1. 1 Portable Hydrocarbon Sensors for Oil Sands Applications M.T. Taschuk 1, Q. Wang 1, S. Drake 1, A. Ewanchuk 2, M. Gupta 1, Y. Zhou 1, D. Ha 1, M. Alostaz 2, A. Ulrich 2, D. Sego 2, Y.Y. Tsui 1 1. Department of Electrical and Computer Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G 2V4 2. Department of Civil and Environmental Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G 2W2 2010 International Oil Sands Tailings Conference, December 5th - 8th, Edmonton, Alberta, Canada

2. 2 © Varian © Paramount Low-Cost Portable Rapid Measurements Low Resolution & Specificity High Cost Unportable Long Turnaround High Resolution & Specificity Concept Performance Tradeoffs 6 ppm NA

3. 3 Concept Low-cost, Rapid Screening Tools © Varian © Paramount

4. 4 Outline Device Physics Why light-emitting diodes (LED)? LED induced fluorescence (LEDIF) Optical Theory & Specifications Device Performance Naphthenic Acids (NA) in Process-Affected (PA) water Hydrocarbon Detection Instrument Outlook Summary

5. 5 Why LEDs? Haitz’s Law Similar to Moore’s Law Power per LED doubles every 2.3 years Cost per Lumen halves every 3 years Impacts many optical technologies: communications lighting chemical sensors fluorescence Source: Nature Photonics 1 (2007) pp. 25

6. 6 Broad bandwidth signals Highly sensitive: ppb LODs typical Minimal sample preparation Non-destructive For LEDs: broad bandwidth degrades signals limits on excitation wavelengths more flexible output LED Induced Fluorescence (LEDIF) Technique Characteristics Hannes Grobe ground state excited states excitation light emitted light

7. 7 Prototype Measurement Process 1.Ultraviolet LEDs emit light UV LEDs Collection Lens Sample Cuvette Parabolic Mirror Spectrometer

8. 8 Prototype Measurement Process 1.Ultraviolet LEDs emit light 2.Parabolic mirror focuses on sample UV LEDs Collection Lens Sample Cuvette Parabolic Mirror Spectrometer

9. 9 Prototype Measurement Process 1.Ultraviolet LEDs emit light 2.Parabolic mirror focuses on sample 3.Sample fluoresces UV LEDs Collection Lens Sample Cuvette Parabolic Mirror Spectrometer

10. 10 Prototype Measurement Process 1.Ultraviolet LEDs emit light 2.Parabolic mirror focuses on sample 3.Sample fluoresces 4.Parabolic mirror captures emission UV LEDs Collection Lens Sample Cuvette Parabolic Mirror Spectrometer

11. 11 Prototype Measurement Process 1.Ultraviolet LEDs emit light 2.Parabolic mirror focuses on sample 3.Sample fluoresces 4.Parabolic mirror captures emission 5.Collection lens couples to spectrometer UV LEDs Collection Lens Sample Cuvette Parabolic Mirror Spectrometer

12. 12 Optics: Excitation: 265 nm – 340 nm Emission: 200 nm – 800 nm f/3 collection; f/4 spectrometer Hardware Commercial, off the shelf components No moving parts Rapid measurement: < 5 seconds Prototype Cost: $10k Prototype Specifications

13. 13 Outline Device Physics Why light-emitting diodes (LED)? LED induced fluorescence (LEDIF) Optical Theory & Specifications Device Performance Naphthenic Acids (NA) in Process-Affected (PA) water Hydrocarbon Detection Instrument Outlook Summary

14. 14 LEDIF of NA Prototype Responsivity 285 nm, N avg = 5, t g = 5 s NA detectable well below 10 mg L -1 in 25 seconds Device performance expected to improve Concentrations by FTIR

15. 15 285 nm, 68 ppm NA, N avg = 5, t g = 5 s LEDIF of NA Unfiltered Process-Affected Water NA signature in unfiltered process-affected water No sample preparation 25 second measurement

16. 16 LEDIF of Hydrocarbons Naphthalene 265 nm, N avg = 1, t g = 5 s LOD < 1 ppm 5 second measurement Can trade speed for sensitivity Fine spectral features broadened by LED bandwidth

17. 17 LEDIF of Hydrocarbons Summary Table CompoundLimit of DetectionMeasurement Time Naphthenic Acids< 5 ppm25 s Napthalene< 1 ppm5 s Phenanthrene< 1 ppm5 s Pyrene< 100 ppb1 s Diesel< 100 ppm5 s Gasoline< 10 ppm5 s Crude Oil< 1 ppm5 s

18. 18 LEDIF of Hydrocarbons Diesel in Soil Diesel-saturated sand samples Preliminary evidence suggests we can distinguish weathered diesel and diesel Further work required to establish calibration curve for weathering 265 nm, N avg = 5, t g = 1 s (WD), t g = 2 s (D)

19. 19 Outline Device Physics Why light-emitting diodes (LED)? LED induced fluorescence (LEDIF) Optical Theory & Specifications Device Performance Naphthenic Acids (NA) in Process-Affected (PA) water Hydrocarbon Detection Instrument Outlook Summary

20. 20 © Varian © Paramount Low-Cost Portable Rapid Measurements Low Resolution & Specificity High Cost Unportable Long Turnaround High Resolution & Specificity Concept Future Work Today 2011

21. 21 Instrumental Outlook Room for Improvement More LEDs: 2X Smaller! Bigger! Improved f/#: 10X Improved Optics: 2X

22. 22 Summary Field portable hydrocarbon sensor developed NA LOD < 5 mg L -1, NA detected in unfiltered PAW Other compounds successfully detected at ppm level Rapid measurements: 25 s for NA, ≦ 5 s for remainder Prototype cost: $10k Future Work Expect 10X to 100X improvement Handheld devices possible Inline, real-time monitors possible 6 ppm NA

23. 23 Acknowledgements

24. 24 Portable Hydrocarbon Sensors for Oil Sands Applications: Additional Slides M.T. Taschuk 1, Q. Wang 1, S. Drake 1, A. Ewanchuk 2, M. Gupta 1, Y. Zhou 1, D. Ha 1, M. Alostaz 2, A. Ulrich 2, D. Sego 2, Y.Y. Tsui 1 1. Department of Electrical and Computer Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G 2V4 2. Department of Civil and Environmental Engineering, University of Alberta, Edmonton, Alberta, Canada, T6G 2W2 2010 International Oil Sands Tailings Conference, December 5th - 8th, Edmonton, Alberta, Canada

25. 25 Off-the-shelf LED ~ 5% of bench top power Trade resolution for power Why LEDs? Comparison with Benchtop Instruments © Varian

26. 26 Excellent agreement with Varian Eclipse data LED related signals removed from prototype signal Further work required to optimize signals LEDIF of NA Comparison with Benchtop Instrument 280 nm270 nm

27. 27 Device Performance Characteristic Spectra 265 nm excitation, 1000 ms acquisition, 5 averages, 1.8 nm smooth 13.7 mg/L Napthanic Acid in Water Good spectra observed Significant scatter from LED at 265 nm and ~500 nm Post processing can separate peaks

28. 28 LEDIF of Hydrocarbons Pyrene LOD < 100 ppb 1 second measurement 265 nm, N avg = 1, t g = 1 s

29. 29 LEDIF of Hydrocarbons Phenanthrene 265 nm, N avg = 1, t g = 5 s LOD < 1 ppm 5 second measurement Can trade speed for sensitivity Fine spectral features broadened by LED bandwidth