1. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Presented at Electric Utilities Environmental Conference (EUEC) Phoenix, AZ February 3 rd, 2010 Presented by Daniel Roesler Principal Investigator and Field Engineer Clean Air Engineering, Inc.

2. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 Why Spike? SO 3 /H 2 SO 4 difficult to measure SO 3 /H 2 SO 4 validation sources don’t exist Measurement Techniques –Based on theory –Have not been validated –May contain biases for common situations SO 3 H 2 SO 4 (vapor) H 2 SO 4 (mist) Dale A. Lundgren, Paul Urone and Thomas Gundersn, "A Stack Gas Sulfate Aerosol Measurement Problem", In Workshop Proceedings on Primary Sulfate Emissions from Combustion Sources, Volume 1, EPA-600/9-78-02tia, (August 1978), pp. 161-178

3. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 Measurement Techniques Manual Methods, Including Controlled Condensation (8, 8A, CleanAir 8B, etc.) Continuous Methods (TDL, FTIR, etc.)

4. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 Dynamic Spiking Concept Dual controlled condensation sampling trains: –One Spiked –One Unspiked Generate SO 3 on demand using platinum catalyst Inject a known amount of SO 3 into spiked train probe tip Compare spiked train recovery to unspiked train recovery Determine method bias based on spike recovery

5. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 SO 3 Generation SO 3 generation via platinum catalyst Catalyst contained inside probe SO 3 generated just prior to injection

6. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 SO 3 Generation Testing

7. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 SO 3 Generation Conditions

8. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 Spiking Probe

9. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 FTIR Detection of SO 3 SO 3 /H 2 SO 4 reacted with FTIR windows, creating buildup of interference that overshadowed SO 2 and SO 3 peaks Only relative accuracy and stability measurements Lacked reference spectra for low concentrations of SO 3

10. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 Spike Recovery

11. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 Conclusion Yes! We can reliably generate a known amount of SO 3 spike within a ±20% range. Yes! We can capture that SO 3 spike using controlled condensation in a field setting.

12. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 What’s Next Make dynamic spiking available for SO 3 /H 2 SO 4 testing immediately (patent pending) Further develop alternative catalyst –Shrink the ±20% recovery range to ±5% –Remove the need for seasoning and pre-ramping Create low level SO 3 reference spectra for FTIR Validate other SO 3 /H 2 SO 4 measurement techniques using SO 3 generation and spiking system, such as new ASTM SO 3 /H 2 SO 4 method

13. Determining the Accuracy of SO 3 /H 2 SO 4 Measurements: Development of a Field Spiking Procedure Copyright 2010 Clean Air Engineering, Inc.EUEC 2010 Questions? Special Thanks This presentation will be available online at http://www.cleanair.com/SO3