1. Continuous Mercury Monitoring (CMM)
Mercury CEM Seminar
Continuous Mercury Monitoring (CMM)
Update of Technology, Applications and Traceability
Mark Calloway
Tekran Instruments Corporation
Tekran Instruments Corporation

2. Presentation Overview
Mercury CEM Seminar
Presentation Overview
CMM Technology Application Updates
Importance of Low-Level Measurement Application
Abatement Systems Monitoring
NIST Traceability and Ongoing Verification
New Industry Installations
Current estimates of the eventual market value of mercury emissions allowances are in the range of $35,000 per pound, in 1999 dollars. (Source: EPA)
Tekran Instruments Corporation

3. CMM Technology Application Updates
Mercury CEM Seminar
CMM Technology Application Updates
Tekran currently has nearly 400 “CMM-Years” of operating experience
Key “Take Aways” include:
CMMs are sophisticated and not as easy to operate and maintain as conventional CMMs
Umbilical failures have occurred on 10 percent of the systems leading to new umbilical designs
RATA testing results indicate high pass rate (>95%) with failures typically associated with deficient integration, testing and commissioning protocol.
NIST Traceability and Ongoing Verification Protocol in progress
Tekran Instruments Corporation

4. Why Should You Care about Speciation?
Mercury CEM Seminar
Why Should You Care about Speciation?
Emission ratio varies with fuel type, combustion conditions and emissions control equipment
Vastly different Hg control technologies required
Hg2+ is efficiently removed with wet scrubbers
Hg0 best removed using injection of carbon absorbents
May be beneficial to convert forms before removal
Note periodic inversion of species where Hg2+ exceeds Hg0.
Conventional wisdom was that PRB plants emitted mostly elemental mercury.
Tekran Instruments Corporation

5. 3300 Series CMM Consists of: Probe (M&C and Tekran designs), Umbilical
Mercury CEM Seminar
3300 Series CMM
Consists of:
Probe (M&C and Tekran designs),
Umbilical
3310 Elemental Calibrator
3315 Ionic Calibrator
3320 Conditioner
2537S Analyzer
Controller (multiple options)
Tekran Instruments Corporation

6. Tekran Series 3300 – Capabilities
Mercury CEM Seminar
Tekran Series 3300 – Capabilities
Speciating
HgT and Hg0 measured directly
Hg2+ determined by subtraction
Typical detection limit (< 0.05 µg/m3) or (~0.005 ppb v/v)
MDL limited by system blanks, not instrumentation
Lower MDL (< 0.01 µg/m3) possible for low Hg applications
Update rate: one sample every 2.5 minutes
Remote Monitoring, Analyses and Alarming
Tekran Instruments Corporation

7. Advanced QA / QC Features
Mercury CEM Seminar
Advanced QA / QC Features
QC capabilities are critical to assure data quality
Detector is separately calibrated (may be used for ongoing CMM component stability and traceability verification)
Automated multi-point system validation with Hg0
High delivery rate mercury calibration source included
Either two-point or multi-point calibration gas values
Several automated injection points within CEM system
Through entire system (ie: at tip of probe stinger)
Immediately upstream of dilution orifice
Direct into mercury analyzer
Standard additions of elemental mercury to matrix (spikes)
Automated determination of dilution ratio
Fully automated, multi-point HgCl2 calibrations!
Tekran Instruments Corporation

8. Model 2537S Mercury Analyzer
Mercury CEM Seminar
Model 2537S Mercury Analyzer
Originally designed as an ambient air mercury analyzer
MDL is < 0.1 ng/m3
Update rate: every 2.5 minutes
Proven reliability under extreme conditions
Has been used in the high Arctic, Antarctica and everywhere in between
Demonstrated long-term stability and accuracy
Capable of continuous unattended operation
Tekran Instruments Corporation

9. Principles of Operation
Mercury CEM Seminar
Principles of Operation
Mercury in sample gas is preconcentrated onto (pat’d) pure gold cartridge
Adsorbed mercury is thermally desorbed
Detected by atomic fluorescence detector
Two cartridges are used to alternately sample and desorb
No gaps in data stream
Provides continuous monitoring of inlet stream
Tekran Instruments Corporation

10. Near-term Impacts of CAMR Vacature
Mercury CEM Seminar
Near-term Impacts of CAMR Vacature
May provide some “breathing room” for CMM and Abatement System Customers and Suppliers
States will continue to take a proactive role in regulation
“Cap and Trade” process and approach unlikely
New Control Requirements - more research and action relative to Hg Abatement options and technologies
Outlet Levels of Hg will be lower yet
Current estimates of the eventual market value of mercury emissions allowances are in the range of $35,000 per pound, in 1999 dollars. (Source: EPA)
Tekran Instruments Corporation

11. Presentation Overview
Mercury CEM Seminar
Presentation Overview
CMM Technology Application Updates
Importance of Low-Level Measurement Application
Abatement Systems Monitoring
NIST Traceability and Ongoing Verification
New Industry Installations
Current estimates of the eventual market value of mercury emissions allowances are in the range of $35,000 per pound, in 1999 dollars. (Source: EPA)
Tekran Instruments Corporation

12. Crystal Balling of CAMR Replacement Legislation (One View)
Mercury CEM Seminar
Crystal Balling of CAMR Replacement Legislation (One View)
MACT-type approach likely
Additional focus on NIST traceability and CMM System Accuracy
Potential renewed investigation of Hg0, Hg2+, and HgP
Potential increased use of CMMs for Abatement System Control and Optimization
Outlet Levels of Hg will be lower yet
Current estimates of the eventual market value of mercury emissions allowances are in the range of $35,000 per pound, in 1999 dollars. (Source: EPA)
Tekran Instruments Corporation

13. Mercury CEM Seminar
“Tomorrow’s” RATAs May All Look Like This! (Actual RATA Results on Tekran 3300 System)
Average Difference = 0.09 ug/m3
Tekran Instruments Corporation

14. Sorbent Traps (avg) = 0.59 ug/m3 Tekran with M&C (avg) = 0.56 ug/m3
Mercury CEM Seminar
Sorbent Traps (avg) = 0.59 ug/m3
Tekran with M&C (avg) = 0.56 ug/m3
Tekran Instruments Corporation

15. Presentation Overview
Mercury CEM Seminar
Presentation Overview
CMM Technology Application Updates
Importance of Low-Level Measurement Application
Abatement Systems Monitoring
NIST Traceability and Ongoing Verification
New Industry Installations
Current estimates of the eventual market value of mercury emissions allowances are in the range of $35,000 per pound, in 1999 dollars. (Source: EPA)
Tekran Instruments Corporation

16. Mercury Abatement Systems Status (10,000 ft. view)
Mercury CEM Seminar
Mercury Abatement Systems Status (10,000 ft. view)
Substantial testing and evaluation completed to date
New technologies being developed and demonstrated
Hg Removal rates are Unit specific and can often exceed 90 %
Unit, Plant and Fleet-wide Hg monitoring and optimization will likely be implemented
If State type rules get traction, utilities will need:
Low-level measurements capability
NIST Traceability and ongoing verification
Fleet-wide optimization program for mercury abatement
Current estimates of the eventual market value of mercury emissions allowances are in the range of $35,000 per pound, in 1999 dollars. (Source: EPA)
Tekran Instruments Corporation

17. Mercury CEM Seminar
Example Mercury Abatement Using Sorbent Injection 500MWe Coal-fired Plant
Average Difference = 0.09 ug/m3
The last 10% removal may cost another 50% more
Tekran Instruments Corporation

18. Presentation Overview
Mercury CEM Seminar
Presentation Overview
CMM Technology Application Updates
Importance of Low-Level Measurement Application
Abatement Systems Monitoring
NIST Traceability and Ongoing Verification
New Industry Installations
Current estimates of the eventual market value of mercury emissions allowances are in the range of $35,000 per pound, in 1999 dollars. (Source: EPA)
Tekran Instruments Corporation

19. NIST Traceability Status
Mercury CEM Seminar
NIST Traceability Status
Most CMMs in the field are not truly traceable to NIST
The protocol was published July 2, 2009 to verify ongoing traceability and stability of CMM systems
The absence of 1 & 2 above means that regulated sources do not enjoy a level playing field – and potentially opens up the market for “gaming”.
EPA, EPRI, NIST and RMB Consulting are developing ongoing calibration and stability protocol for CMMs.
Tekran Instruments Corporation

20. Mercury CEM Seminar
NIST Traceability
Tekran’s 3310 Hg0 Calibration Results – largest deviation (2-40 ug/m3) < 1%
Tekran’s 3315 Hg2+ Solutions Traceable to NIST – Concentrations from <1 to >100 ug/m3)
Tekran Instruments Corporation

21. Initial Certification – Hg0
Mercury CEM Seminar
Initial Certification – Hg0
Uses “bracketing”
Compare certified reference calibrator to unknown candidate calibrator
Three candidate readings, each bracketed by a reference reading before and after
Ratio of responses used to determine candidate’s actual output concentration
Eliminates effects of detector drift
Tekran Instruments Corporation

22. Initial Certification – Hg0
Mercury CEM Seminar
Initial Certification – Hg0
Certification done at a minimum of three different concentrations for any user calibrator
Low, medium & high points for linearity check for any span range
High point is also used for daily span checks
Each certified concentration requires three consecutive bracketed readings
Entire sequence repeated twice
Yields two groups of three readings, separated by a few hours
Called a 3x3x2
May be done at the vendors’ site or on site, using a travelling “reference” calibrator”
Tekran Instruments Corporation

23. Standard Certification Points – Hg0
Mercury CEM Seminar
Tekran Instruments Corporation

24. Mercury CEM Seminar
Ongoing QA/QC – Hg0
Calibrators are complex devices, with the possibility of failure while in the field
EPA is demanding periodic QA/QC checks of all field calibrators to ensure that they are still producing the correct concentrations
Tekran Instruments Corporation

25. Periodic QA/Q Checks – Hg0
Mercury CEM Seminar
Periodic QA/Q Checks – Hg0
Once per quarter, calibrator must be checked against an independent mercury standard at a single concentration (1x3x1)
As a reference, user may use either:
Independent “reference” calibrator
Hg gas cylinder
Method 30B cartridges
Internal permeation source (Tekran Only)
1, 2 and 3, above will require on-site testing
Tekran Instruments Corporation

26. Field QA/QC Checks - Tekran
Mercury CEM Seminar
Field QA/QC Checks - Tekran
Tekran has a significant advantage
Each CEM system has an independent, stable mercury source readily available
Model 2537 internal permeation source
Can use this Tekran permeation source as an independent check on 3310 calibrator
Tekran Instruments Corporation

27. How does Perm Ratio Test Work ?
Mercury CEM Seminar
How does Perm Ratio Test Work ?
Step 1: Whenever a 3310 calibrator is “freshly certified”
Perform internal 2537 perm source “lamp adjustment”. Record peak areas
Feed 3310 output directly into (Direct Cal) Record peak areas
Calculate ratio of peak areas. Record this value as the Initial Ratio and also record the 3310 certified concentration used for the test
Tekran Instruments Corporation

28. How does Perm Ratio Test Work ?
Mercury CEM Seminar
How does Perm Ratio Test Work ?
Step 2: Periodically (at least once per week)
Perform internal 2537 perm source “lamp adjustment”. Record peak areas
Feed 3310 output directly into (Direct Cal) Record peak areas
Calculate “Current Ratio” of peak areas. Record this Current Ratio. Use it to calculate an updated 3310 Current concentration
If the ratio is the same, it means that both the perm source and the calibrator still agree with respect to each other
Must agree with Initial Ratio to within 5%
Tekran Instruments Corporation

29. Advantages – Tekran Perm Ratio Test
Mercury CEM Seminar
Advantages – Tekran Perm Ratio Test
Requires only running an automated sequence periodically
Fully automated
Completely unattended
Data may be extracted manually and compiled into an ongoing QA/QC report or -
New S/W add-on from Tekran will fully automate process
Compiles latest report
Flags warnings and errors
Keeps history of results
Test can be run often (even daily) providing early indication of calibrator failure
Sequence can built in to daily span check operations
Will not result in any additional missing data if sequence is properly designed and scheduled
Tekran Instruments Corporation

30. Sample Excel Perm Source Ratio Report
Mercury CEM Seminar
Sample Excel Perm Source Ratio Report
Note: This particular calibrator has shifted by <0.5% (<0.03 µg/m3 in five months!
Tekran Instruments Corporation

31. Long Term Field QA/QC – Three Sites
Mercury CEM Seminar
Long Term Field QA/QC – Three Sites
Note: Short term variations are indicative of temporary instrument contamination, not calibrator failure
Tekran Instruments Corporation

32. Current Status – Hg0 Certifications at Tekran
Mercury CEM Seminar
Current Status – Hg0 Certifications at Tekran
Tekran has two vendor primes
Certified October 2007 (Run Aug 2007 ? )
Certifications have (technically) expired
Would like to:
Certify more calibrators with NIST
Recertify the initial two Vendor Prime units
However …
NIST not yet ready to accept new calibrators
Given the current state of Hg0 certifications at NIST, we are holding off until all NIST technical issues are resolved
The good news: Dec 2008: NIST verified (for the third time) that their “NIST prime” calibrator (a Tekran 3310) has not shifted significantly after three years
Tekran Instruments Corporation

33. Remaining Issues Hg0 Traceability
Mercury CEM Seminar
Remaining Issues Hg0 Traceability
Finalize uncertainty calculations
Must be simple and doable in the field
Existing interim calculations seem to have too small an added uncertainty during each subsequent generation of tracing
Consider upgrading NIST Hg analysis equipment to reduce uncertainties at low concentrations
Tekran Instruments Corporation

34. Other Industry Installations
Waste to Energy
Steel Smelting
Medical Incineration
DOE Nerve Gas Incineration

35. Mercury CEM Seminar
Summary
Utilities, Systems Integrators, etc. have had a steep learning curve relative to CMM Systems design, operation, maintenance and calibration.
CMM Systems are relatively complex and require more resources than conventional CEM systems.
Low-level accuracy and reliability of CMMs is critical with tightened state regulation
Abatement Systems technologies continue to be developed and improve -
Tekran Instruments Corporation