Frontier GeoSciences Inc. [email protected]Bob Brunette Hg and Air Quality–Sources, Effects, Control WESTAR Measuring Total And Speciated Mercury Measuring Total And Speciated Mercury In Process Gas Emissions In Process Gas Emissions Solid Sorbent Based Methods: US EPA 324 Solid Sorbent Based Methods: US EPA 324 and FAMS and FAMS Hg Monitoring And Monitoring Hg Monitoring And Monitoring WESTAR Fall Meeting WESTAR Fall Meeting Mercury and Air Quality – Sources, Effects, and Mercury and Air Quality – Sources, Effects, and Controls Controls San Diego, California San Diego, California September 22, 2005 September 22, 2005 Bob Brunette Bob Brunette Frontier Geosciences Inc Frontier Geosciences Inc 414 Pontius Avenue North 414 Pontius Avenue North Seattle, Washington 98109 Seattle, Washington 98109 [email protected][email protected]206 957 1461 206 957 1461
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• History Of Solid Sorbent Methods: US EPA 324 and FAMSHistory Of Solid Sorbent Methods: US EPA 324 and FAMS
• Measuring Total and Speciated Hg In Process GasMeasuring Total and Speciated Hg In Process Gas– US EPA 324 and FAMS Methods US EPA 324 and FAMS Methods
– US EPA 1631 & Applications To Coal-Fired UtilityUS EPA 1631 & Applications To Coal-Fired Utility
• Hg Control Systems EvaluatedHg Control Systems Evaluated
• US EPA Method 1630:US EPA Method 1630: Determination of Methyl Mercury in Water and Tissues by Distillation, Determination of Methyl Mercury in Water and Tissues by Distillation, Extraction, Aqueous Phase Ethylation, Purge and Trap, Isothermal GC Separation, Cold Vapor Extraction, Aqueous Phase Ethylation, Purge and Trap, Isothermal GC Separation, Cold Vapor Atomic Fluorescence Spectrometry.Atomic Fluorescence Spectrometry.
• US EPA Method 1631:US EPA Method 1631: Determination of Mercury in Water by Oxidation, Purge and Trap and Determination of Mercury in Water by Oxidation, Purge and Trap and Cold Vapor Atomic Fluorescence Spectrometry.Cold Vapor Atomic Fluorescence Spectrometry.
• US EPA Method 1637:US EPA Method 1637: Determination of Trace Elements in Ambient Waters by Off-Line Determination of Trace Elements in Ambient Waters by Off-Line Chelation, Preconcentration and stabilized Temperature Graphite Furnace Atomic Absorption.Chelation, Preconcentration and stabilized Temperature Graphite Furnace Atomic Absorption.
• US EPA Method 1638:US EPA Method 1638: Determination of Trace Elements in Ambient Waters by Inductively Determination of Trace Elements in Ambient Waters by Inductively Coupled Plasma-Mass Spectrometry.Coupled Plasma-Mass Spectrometry.
• US EPA Method 1639:US EPA Method 1639: Determination of Trace Elements in Ambient Waters by Stabilized Determination of Trace Elements in Ambient Waters by Stabilized Temperature Graphite Furnace Atomic Absorption.Temperature Graphite Furnace Atomic Absorption.
• US EPA Method 1640:US EPA Method 1640: Determination of Trace Elements in Ambient Waters by On-Line Determination of Trace Elements in Ambient Waters by On-Line Chelation Preconcentration and Inductively Coupled Plasma-Mass Spectrometry.Chelation Preconcentration and Inductively Coupled Plasma-Mass Spectrometry.
• US EPA Method 1669:US EPA Method 1669: Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Levels.Levels.
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
Why Measure Hg At The Sub PPB Range?Why Measure Hg At The Sub PPB Range?Historical Perspective – Hg In Waste Water EffluentsHistorical Perspective – Hg In Waste Water Effluents
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
How Accurate Is US Utility Hg Emission InventoryHow Accurate Is US Utility Hg Emission InventoryBased On Coal Hg Measurements?Based On Coal Hg Measurements?
• 25 Year Record Of Coal Hg Based On ASTM 368425 Year Record Of Coal Hg Based On ASTM 3684
• 1999 ICR Prescribed The Use Of ASTM 3684 Method1999 ICR Prescribed The Use Of ASTM 3684 Method
• ASTM Method Has Shown High LOD/LOQ Relative ASTM Method Has Shown High LOD/LOQ Relative To The Range Of Mercury Concentrations Found In To The Range Of Mercury Concentrations Found In Coal.Coal.
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
Benefit Of Low-Level Sensitive Analytical MethodsBenefit Of Low-Level Sensitive Analytical Methods
““EPA is now aware of several studies in which the techniques EPA is now aware of several studies in which the techniques employed in the above guidance (EPA-1631 CVAFS and employed in the above guidance (EPA-1631 CVAFS and other 1600 series methods) have been applied and have other 1600 series methods) have been applied and have been of great benefit in determining that either an been of great benefit in determining that either an environment problem does not exist or that the magnitude environment problem does not exist or that the magnitude of the problem is considerably less than initially of the problem is considerably less than initially envisioned. Therefore, the added costs associated with the envisioned. Therefore, the added costs associated with the sample handling and quality control protocols contained in sample handling and quality control protocols contained in the draft guidance are often trivial when compared to the the draft guidance are often trivial when compared to the cost saved by avoiding unnecessary pollution controls that cost saved by avoiding unnecessary pollution controls that might otherwise have been required.”might otherwise have been required.”
• Source - U.S. EPA Fact Sheet – March 1996Source - U.S. EPA Fact Sheet – March 1996
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
Barrier To Evaluate Hg Control Systems -Barrier To Evaluate Hg Control Systems -Diagnostic Tools Needed To Evaluate Control SystemsDiagnostic Tools Needed To Evaluate Control Systems
• Existing Impinger Methods: (Ontario Hydro/101A/M29)Existing Impinger Methods: (Ontario Hydro/101A/M29)– Difficult To Implement In FieldDifficult To Implement In Field– ExpensiveExpensive– Poor Field QA/QCPoor Field QA/QC– Few Data Points Generated For Effort/Cost Few Data Points Generated For Effort/Cost
($10K/Sample for ~ 3-4 Runs)($10K/Sample for ~ 3-4 Runs)– Field and Analytical Methods Are Antiquated (CVAA)Field and Analytical Methods Are Antiquated (CVAA)– High Detection LimitHigh Detection Limit– EPRI/DOE Hg Measurement Workshop – retire OH?EPRI/DOE Hg Measurement Workshop – retire OH?– Not Capable Of Continuous Emission MonitoringNot Capable Of Continuous Emission Monitoring
• Hg Continuous Mercury Monitors (CMM):Hg Continuous Mercury Monitors (CMM):– Alpha/Beta Development StageAlpha/Beta Development Stage– Having Difficulty Applied To Coal Fired Flue GasHaving Difficulty Applied To Coal Fired Flue Gas– Expensive (Cost, O&M, Dedicated CEM Staff)Expensive (Cost, O&M, Dedicated CEM Staff)– Smelter/Roaster Process Gas Too Complex – High Level HgSmelter/Roaster Process Gas Too Complex – High Level Hg
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
US EPA Method 324 and FAMSUS EPA Method 324 and FAMSFully Validated MethodsFully Validated Methods
1.1. US EPA PBMS Validation Study – 2000US EPA PBMS Validation Study – 2000– Validation Against Gold Standard – ASTM Ontario Hydro MethodValidation Against Gold Standard – ASTM Ontario Hydro Method
2.2. US Dept Of Energy Validation Study – 2001US Dept Of Energy Validation Study – 2001– Validation Against Gold Standard – ASTM Ontario Hydro MethodValidation Against Gold Standard – ASTM Ontario Hydro Method
3.3. US EPA 301h Validation Study - 2004US EPA 301h Validation Study - 2004– Validation Against Gold Standard – ASTM Ontario Hydro MethodValidation Against Gold Standard – ASTM Ontario Hydro Method
4.4. US Dept Of Energy Validation Study – 2004US Dept Of Energy Validation Study – 2004
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
US EPA Method 324US EPA Method 324- Principles Of Operation -- Principles Of Operation -
• High Purity Solid SorbentHigh Purity Solid Sorbent
• Captures All Species Of Gas Phase MercuryCaptures All Species Of Gas Phase MercuryFSTM = PHg (Semi-Iso) + Hg(0) + Hg(II)FSTM = PHg (Semi-Iso) + Hg(0) + Hg(II)
• Trap Hg Capacity - 5% (of the mass of the trap)Trap Hg Capacity - 5% (of the mass of the trap) Hg(0) = 7mg/trap Hg(II) = 1mg/trapHg(0) = 7mg/trap Hg(II) = 1mg/trap (Or a 1 Hour Test @ 233,000 ug Hg/m^3)(Or a 1 Hour Test @ 233,000 ug Hg/m^3)
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
US EPA 324 and FAMS Special FeaturesUS EPA 324 and FAMS Special Features
• Fixed Probe – No traversing stackFixed Probe – No traversing stack- Gas Phase Constituents Do not Behave Like ParticlesGas Phase Constituents Do not Behave Like Particles
- Gas Phase Constituents Are Not Influenced By Gas VelocityGas Phase Constituents Are Not Influenced By Gas Velocity
- Traverse and Iso-Kinetics Designed For Capturing ParticulateTraverse and Iso-Kinetics Designed For Capturing Particulate
- Greater Than 95% Of Hg In Flue Gas Is Gas PhaseGreater Than 95% Of Hg In Flue Gas Is Gas Phase
• Total Hg – Keep Trap Above Dew PointTotal Hg – Keep Trap Above Dew Point
25% Of Existing Coal-Fired Power Plants Have an FGD/SDA25% Of Existing Coal-Fired Power Plants Have an FGD/SDA
• Liquid Polymer AdditiveLiquid Polymer Additive
• Used Affectively For Hg Wastewater RemovalUsed Affectively For Hg Wastewater Removal
• Oxidizes Elemental Hg And Retains – 1 stepOxidizes Elemental Hg And Retains – 1 step
• Proof Of Concept: 15-25% Hg(0) Hg RemovalProof Of Concept: 15-25% Hg(0) Hg Removal
• Application To Existing Wet Scrubber/FGD/ESPApplication To Existing Wet Scrubber/FGD/ESP– No Additional Capital EquipmentNo Additional Capital Equipment– Add Polymer To Reservoir/Add WaterAdd Polymer To Reservoir/Add Water
• Additionally Removes Suite Of Metals From Wastewater Down Additionally Removes Suite Of Metals From Wastewater Down To 95% Reductions (As, Cd, Cr, Cu, Ni, Pb, Zn)To 95% Reductions (As, Cd, Cr, Cu, Ni, Pb, Zn)
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
Coal-Fired - Hg Specific ControlsCoal-Fired - Hg Specific ControlsActivated Carbon InjectionActivated Carbon Injection
• The Most Studied And Promising TechnologyThe Most Studied And Promising Technology• EPRI/DOE Funding and Research 2000-2007EPRI/DOE Funding and Research 2000-2007• Phase I and II (Full Scale Evaluations 2003-2007)Phase I and II (Full Scale Evaluations 2003-2007)
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
Challenges Of Carbon Injection Challenges Of Carbon Injection In Coal-Fired Flue GasIn Coal-Fired Flue Gas
Activity Carbon Injection (ACI)Activity Carbon Injection (ACI)• Large Mass Of Carbon Required To Adsorb HgLarge Mass Of Carbon Required To Adsorb Hg• Limited Hg Capacity (3%)Limited Hg Capacity (3%)• Low Mercury Capture Efficiency (contact time)Low Mercury Capture Efficiency (contact time)• Limited Temperature Operation Range (> 75C)Limited Temperature Operation Range (> 75C)• Only Operates Well In Dry GassesOnly Operates Well In Dry Gasses• Mixed Carbon/Fly Ash Can Not Be Used For CementMixed Carbon/Fly Ash Can Not Be Used For Cement
Generally Not Commercially Viable Generally Not Commercially Viable In Application To Most Coal-Fired Power PlantsIn Application To Most Coal-Fired Power Plants
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
ConclusionsConclusions
• US EPA 324 and FAMS – Accurate, Inexpensive, US EPA 324 and FAMS – Accurate, Inexpensive, Precision, High Data Generation MethodPrecision, High Data Generation Method
• Family Of Activated Carbons:Family Of Activated Carbons:– Most Promising Technique To Date (Coal-Fired)Most Promising Technique To Date (Coal-Fired)
– Phase II – Long Term Tests To Aid In Longevity of SorbentsPhase II – Long Term Tests To Aid In Longevity of Sorbents
– Most Promising Sorbent (Halogenated/Silica Based Sorbents)Most Promising Sorbent (Halogenated/Silica Based Sorbents)
• Low Cost/Low Impact Injection System Preserves Fly AshLow Cost/Low Impact Injection System Preserves Fly Ash
Bob Brunette Hg and Air Quality–Sources, Effects, Control
WESTAR
Conclusions (Cont’d)Conclusions (Cont’d)
• Most Emissions Sources Don’t Know Their Source Hg Most Emissions Sources Don’t Know Their Source Hg Concentrations or Emissions With ConfidenceConcentrations or Emissions With Confidence
• Recommend Hg Baseline Study Prior Hg Control DecisionsRecommend Hg Baseline Study Prior Hg Control Decisions
• ““Co-Benefit” Hg Removal From Existing APCDCo-Benefit” Hg Removal From Existing APCD– Average Hg Removal Is 30% Across IndustryAverage Hg Removal Is 30% Across Industry
– Other Industry Specific Show 99% Hg RemovalOther Industry Specific Show 99% Hg Removal
• Hg Specific Controls Are In Phase II AssessmentHg Specific Controls Are In Phase II Assessment– ““Long Term Effectiveness Of Controls UncertainLong Term Effectiveness Of Controls Uncertain
– Economy Of Hg Specific Controls UncertainEconomy Of Hg Specific Controls Uncertain
– Phase III Testing DOE/EPRI/EPA 2005-2010Phase III Testing DOE/EPRI/EPA 2005-2010