.307

Arithmetic Mean a (ug/dscm): 1.55 2.03 0.48

BAF b 1.31

Standard Deviation b 0.33

Confidence Coefficient d 0.25

Relative Accuracy e (% of RM) 36.2%

a Arithmetic Mean = 1/n S d i

b BAF = 1 + I 1/n S d i I / HgCEMS(avg)

c Standard Deviation = [ (S d i 2 - (S d i ) 2 / n) / (n-1) ] 1/2

d Confidence Corfficient = t 0.975 * Standard Deviation / n 1/2 , where t 0.975 = 2.306

e Relative Accuracy = ([Difference Arithmetic Mean] + [Confidence Coefficient]) / RM Arithmetic Mean *

100

### 4-75 Table 4-68. Phase 2 RA Results for Tekran

CEMS Avg. OH Total Hg Difference

Run Response Response (d)

Number Use Date Time (ug/dscm) (ug/dscm) (ug/dscm)

1 Yes 7/7/2005 10:45 - 12:45 2.41 2.77 0.36

2 No 7/7/2005 14:35 - 16:35 1.931 1.82 -0.111

3 Yes 7/8/2005 10:00 - 12:00 2.08 2.29 0.21

4 Yes 7/8/2005 13:55 - 15:55 1.40 1.86 0.46

5 Yes 7/9/2005 9:25 - 11:25 1.37 1.78 0.41

6 Yes 7/9/2005 13:10 - 15:10 1.44 1.67 0.23

7 Yes 7/10/2005 9:25 - 11:25 1.55 1.60 0.05

8 Yes 7/10/2005 12:40 - 14:40 1.57 1.87 0.30

9 Yes 7/11/2005 09:15 - 11:15 2.16 2.45 0.29

10 No 7/11/2005 14:00 - 16:00 1.915 2.33 0.415

11 Yes 7/12/2005 9:45 - 111:45 1.65 1.94 0.29

12 No 7/12/2005 13:00 - 15:00 1.307 1.36 0.05

Arithmetic Mean a (ug/dscm): 1.7 2.0 0.3

BAF b 1.17

Standard Deviation c 0.1

Confidence Coefficient d 0.1

Relative Accuracy e (% of RM) 18.8%

a Arithmetic Mean = 1/n S d i

b BAF = 1 + I 1/n S d i I / HgCEMS(avg)

c Standard Deviation = [ (S d i 2 - (S d i ) 2 / n) / (n-1) ] 1/2

d Confidence Corfficient = t 0.975 * Standard Deviation / n 1/2 , where t 0.975 = 2.306

e Relative Accuracy = ([Difference Arithmetic Mean] + [Confidence Coefficient]) / RM Arithmetic Mean *

100

### 4-76 Table 4-69. Phase 2 RA Results for Thermo

CEMS Avg. OH Total Hg Difference

Run Response Response (d)

Number Use Date Time (ug/dscm) (ug/dscm) (ug/dscm)

1 Yes 7/7/2005 10:45 - 12:45 2.19 2.77 0.58

2 Yes 7/7/2005 14:35 - 16:35 1.789 1.82 0.03

3 Yes 7/8/2005 10:00 - 12:00 1.94 2.29 0.35

4 Yes 7/8/2005 13:55 - 15:55 1.46 1.86 0.40

5 Yes 7/9/2005 9:25 - 11:25 2.19 1.78 -0.41

6 Yes 7/9/2005 13:10 - 15:10 -0.32 1.67 1.99

7 Yes 7/10/2005 9:25 - 11:25 -0.261 1.6 1.86

8 No 7/10/2005 12:40 - 14:40 -0.21 1.87 2.08

9 No 7/11/2005 09:15 - 11:15 -0.20 2.45 2.65

10 No 7/11/2005 14:00 - 16:00 -0.109 2.33 2.44

11 Yes 7/12/2005 9:45 - 111:45 0.38 1.94 1.57

12 Yes 7/12/2005 13:00 - 15:00 3.03 1.36 -1.67

Arithmetic Mean a (ug/dscm): 1.16 2.00 0.84

BAF b 1.72

Standard Deviation c 1.37

Confidence Coefficient d 1.05

Relative Accuracy e (% of RM) 94.5%

a Arithmetic Mean = 1/n S d i b BAF = 1 + I 1/n S d i I / HgCEMS(avg)

c Standard Deviation = [ (S d i 2 - (S d i ) 2 / n) / (n-1) ] 1/2

d Confidence Corfficient = t 0.975 * Standard Deviation / n 1/2 , where t 0.975 = 2.306

e Relative Accuracy = ([Difference Arithmetic Mean] + [Confidence Coefficient]) / RM Arithmetic Mean *

100



### 4.2.3 Additional Testing

4.2.3.1 Instrumental Reference Method Testing

The instrumental reference method (IRM) evaluations were performed towards development of an instrumental alternativ e to the Ontario Hydro reference method as used to perform Hg CEMS Relative Accuracy Test Audits (RATA). Results of the IRM testing are shown in Table 4-70. The techni que of dynamic spiking was employed as an approach to assess matrix interferences a nd begin determination of appropriate method performance criteria.

Known mass and volumetric feed rates of elemental and oxidized Hg were dynamically introduced at the probe of an Hg CEMS and the resulting recoveries calculated. By holding the sampling rate at a known constant, the resulting diluted

concentration was determined. The elemen tal and oxidized Hg dynamic spikes were

### 4-77 introduced at a volumetric flow that did not dilute the total stack sample flow rate by

more than 10%.

The Tekran Hg CEMS was used to perform the IRM test procedures because it is capable of extracting a high volume of stack gas through the probe at a controlled and measured flowrate and it was already appr opriately configured for dynamic spiking. The probe allows for introduction of gas at th e entrance of the dilution orifice which is downstream of the inertial separator/filter, and the probe tip upstream of the inertial separator/filter. Both of these injection lo cations were used to perform the IRM test.

Table 4-70. IRM Daily Hg Tests During RATA
Hg Source Tekran

Test date μg/m 3 Pre-Run Post-Run zero (N 2 ) elemental 0.000 * n/a 2.2 elemental (cylinder gas) 1.957 * n/a zero (N 2 ) Ionic 0.444 n/a 7/6/2005

2.6 Ionic 1.974 n/a zero (N 2 ) elemental 0.000 0.000 2.2 elemental (cylinder gas)** 2.014 2.019 zero (N 2 ) elemental 0.000 0.000 2.455 elemental (3310 gas)** 2.313 2.230 zero (N 2 ) Ionic 0.097 0.142 7/7/2005

2.6 Ionic 1.456 1.451 zero (N 2 ) elemental 0.000 0.000 2.455 elemental (3310 gas) 2.071 2.008 zero (N 2 ) Ionic 0.114 0.131 7/8/2005

2.6 Ionic 1.797 1.776 zero (N 2 ) elemental 0.000 0.000 2.455 elemental (3310 gas) 1.957 1.985 zero (N 2 ) Ionic 0.108 0.131 7/9/200

2.6 Ionic 1.752 1.712 zero (N 2 ) elemental 0.000 0.000 2.455 elemental (3310 gas) 1.923 2.014 zero (N 2 ) Ionic 0.142 0.097 7/10/2005

2.6 Ionic 1.741 1.680 zero (N 2 ) elemental 0.000 0.000 2.455 elemental (3310 gas) 1.923 1.991 zero (N 2 ) Ionic 0.108 0.085 7/11/2005

2.6 Ionic 1.763 1.712 zero (N 2 ) elemental 0.000 0.000 2.455 elemental (3310 gas) 2.008 2.143 zero (N 2 ) Ionic 0.114 0.097 7/12/2005

2.6 Ionic 1.786 1.900

* Measured at orifice; all measurement s after 7/6/05 were made at the probe. ** Supply of 2.2 μ g/m 3 cylinder gas was insufficient to complete test series.



### 4.2.3.2 Screening of Sor bent Trap Data with Hg CEMS

RMB Associates collected sorbent trap samples per Part 75 Section K during the 6 days of RATA testing. Those data were not available for inclusion in this report.

### 5-1 

# Section 5. Quality Assurance/Quality Control

The Quality Assurance/Quality Contro l (QA/QC) requirements, emission measurement, and data quality objectives for this test project are summarized in this section. The QC procedures and acceptance crit eria specified in the EPA methods and the QAPP were used. The procedures include d, but were not limited to, (1) sampling equipment calibrations, (2) procedural elements of the methods, such as leak checks, placement of the sampling probe, verification of the integrity of mete ring systems prior to the start and at the completion of each sampli ng run, etc., and (3) the use of QC samples and analytical approaches such as reagent blank samples, method blanks, matrix spike samples, duplicate analysis, and surrogate spiking for both manual methods and CEMS. The performance and results of all QC proce dures were recorded on appropriate forms, data sheets, field logs, and la boratory notebooks, as appropriate.

This QA/QC section is divided into tw o parts. The first part, 5.1, provides a summary of the Phase 1 November 2004 th rough February 2005, and the second part, 5.2, provides a summary of the Phase 2 testing performed March through September 2005.



## 5.1 Phase 1 Certification Testing

5.1.1 QA/QC Issues

It was discovered very late in the test program that a deviation from the OntarioHydro method had occurred during the laborat ory analysis. The brown residue found in

KMnO 4 

### /H 2 

### SO 4 

### impinger samples was not cleared (see Section 13.3.5 of Ontario Hydro method) prior to extracting an aliquot for analysis. This is a critical step which greatly affects the analytical result. By the time MRI was made aware of this method deviation the samples had already been discarded and it was too late to perform any reanalysis. Omission of this step adversely affects both precision and accurac y. For that reason the elemental mercury from the KMnO 4 

### /H 2 

### SO 4 

### impinger samples are considered suspect. More information on this method deviation is provided in Section 5.2.1.

The field blank KCl impinger result was > 30% of the results for the field samples. This, coupled with extremely low Run 1 KCl impinger results, casts doubt on those sample results. However, since the oxid ized mercury captured in the KCl impinger comprises on average < 10% of the total capt ured mercury, the impact is minimal. The paired train relative devi ation (RD) criterion of ≤ 10% RD was met for 8 of the 12 runs.

The RA results for three of th e four CEMS evaluated were greater than the 20% criteria and had differences greater than 1 μ g/m 3 

### for 9 runs. Two of the four CEMS met the remaining initial certification criteria listed in Table 5-1. Minor variances from the data quality criteria are noted in th e remainder of this section.

### 5-2 5.1.2 Ontario Hydro Samp ling Equipment Calibration

QC procedures, acceptability limits for sampling equipment calibrations, and calibration results are presented in Table 5-2. Calibration data sheets and equipment

condition checklists used duri ng calibration are provided in Appendix C of Volume 2 of this report. Equipment used for sample analysis was calibrated according to the procedures in the approved met hods and manufacturers’ manuals.

5.1.3 Hg CEMS Emission Measureme nt and Data Quality Objectives

The QC procedures, acceptability limits, and calibration results are presented in

Table 5-2. Detailed information for these results was presented in Sect ion 4 of this report.

5.1.4 Ontario Hydro Emi ssion Measurement and Data Quality Objectives

Specific QC procedures were followed to en sure the continuous generation of useful and valid data. Table 5-3 presents a summar y of criteria for assessing overall emission measurement and data quality for the initia l RATA test. Section 5.4.1 presents a brief summary of the QA sample results for the RA TA. All samples were analyzed within the 28-day holding time; however, shipping and storage temperatures for HNO 3 

### /H 2 

### O 2 

### and

KMnO 4 

### /H 2 

### SO 4 

### samples could not be verified.

5.1.4.1 QA Sample Results

It was discovered very late in the test pr ogram that the laborator y did not perform the Ontario-Hydro method closely. They had not cleared the brown residue found in

KMnO 4 

### /H 2 

### SO 4 

### impinger samples prior to extracting an aliquot for analysis. This is a critical step which greatly a ffects the analytical result. By the time MRI was made aware of this method deviation, the samples had alr eady been discarded and it was too late to perform any reanalysis. Omission of this step adversely affects both precision and accuracy. For that reason the elemental mercury from the KMnO 4 

### /H 2 

### SO 4 

### sample fractions are considered suspect. More inform ation on this method deviation is provided

in Section 5.2.1.

Blanks

Results of blank analysis are shown in Ta ble 5-4. Results for 4 of the 5 field blank train components indicated detectable levels of mercury, with the KCl impinger result at greater than 10 times the detection limit. Re sults from the field blank train analysis showed that mercury levels were > 30% of th e field sample results for the KCl impingers and 5 of the 24 filters. These sample results have been flagged.5-3Table 5-1. Summary of Phase 1CEMS Certification CriteriaCriteria met? (Y/N)Test Method of determination FrequencyCriteria Forney Horiba Tekran Thermo7-DayCalibrationError TestOnce per day for 7-dayconsecutive daysAt 24-hr intervalsfor 7 consecutivedaysError must be≤1μg/m3(alternativewhen span is defined at 10μg/m3). N Y Y YLinearity Test At beginning of testprogram, then quarterlyOnce, atbeginning of testprogramError must be≤10% or≤1μg/m3,whichever is least restrictive. N N Y YCycle TimeTestOnce, at beginning of testprogramOnce, atbeginning of testprogramCycle times must be≤15 minutes.N N Y YSystemIntegrity TestAt beginning of testprogram, then weeklyOnce, atbeginning of testprogramError must be≤5% of span fromcertified gas value (i.e., within±0.5μg/m3of certified gas value).N Y Y YMeasurementError TestPerformance of Linearityand Converter EfficiencytestsOnce, atbeginning of testprogramError must be≤5% of span fromcertified gas value (i.e., within±0.5μg/m3of certified gas value).N N Y YZero andUpscale DriftTestDetermines magnitude ofdrift at 24-hr intervals7 consecutivedaysError must be≤5% of span (i.e.,within ±0.5μg/m3of certified gasvalue).N Y N NRelativeAccuracyb(RATA)One set of 12 test runs, atbeginning of test program,and again after 6 monthsAfter initialcertificationchecks≤1μg/m3difference (alternativewhen average RM indicates Hgconcentration is < 5.0 ug/m3).N N YaYaaUsing Run 4 Avg. result.bA method deviation from the OH reference method makes all RATA results suspect.5-4Table 5-2. Phase 1 Calibration, QC Procedures, and Criteria for Ontario Hydro Sampling EquipmentParameterCalibration techniqueReference standardAcceptance limitFrequencyCriteria met?(yes/no)Sampling nozzleMeasure 3 diameters to nearest0.001 in and averagemeasurementsMicrometerDifference between high and lowmeasurements,#0.004 inPrior to samplingYesDry gas meteringsystem— volumeCompare with calibrated criticalorifices, 40CFR 60, Appendix A,Method 5, Section 5.3Calibrated criticalorificeDifference between individual calibrationfactor values and average value,#±0.02After test seriesYesUse field test data to compute acalibration check value, EPAMethod 5, ALT-007NADifference between calibration check valuemust be#±5% of initial calibration factorAfter test seriesYesDry gas meter temperaturesensors (thermocouples)Compare to mercury-in-glassthermometerASTM thermometer#±5.4EF difference from referenceBefore and after testseriesYesGas stream (stack)temperature sensor(thermocouple)Compare to value generated bydry well monitored withpotentiometer thermocouplesystemHart Model 9100A drywell calibration systemDifference of#±1.5% of minimumabsolute stack temperature from absolutereference temperature (unsaturated gasstreams);#±1EF difference from reference(saturated gas streams)Before and after testseriesYesFinal impinger outlettemperature sensor(thermocouple)Compare to mercury-to-glassthermometerASTM thermometer#±2EF difference from referenceBefore and after testseriesYesFilter temperature sensor(thermocouple)Compare to mercury-to-glassthermometerASTM thermometer#±5.4°F difference from referenceBefore and after testseriesYesAneroid barometerCompare to calibrated mercurybarometerMercury columnbarometer#±0.1 in Hg difference from referenceBefore and after testseriesYesType S pitot tubeMeasure dimensions according to40CFR 60, Appendix A, Method2 for baseline coefficient of 0.84Micrometer and anglefinderMeets dimensional criteria specified inMethod 2, Section 6.1 and Figures 2-2 and2-3Before and after testseriesYes5-5Table 5-3. Phase 1 Test Criteria forEmission Measurement and Data QualityTestparametersMatrixMethod of determinationFrequencyAccuracy objectivePrecision objectiveCriteria met?(Yes/No)HgOntario Hydro trainsamplesAnalysis of blank train samplecomponents (field blank)Once to demonstratesystem control (no grosscontamination)Hg levels >30% of measuredresults must be flaggedSee Note 1Analysis of field reagent solutions(solution blank)Each time new reagentsare preparedHg levels >10% of measuredresults must be flaggedSee Note 2Duplicate train analyses Each runRD must be within 10% of each other No, see Notes 6and 7Duplicate analysisEvery sample analyzedResults must be within 10% of eachotherNo, see Notes 3and 7Triplicate analysisEvery 10thsampleanalyzedResults must be within 10% of eachotherNo, see Notes 3and 7Matrix spikesEvery 10th sampleanalyzed65%-135% recovery< 40% RPDYesSpiked lab reagent blankssimulating front-half and back-halftrain componentsTwo lab control spikesfor each component (orcombined components)at 10X the estimateddetection limit65%-135% recovery< 40% RPDSee Note 4Continuing calibration check Check standard every10 samples90% to 110% recovery NA Yes; see Note 5QC check standard (certifiedstandard, independent of workingcalibration standards)After each initialcalibration85% to 115% recoveryNAYesMoisturepressuretemperaturevelocityGas stream beingmeasuredSecondary technical review of fieldtest data and equipment calibrationrecords relative to EPA Methods 1-5Ongoing during testingValidated by meeting posttestequipment calibration tolerancesNA, but multiple test runs may be usedas indication of overall operationvariabilityYesAnalysis of ambient airOnce prior to bagsample analysis±0.2 percent by volume forambient air oxygenMethod 3B criteriaYesO2and CO2byOrsatGas bag samplesTriplicate analysis of bag samplesEach bag sampleNAMethod 3B criteriaYesNote 1Mercury was reported in filter blank results at 0.017μg. This level was > 30% of sample results for 5 of 24 filtersamples. Mercury was also reported in the KCl impinger results at> 30% of all KClsample values. The reported results have been flagged.Note 2Mercury was reported in the HNO3/H2O2impinger blank result at 0.004μg. This level was > 10% of sample results for 21 of 24 impinger samples. The reported results have been flagged.Note 3Replicate results on approximately 10% of samples submitted wereabove the ±10% difference criteria. Analytical values for particle-bound samples were near the detection limit and do notsignificantly impact data quality. The KCl and HNO3/H2O2impinger samples have been reanalyzed and met the acceptance criteria. The reanalyzed results have been incorporated into thisreport.Note 4Only a single spiked lab reagent blank was performed and showed 98% recovery.Note 5 A filter sample and a H2O2impinger sample were slightly outside of the acceptance criteria at 86% and 112%, respectively.Note 6 The RD was not met for 4 of the 12 runs. Runs 3, 6, and12 had RDs of 13%, 13%, and 15%, respectively. Run 4 had an RD of 12% and variations of the train and train duplicate were used inthe Relative Accuracy calculations.Note 7 A method deviation (omission of clarification step of KMnO4/H2SO4sample prep) makes all results for this sample fraction suspect.

### 5-6 Table 5-4. Phase 1 RA Blank Analysis Results

Description Hg

result Detection

limit (μg)

Field Blank Train ( μ g)

Filter 0.017 0.005

Probe Rinse < 0.006 0.006

0.1 N KCl (Impingers 1-3) 0.475 0.010

5% HNO 3 /10% H 2 O 2 (Impinger 4) 0.014 0.007

4% KMnO 4 /10% H 2 SO 4 (Impingers 5-7) 0.014 0.020

Field Solution Blanks

Filter ( μ g) < 0.005 0.005

0.1 N HNO 3 ( μ g) < 0.005 0.005

0.1 N KCl ( μ g) 0.002 0.001

5% HNO 3 /10% H 2 O 2 ( μ g) 0.004 0.002

4% KMnO 4 /10% H 2 SO 4 ( μ g) < 0.001 0.001

10% Hydroxylamine ( μ g/mL) * 0.0157 0.020

Laboratory Method Blanks ( μ g)

Filter < 0.0010 0.001

0.1 N HNO 3 < 0.0010 0.001

0.1 N KCl < 0.0200 0.001

5% HNO 3 /10% H 2 O 2 < 0.0010 0.001

4% KMnO 4 /10% H 2 SO 4 < 0.0200 0.0011

* At 0.0157 μ g/mL, estimated maximum amounts in the KCl and KMnO 4 impingers

are 0.002 μ g and 0.008 μ g, respectively.

Results shown in bold have values > 10 times the detection limit.

### 5-7 Results for three of the six solution blanks indicated detectable levels of mercury, with hydroxylamine result at greater than 10 times the detection limit. The blank results for hydroxylamine are shown in units of μ g/mL because the amount used per train component varied. The maximum amounts estimated to have been used in the KCl and

KMnO 4 

### impingers were around 0.2 mL and 0.5 mL, respectively. Therefore, the estimated maximum amounts of mercury cont ributed to those train components was

0.002 μ g and 0.008 μ g, respectively.

Replicate Sample Analyses

Percent differences for duplicate and trip licate analysis are shown in Table 5-5. Approximately 10% of the sample replicates had > 10% difference. These samples were reanalyzed and the revised results were within the acceptance criteria.

Spikes and Audit Sample

Matrix spike results are found in Table 5- 6. All of the matrix spikes met the QA criteria of ±10%. Also, the audit sample re sult was within the QC criteria. The blank spike was only performed on the filter portion of the train and analyzed once. However, the percent recovery was with in the accuracy objective.

Continuing Calibration Checks

Results of continuing calibration checks are provided in Table 5-7. All of the

calibration checks met the ±10% criteria with the exception of two (a filter and a H 2 

### O 2 

### impinger sample) which were slightly out side those criteria at 86% and 112%, respectively.

### 5-8 Table 5-5. Percent Difference for Ph ase 1 Mercury Analysis Results

Percent Difference (%)

Particle bound Oxidized Elemental

Field ID Lab ID Filter a Probe

rinse KCl Iipingers HNO 3 /H 2 O 2 Impinger KMnO 4 /H 2 SO 4 Impingers

Run 1 Lab 1 N/A a N/A 8% 0% 1% Run 1 dup train Lab 2/3 N/A N/A 3% 8% 1%

Run 2 Lab 4 N/A N/A 1% 2% 1% Run 2 dup train Lab 5 N/A 9% 5% 10% 7%

Run 3 Lab 7 N/A 0% 2% 3% 1% Run 3 dup train Lab 8 N/A 0% 3% 0% 1%

Run 4 Lab 9 N/A N/A 1% 8% 1% Run 4 dup train Lab 10 N/A N/A 3% 0% 3%

Run 5 Lab 11 N/A N/A 4% 10% 9% Run 5 dup train Lab 12 N/A 7% 3% 10% 6%

Run 6 Lab 13 N/A N/A 0% 4% 1% Run 6 dup train Lab 14/15 N/A N/A 3% 7% 1%

Run 7 Lab 16 N/A 5% 1% 0% 2% Run 7 dup train Lab 17 10% 5% 3% 7% 6%

Run 8 Lab 19 7% N/A 0% 0% 1% Run 8 dup train Lab 20 0% N/A 1% 0% 2%

Run 9 Lab 21 N/A 8% 3% 0% 2% Run 9 dup train Lab 22 N/A 4% 1% 0% 3%

Run 10 Lab 23 N/A 8% 2% 3% 0% Run 10 dup train Lab 24 N/A N/A 2% 0% 0%

Run 11 Lab 25 0% N/A 3% 0% 2% Run 11 dup train Lab 26/27 N/A 6% 1% 7% 2%

Run 12 Lab 28 N/A 0% 2% 8% 1% Run 12 dup train Lab 29 N/A 5% 1% 8% 0%

Field Blank Lab 31 N/A N/A 0% 0% N/A

Blank Train Lab 32 6% N/A 0% 0% 0%
The QA objective is < 10% Difference [%Diff = (1 – (Analysis 1 / Analysis 2) ) * 100; for triplicate analysis, the values with greatest difference are used].

a An "N/A" indicates that Percent Difference calculation is not applicable due to one or more value below being the detection limit.

Values shown in bold did not initially meet the ≤ 10% Diff. objectives and were re analyzed; reanalysis results are reported.5-9Table 5-6. Phase 1 RA Spikeand Audit Sample ResultsSpike recoveries (as % of spiked)Particle bound Oxidized ElementalField IDLab IDFilter Probe rinse KCl imp. HNO3/H2O2imp. KMnO4/H2SO4imp.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Matrix SpikeRun 2 Lab 60.0250 0.0262 105% 0.025 0.02599.2% 0.250 0.268 107% 0.0250.024 96.0% 0.250 0.258 103%Run 7 Lab 180.0250 0.0253 101% 0.025 0.025100% 0.250 0.241 96.4% 0.0250.023 92.8% 0.2500.241 96.6%Run 12 Lab 300.0250 0.0243 97.2% 0.025 0.025 100% 0.250 0.267 107% 0.0250.023 90.0% 0.250 0.261 104%RPD: 8% RPD: 1% RPD: 10% RPD: 7% RPD: 8%Blank Spike0.0200 0.0196 98.0% Not performed Not performed Not performed Not performedAudit (QC Check) SampleAudit Amount (μg) Amount Found (μg) % Rec.1020 Lab 34 2.8 2.65% 94.6%% Recovery = (Amount Found in Spiked Sample – Average Amount Found in Unspiked Sample) / Amount Spiked x 100.Values shown in bold do not meet the QA objectives.5-10Table 5-7. Phase 1 Continuing OH Calibration Check StandardsSpike recoveries (as % of spiked)Particle bound Oxidized ElementalFilter Probe rinse KCl imp. HNO3/H2O2imp. KMnO4/H2SO4imp.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.0.005 0.0051 102% 0.005 0.0048 96% 0.250 0.246 98% 0.0050.005 102% 0.250 0.245 98%0.005 0.0046 92% 0.005 0.0052 104% 0.250 0.240 96% 0.0050.005 104% 0.250 0.248 99%0.005 0.0045 90% 0.005 0.0050 100% 0.250 0.234 94% 0.0050.005 108% 0.250 0.250 100%0.005 0.0048 96% 0.005 0.0053 106% 0.250 0.248 99% 0.0050.005 98.0% 0.250 0.236 94%0.005 0.0046 92% 0.005 0.0054 108% 0.250 0.228 91% 0.0050.005 92.0% 0.250 0.252 101%0.005 0.0046 92% 0.005 0.0053 106% 0.250 0.249 99% 0.0050.005 94.0% 0.250 0.239 95%0.005 0.0046 92% 0.005 0.0051 102% 0.250 0.242 97% 0.0050.005 96.0% 0.250 0.236 94%0.005 0.0053 106% 0.005 0.0054 108% 0.250 0.248 99% 0.005 0.006112%0.250 0.233 93%0.005 0.004386%0.005 0.0051 102% 0.250 0.24397% – – – 0.250 0.252 101%0.005 0.0046 92% 0.005 0.0051 102% – – – – – – – – –0.005 0.0045 90% 0.005 0.0052 104% – – – – – – – – –Note: Accuracy objective is 90% to 110% recovery. Values in bold are outside the objective.

### 5-11 5.1.5 Phase 1 Summary

QA audits were carried out for the manual Ontario Hydro Method and the CEMS. Sampling procedures and analyt ical data were evaluated ag ainst the quality objectives presented in the QAPP and th e Site Specific Test Plan.

The Ontario Hydro data did not meet the data quality and measurement criteria for this work assignment as described earlie r in Section 5.1.1 and 5.1.4.1. The omission of a critical sample preparation step in the la boratory causes concerns regarding the OH data quality.

Two CEMS met the Part 75 data quality and measurement criteria. The remaining

two CEMS did not meet all the criteria.

An assessment of the overall quality of the data generated for Phase 1 was conducted and the OH data were found to be suspect. Th e data assessment included a review of the sample collection preparation and analysis data.



## 5.2 Phase 2 Certification Testing

5.2.1 QA/QC Issues

Because the Phase 2 Relative Deviation (RD) for KMnO4/H 2 

### SO 4 

### replicate impinger samples was unexplainably large (seven out of 12 replicate results had an RD larger than 16%, with the highest at 47% RD), these samp les were reanalyzed. When the reanalyzed results were also unexplainably large with no reproducibility between the first and second analyses, the contract laboratory was ques tioned and it was discovered that the brown

residue found in the KMnO 4 

### /H 2 

### SO 4 

### impinger samples had not been clarified prior to extracting an aliquot for analysis. This is a critical step which a ffects the analytical accuracy and precision.

Because the highest amount of mercury is found in the KMnO 4 

### /H 2 

### SO 4 

### impingers,

with much of it located in the brown resi due on the side of the sample bottle, all

KMnO 4 

### /H 2 

### SO 4 

### impinger results had to be considered nonrepresentative of the samples. A second laboratory (ARCADIS G&M, Inc.) was contracted to reanalyze the remaining

KMnO 4 

### /H 2 

### SO 4 

### samples from Phase 2 sampling (Phase 1 samples had long since been discarded). The four KMnO 4 

### /H 2 

### SO 4 

### samples which had been spiked were missing a 100- mL to 200-mL volume with no corresponding anal ytical data. This is likely because the original laboratory often pr epares extra aliquots in case there is some problem with preparation. The laboratory did provide some additional analytical spike data, but it was not sufficient to account for the missing 100-mL to 200-mL volume.

In order to determine the mercury values for the KMnO 4 

### /H 2 

### SO 4 

### samples, the analytical results for each aliquot (as repor ted by the original laboratory) was multiplied by the aliquot volume, then summed and adde d to the ARCADIS labs’ analytical result

### 5-12 times the remaining sample volume to obtai n a total mass. Because the four spiked samples from the original la boratory were missing an addi tional 100-mL to 200-mL of sample, those results are biased low sin ce the unknown amount of mercury in those missing volumes cannot be added to the total.

The analytical results from the Phase 1 KMnO 4 

### /H 2 

### SO 4 

### samples must be considered suspect and the difficulties discussed above would account for the difficulty in meeting

the RD criteria of < 10% RD. Because the Phase 2 KMnO 4 

### /H 2 

### SO 4 

### samples were reanalyzed, these results were mostly salvageable, with the exception of the spiked samples (Runs 2, 7, 10, and 12) which are biased low because a significant volume of the sample was missing prior to reanalysis.

The field blank HNO 3 

### /H 2 

### O 2 

### impinger results for mercury were > 30% of field sample results. However, since the elemental mercury captured in the HNO 3 

### /H 2 

### O 2 

### impinger comprises on average < 3% of th e total captured mercury, the impact was

minimal.

The RD criterion of ≤ 10% RD was met for 8 of the 12 runs. A review of other sampling parameters (O 2 

### , CO 2 

### , and H 2 

### O) were within 8% of each other for all runs and do not appear to have contri buted to the RD values. Desp ite the large RD observed for the OH method results, three CEMS had differences less than 1 μ g/m 3 

### as compared to

the OH results for all 12 runs.

5.2.2 Hg CEMS Emission Measureme nt and Data Quality Objectives

The QC procedures, acceptability limits, and calibration results are presented in Table 5-8. Detailed results were pres ented in Section 4 of this report.

5.2.3 Ontario Hydro Samp ling Equipment Calibration

QC procedures, acceptability limits for sampling equipment calibrations, and calibration results are presented in Table 5-9. Calibration data sheets and equipment

condition checklists used duri ng calibration are provided in Appendix C of Volume 3 of this report. Equipment used for sample analysis was calibrated according to the procedures in the approved met hods and manufacturers’ manuals.5-13Table 5-8. Summary of Phase 2CEMS Certification CriteriaCriteria met? (Y/N)Test Method of determination Frequency CriteriaDurag Opsis Tekran Thermo7 DayCalibrationError TestOnce per day for 7consecutive daysAt 24-hr intervalsfor 7 consecutivedaysError must be≤1μg/m3(alternative when span is definedat 10μg/m3). Y Y Y NLinearity Test At beginning of testprogram, then quarterlyOnce, atbeginning of testprogramError must be≤10% or≤1μg/m3,whichever is least restrictive.N N YaNCycle TimeTestOnce, at beginning of testprogramOnce, atbeginning of testprogramCycle times must be≤15 minutes.Y Y Y YSystemIntegrity TestAt beginning of testprogram, then weeklyOnce, atbeginning of testprogramError must be≤5% of span fromcertified gas value (i.e., within ±.5μg/m3of certified gas value).YcYbYcNMeasurementError TestPerformance of Linearityand Converter EfficiencytestsOnce, atbeginning of testprogramError must be≤5% of span fromcertified gas value (i.e., within ±.5μg/m3of certified gas value).YaN YaNZero andUpscale DriftTestDetermine magnitude ofdrift at 24hr intervals7 consecutivedaysError must be≤5% of span (i.e.,within ± 0.5μg/m3of certified gasvalue).Y N YcNRelativeAccuracy(RATA)dOne set of 12 test runs, atbeginning of testprogram, and again after6 monthsAfter certificationchecks≤20%; or, for low emitters withavg conc < 5μg/m3,≤1μg/m3difference. Y Y Y NaPassed first of two tests in July.bPassed the test performed in June.cPassed the test performed in May.dA method deviation with missing sample volume caused Runs 2, 7, 10, and 12 to be biased low which resulted in larger thanacceptable RD values and suspect data for these Reference Method results.5-14Table 5-9. Phase 2 Calibration, QC Procedures, and Criteria for Ontario Hydro Sampling EquipmentParameterCalibration techniqueReference standardAcceptance limitFrequencyCriteria met?(yes/no)Sampling nozzleMeasure 3 diameters to nearest0.001 in and averagemeasurementsMicrometerDifference between high and lowmeasurements,#0.004 inPrior to samplingYesDry gas metering system—volumeCompare with calibrated criticalorifices, 40CFR 60, Appendix A,Method 5, Section 5.3Calibrated criticalorificeDifference between individual calibrationfactor values and average value,#±0.02After test seriesYesUse field test data to compute acalibration check value, EPAMethod 5, ALT-007NADifference between calibration check valuemust be#±5% of calibration factorAfter test seriesYesDry gas meter temperaturesensors (thermocouples)Compare to mercury-in-glassthermometerASTM thermometer#±5.4EF difference from referenceBefore and after testseriesYesGas stream (stack)temperature sensor(thermocouple)Compare to value generated bydry well monitored withpotentiometer thermocouplesystemHart Model 9100A drywell calibration systemDifference of#±1.5% of minimumabsolute stack temperature from absolutereference temperature (unsaturated gasstreams);#±1EF difference from reference(saturated gas streams)Before and after testseriesYesFinal impinger outlettemperature sensor(thermocouple)Compare to mercury-to-glassthermometerASTM thermometer#±2EF difference from referenceBefore and after testseriesYesFilter temperature sensor(thermocouple)Compare to mercury-to-glassthermometerASTM thermometer#±5.4°F difference from referenceBefore and after testseriesYesAneroid barometerCompare to calibrated mercurybarometerMercury columnbarometer#±0.1 in Hg difference from referenceBefore and after testseriesYesType S pitot tubeMeasure dimensions accordingto 40CFR 60, Appendix A,Method 2 for baseline coefficientof 0.84Micrometer and anglefinderMeets dimensional criteria specified inMethod 2, Section 6.1 and Figures 2-2 and2-3Before and after testseriesYes

### 5-15 5.2.4 Ontario Hydro Emi ssion Measurement and Data Quality Objectives

Specific QC procedures were followed to en sure the continuous generation of useful and valid data. Table 5-10 presents a summary of criteria for a ssessing overall emission measurement and data quality for the RATA test. Section 6.4.1 presents a brief summary of the QA sample results for the RATA. All samples were analyzed within the 28-day holding time; however, shipping a nd storage temperatures for HNO 3 

### /H 2 

### O 2 

### and

KMnO 4 

### /H 2 

### SO 4 

### samples could not be verified.

5.2.5 QA Sample Results

It was discovered very late in the test pr ogram that the laborator y did not perform the Ontario Hydro method closely. They had not cleared the brown residue found in

KMnO 4 

### /H 2 

### SO 4 

### impinger samples prior to extracting an aliquot for analysis. This is a critical step which greatly aff ects the analytical result. As soon as MRI was made aware of this method deviation, a second laboratory was contacted to reanalyze the KMnO 4 

### /H 2 

### SO 4 

### samples. Four of the 12 runs were not co mpletely reanalyzed (see discussion in 5.2.1). Omission of this step adversely affects both precision and accuracy. For that reason, the elemental mercury from the Run 2, 7, 10, and 12 KMnO 4 

### /H 2 

### SO 4 

### samples are considered biased low and are suspect. More informa tion on this method deviation was provided in

Section 5.2.1.

Blanks

Results of blank analysis are shown in Table 5-11. Results for the filter, HNO 3 

### /H 2 

### O 2 

### , and KMnO 4 

### field blank train components indicated de tectable levels of mercury, with the

HNO 3 

### /H 2 

### O 2 

### impinger result at greater than 10 times the detection limit. Results from blank train analysis showed that mercury levels were > 30% of sample results for

HNO 3 

### /H 2 

### O 2 

### impingers for all runs except Run 1. Me rcury levels were also > 30% of sample results for 5 of the 24 filters. These sample results have been flagged.

Results for three of the six solution blanks indicated detectable levels of mercury. The blank results for hydroxylam ine are shown in units of μ g/mL because the amount used per train component varied. The maximu m amount estimated to have been used in

the KCl and KMnO 4 

### impingers were around 0.2 mL. Ther efore, the estimated maximum amount of mercury contributed to the train components was 0.00004 μ g.

Replicate Sample Analyses

Percent differences for duplicate and triplic ate analysis are shown in Table 5-12. The

Run 11 filter and the Solution Blank HNO 3 

### /H 2 

### O 2 

### impinger sample replicates had > 10% difference. These samples were not reanalyzed.5-16Table 5-10. Phase 2 RA Test Criteria forEmission Measurement and Data QualityTestparametersMatrixMethod of determinationFrequencyAccuracy objectivePrecision objectiveCriteria met?(Yes/No)HgOntario Hydro trainsamplesAnalysis of blank train samplecomponents (field blank)Once to demonstratesystem control (no grosscontamination)Hg levels >30% of measuredresults must be flaggedYes, see Note 1Analysis of field reagent solutions(solution blank)Each time new reagentsare preparedHg levels >10% of measuredresults must be flaggedYes, see Note 2Duplicate train analyses Each runRD must be within 10% of each other for9 or 12 runsNo, see Notes 3and 6Duplicate analysisEvery sample analyzedResults must be within 10% of eachotherNo, see Notes 4and 6Triplicate analysisEvery 10thsampleanalyzedResults must be within 10% of eachotherNo, see Notes 4and 6Matrix spikesEvery 10th sampleanalyzed65%-135% recovery< 40% RPDYesSpiked lab reagent blankssimulating front-half and back-halftrain componentsTwo lab control spikesfor each component (orcombined components)at 10X the estimateddetection limit65%-135% recovery< 40% RPDSee Note 5Continuing calibration check Check standard every10 samples90% to 110% recovery NA YesQC check standard (certifiedstandard, independent of workingcalibration standards)After each calibration85% to 115% recoveryNAYesMoisturepressuretemperaturevelocityGas stream beingmeasuredSecondary technical review of fieldtest data and equipment calibrationrecords relative to EPA Methods 1-5Ongoing during testingValidated by meeting posttestequipment calibration tolerancesNA, but multiple test runs may be usedas indication of overall operationvariabilityYesAnalysis of ambient airOnce prior to bagsample analysis±0.2 percent by volume forambient air oxygenMethod 3B criteriaYesO2and CO2byOrsatGas bag samplesTriplicate analysis of bag samplesEach bag sampleNAMethod 3B criteriaYesNote 1 Mercury was reported in the HNO3/H2O2impinger results at > 30% of Runs 2-12 sample values. The reported results have been flagged.Note 2 Mercury was reported in the HNO3/H2O2impinger blank result at 0.006μg. This level was > 10% of sample result for one impingersample from Run 6. The reported result has been flagged.Note 3 The RD was met for only 4 of the 12 runs.Note 4 Replicate results for Run 11 filter and field blank train HNO3/H2O2impinger were > 10% of each other. These samples were not reanalyzed.Note 5 Recoveries were outside criteria for one HNO3/H2O2impinger and for two KMnO4/H2SO4impingers. The RPD was outside criteria for the HNO3/H2O2and KMnO4/H2SO4fractions.Note 6 A method deviation with resultant missing sample volume caused Runs 2, 7, 10, and 12 to be biased low, which resulted insuspect data for these Reference Method results.

### 5-17 Table 5-11. Phase 2 Blank Analysis Results

Description Hg

result Detection

limit (μg) Field Blank Train-2 ( μ g)

Filter 0.006 0.001

Probe Rinse < .007 0.001 0.1 N KCl (Impingers 1-3) < .012 0.001
5% HNO 3 /10% H 2 O 2 (Impinger 4) 0.032 0.001
4% KMnO 4 /10% H 2 SO 4 (Impingers 5-7) < .016 0.0011

Field Blank Train-4 ( μ g)

Filter 0.010 0.001

Probe Rinse < .008 0.001 0.1 N KCl (Impingers 1-3) < .014 0.001
5% HNO 3 /10% H 2 O 2 (Impinger 4) 0.057 0.001
4% KMnO 4 /10% H 2 SO 4 (Impingers 5-7) 0.019 0.0011

Field Solution Blanks Filter ( μ g) < .005 0.001

0.1 N HNO 3 ( μ g) < .006 0.001 0.1 N KCl ( μ g) < .001 0.001
5% HNO 3 /10% H 2 O 2 ( μ g) 0.006 0.001
4% KMnO 4 /10% H 2 SO 4 ( μ g) 0.003 0.0011 10% Hydroxylamine ( μ g/mL) * 0.0002 0.0008

Laboratory Method Blanks ( μ g)

Filter < .005 0.001

0.1 N HNO 3 < .001 0.001 0.1 N KCl (low calibration curve) < .001 0.001 0.1 N KCl (high calibration curve) < .02 0.019
5% HNO 3 /10% H 2 O 2 < .001 0.001
4% KMnO 4 /10% H 2 SO 4 (low calibration curve) < .001 0.0011
4% KMnO 4 /10% H 2 SO 4 (high calibration curve) < .02 0.022

### 5-18 Table 5-12. Percent Difference for Ph ase 2 Mercury Analysis Results
Percent Difference (%)

Particle Bound Oxidized Elemental
Probe KCl HNO 3 /H 2 O 2 KMnO 4 /H 2 SO 4 Field ID Filter a rinse impingers impinger impingers

Run 1 0% 0% 1% 1% 2% Run 1 dup train 5% 9% 2% 1% 2%

Run 2 N/A N/A 3% 9% 1% Run 2 dup train N/A N/A 3% 2% 0%

Run 3 N/A N/A 3% 3% 1% Run 3 dup train N/A N/A 7% 2% 1%

Run 4 0% 0% 4% 3% 2% Run 4 dup train N/A 0% 4% 3% 5%

Run 5 N/A 0% 8% 1% 1% Run 5 dup train N/A 4% 1% 2% 7%

Run 6 N/A 4% 2% 2% 3% Run 6 dup train N/A 5% 5% 0% 4%

Run 7 N/A 4% 1% 0% 2% Run 7 dup train N/A N/A 6% 1% 3%

Run 8 N/A 8% 2% 3% 3% Run 8 dup train N/A N/A 0% 4% 2%

Run 9 N/A N/A 0% 4% 0% Run 9 dup train N/A N/A 6% 0% 3%

Run 10 0% 0% 0% 2% 0% Run 10 dup train N/A 6% 1% 2% 1%

Run 11 14% N/A 3% 1% 7% Run 11 dup train N/A 5% 8% 2% 3%

Run 12 N/A N/A 7% 2% 5% Run 12 dup train N/A N/A 8% 1% 3%

Field Solution Blank N/A N/A N/A 20% 0%
Blank Train-1 N/A N/A 1% 0% 1%
Blank Train-2 0% N/A N/A 6% N/A
Blank Train-3 N/A N/A 0% 2% 0%
Blank Train-4 0% N/A N/A 2% 6%
Blank Train-5 N/A N/A 1% 2% 1%

a The Method Blank exceeded 10% of the measured value for all filter results; therefore, results should be considered suspect.

The QA objectives are < 10% Difference [%Diff = (1 - (Analysis 1 / Analysis 2) ) * 100; for triplicate analysis, the values wi th greatest difference are used].

Values shown in bold do not meet the QA objectives.5-19Table 5-13. Phase 2 RA Spikeand Audit Sample ResultsSpike recoveries (as % of spiked)Particle bound Oxidized ElementalField IDLab IDFilter Probe rinse KCl imp. HNO3/H2O2imp. KMnO4/H2SO4imp.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Spiked(μg)Found(μg) % Rec.Matrix SpikeRun 2 Rep Lab 6 0.0250 0.0245 98.0% 0.025 0.0270 108% 0.250 0.229 91.8% 0.025 0.0236 94.4% 0.250 0.264 105%Run 7 Rep Lab 18 0.0250 0.0254 102% 0.025 0.0232 92.8% 0.025 0.024 95.2% 0.025 0.0256 102% 0.250 0.242 96.6%Run 10 Rep Lab 26 0.0250 0.0280 112% 0.025 0.0270 108% 0.025 0.027 107% 0.025 0.0249 100% 0.250 0.236 94.2%Run 12 Rep Lab 32 0.0250 0.0273 109% 0.025 0.0243 97.2% 0.025 0.023 91.6% 0.025 0.0247 98.8% 0.250 0.258 103%RPD: 13% RPD: 16% RPD: 16% RPD: 8% RPD: 11%Blank SpikeFilter Spike 0.0200 0.0201 100.5%Blank Train-1 Spike < 0.005 none < 0.007 none 0.996 0.860 86.3% 0.050 0.01938%7.968 5.93 74.4%Blank Train-2 Spike < 0.005 none < 0.007 none 0.996 0.897 90.1% 0.050 0.058 115% 7.968 4.0550.8%Blank Train-3 Spike < 0.005 none < 0.007 none 0.996 0.941 94.4% 0.050 0.113227%7.968 2.9336.8%RPD: 9% RPD:149%RPD:70%Audit (QC Check) SampleAudit Amount (ng/mL) Amount Found (ng/mL) % Rec.1017 Lab 40 2.8 2.82 100.7%% Recovery = (Amount Found in Spiked Sample – Average Amount Found in Unspiked Sample) / Amount Spiked x 100.Note: Results outside of QC criteria are shown in bold.

### 5-20 Spikes and Audit Sample

Matrix spike results are found in Table 5-13. All of the matrix spikes met the QA criteria of ±10%. Also, the audit sample result was with in the QC criteria. Blank spikes for the HNO 3 

### /H 2 

### O 2 

### and KMnO 4 

### /H 2 

### SO 4 

### impingers are noteworthy due to the erratic recoveries and poor precision (large RPDs). These samples were reanal yzed along with all of the sample KMnO 4 

### /H 2 

### SO 4 

### impingers.

Continuing Calibration Checks

Results of continuing calibration checks are pr ovided in Table 5-14. All of the calibration

checks met the ±10% criteria.

5.2.6 Phase 2 Summary

QA audits were carried out for the manual Ontario Hydro Method and the CEMS. Sampling procedures and analytical data were evaluated against the quality objec tives presented in the QAPP and the Site Specific Test Plan.

The Ontario Hydro data met the data quality and measurement crite ria for this work assignment as described earlier in Section 5.2.1 and 5.2.4.1. None of the CEMS met all of the draft PS-12A and Part 75 data quality and m easurement criteria. The RD criteria of ≤ 10% for

four of the 12 OH test runs were not met b ecause of a method deviation by the contract laboratory which resulted in data from Runs 2, 7, 10, and 12 being suspect.

An assessment of the overall qua lity of the data generated for this work assignment was conducted and the data were found to be acceptabl e for 8 of the 12 Phase 2 RATA runs. Because of a method deviation, the data from Runs 2, 7, 10, and 12 are biased low and should be considered suspect.5-21Table 5-14. Phase 2 Continuing OH Calibration Check StandardsSpike recoveries (as % of spiked)Particle bound Oxidized ElementalFilter Probe rinse KCl imp. HNO3/H2O2imp. KMnO4/H2SO4imp.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.Spiked(μg)Found(μg)% Rec.0.005 0.0048 96.0% 0.005 0.0050 100% 0.005 0.0052 104% 0.005 0.0046 92.0% 0.250 0.253 101%0.005 0.0049 98.0% 0.005 0.0052 104% 0.005 0.0047 94.0% 0.005 0.0046 92.0% 0.250 0.255 102%0.005 0.0049 98.0% 0.0050.0046 92.0% 0.005 0.0051 102% 0.005 0.0049 98.0% 0.250 0.244 97.6%0.005 0.0050 100% 0.005 0.004692.0% 0.005 0.0048 96.0% 0.005 0.0047 94.0%0.250 0.252 101%0.005 0.0054 108% 0.005 0.0052 104% 0.250 0.2592 104% 0.0050.0047 94.0% 0.250 0.256 102%0.005 0.0047 94.0% 0.005 0.0048 96% 0.250 0.2595 104% 0.0050.0055 110% 0.005 0.0048 96.0%0.005 0.0048 96.0% 0.005 0.0054 108% 0.005 0.004998.0% 0.005 0.0047 94.0%0.005 0.0051 102% 0.005 0.0050 100%0.005 0.0045 90.0%0.005 0.0047 94.0%0.005 0.0050 100% 0.005 0.0055 110%0.005 0.005 106% 0.005 0.0048 96.0%0.005 0.0054 108% 0.005 0.004 86.0% 0.250 0.2518 101%0.005 0.0054 108% 0.005 0.005 92.0% 0.250 0.2500 100%0.005 0.0050 100% 0.0050.0054 86.0% 0.250 0.2503 100%0.005 0.0052 104%0.005 0.0049 98.0%0.005 0.0048 96.0%0.005 0.0048 96.0%0.005 0.0051 102%

### 6-1 

# Section 6. Hg CEMS Conclusions and Recommendations

6.1 Performance Findings

While all of the Hg CEMS participating in this test program had some difficulty at times meeting the certificati on criteria and providing conti nuous data, much was learned

as a result of field evaluation which was evidenced by improvements made to the Hg CEMS over the course of this program. Tabl e 6-1 provides an overall summary of the Phase 1 and 2 performance results. The ability of each Hg CEMS to provide continuous data is summarized in the long-te rm monitoring summary, Figure 6-1.

In general, the Hg CEMS consisted of a sample extraction component (probe), a sample conditioning component (dilution probe—converter—SO 2 

### neutralizer), and an analytical component (CVAA, CVAF, or UV det ection). The analytical component of the systems is well established and did not gene rally contribute to measurement problems. However, multiple problems were observed with the sample transfer and conditioning of the stack gas. The most commonly observed problems related to either physical plugging of the probe during sample transfer or fouli ng of the converter. Often it would take some time for this type of problem to be evident. In some cases, more than one attempt was necessary to meet performance criteria and system maintenance was required.

The challenges to the Hg CEMS were more mechanical or physical than chemical. These challenges have provided a test bed fo r Hg CEMS improvement. Also, many of the challenges to the Hg CEMS are also app licable to non-mercury continuous emissions monitoring systems.



## 6.2 Conclusions and Recommendations

This test program demonstrated that the source characteristics can have a significant effect on Hg CEMS performance. Regardless of the vendor supplying the Hg CEMS, the CEMS should be appropriately modified for th e source. For instance, the source sampled for this demonstration project has a wet emi ssion matrix and thus requires an Hg CEMS with efficient sample transfer and conditioning capabilities in order to function properly.

Because of the extent to which source characteristics influence Hg CEMS performance, it is suggested that:

• 

### Potential purchasers review availabl e Hg CEMS performance testing data

obtained from sources similar to their own.

• 

### Potential purchasers ask vendors to pr ovide specific experience, including ongoing improvements that the vendor has made as a result of their experience

at similar sources.

### 6-2 Because the source characteristics can gr eatly affect the performance of the Hg CEMS and because it may take some tim e for problems to manifest, it is also suggested that:

• 

### An Hg CEMS considered for purchase be operated on-site for six months to demonstrate its capability to perform (reliability and accuracy) under the site-specific conditions before acceptance.

• 

### The above should be part of a performance warranty agreement.6-3Table 6-1. Summary of CEMS Certification Criteria and PerformancePhase 1 Criteria Met? (Y/N) Phase 2 Criteria Met? (Y/N)Test Criteria Forney Horiba Tekran Thermo Durag Opsis Tekran Thermo7 Day Calibration ErrorTestError must be≤1μg/m3(span is definedat 10μg/m3).N Y Y Y Y Y Y NLinearity TestError must be≤10% or≤1μg/m3,whichever is least restrictive.N N Y Y N N YbNCycle Time TestCycle times must be≤15 minutes.N N Y Y Y Y Y YSystem Integrity Test(includes ConverterEfficiency)Error must be≤5% of span from certifiedgas value (i.e., within ±.5μg/m3ofcertified gas value).N Y Y Y YdYcYdNMeasurement Error TestError must be≤5% of span from certifiedgas value (i.e., within ±.5μg/m3ofcertified gas value).N N Y Y YbN YbNZero and Upscale Drift TestError must be≤5% of span (i.e., within±0.5μg/m3of certified gas value).N Y N N Y Y YdNRelative Accuracy (RATA)≤20%; or, for low emitters with avg conc<5μg/m3, difference within ±1.0μg/m3.N N YaYaY Y Y NaUsing Run 4 Avg. resultbPassed the first of two tests performed in July.CPassed the testperformed in June.dPassed the test performed in May.6-4Figure 6-1. Phase 1 and 2 Long-Term Monitoring PeriodsInstrument downfor design upgrade