2. Near Infrared (NIR) Spectroscopy and Calibration in Biomass Characterisation Paul Geladi

3. Paul Geladi Head of Research NIRCE Unit of Biomass Technology and Chemistry Swedish University of Agricultural Sciences Umeå Technobothnia Vasa paul.geladi@btk.slu.se paul.geladi@syh.fipaul.geladi@btk.slu.sepaul.geladi@syh.fi

4. Content What is biomass? What is NIR spectroscopy? Examples What is calibration? Advanced topics

5. Content What is biomass? What is NIR spectroscopy? Examples What is calibration? Advanced topics

6. Biomass Non-food Food & feed Bioenergy Pulp and paper Forestry Building materials Textiles Consumer products Feed and safety

7. Where is biomass found? Biotechnology Natural products Bioenergy

8. What is special about biomass? O-H C-H N-H C=O different atom sizes = good IR+NIR energy = movements of bonds

9. O HH O HH O HH O HH  

10. Content What is biomass? What is NIR spectroscopy? Examples What is calibration? Advanced topics

11. Near Infrared Spectra (NIR) 780-2500nm Suitable for all organic and bio materials Robust for industrial use Good penetration depth Many modes of measuring Powerful multivariate results Cosmic Gamma Xray Ultraviolet Visible NIR Infrared Microwaves

12. Near Infrared Spectra Fast Simple sample preparation Nondestructive Online for process applications Need for calibration Opportunity for data analysis

14. Near Infrared Spectra? Visible Infrared Raman Polarization Visible Near infrared Infrared Raman 400nm780nm2500nm15000nm

15. Content What is biomass? What is NIR spectroscopy? Examples What is calibration? Advanced topics Plans for a network of excellence Acknowledgement

16. EXAMPLES 1 Organic synthesis Liquid Fiberoptic transflectance Over time

18. Fibers in Fibers out Mirror

19. Wavelength ”Absorbance” H2OH2O visible near infrared

20. Wavelength Absorbance Organic synthesis over time

21. CONCLUSION 1 Possible to follow a reaction over time Identify reagents, products, intermediates Reaction kinetics

22. EXAMPLES 2 Whole grain and flour Solid FT-NIR reflectance Genetic variation

24. Wavelength Pseudoabsorbance FLOUR

25. Wavelength Pseudoabsorbance WHOLE GRAINS

26. CONCLUSION 2 Grain and flour different Genetic information Location information Accurate protein content

27. Where used? Food Feed Biofuel Fossil fuel Plastics Wood and pulp Environmental and waste Clinical and pharma In vivo

28. Rapid process monitoring for biofuels Canary reed grass Pellet / Briquette press The role of humidity

29. Biofuel energy unit Briquette machine

30. Mixing drum with window for measurement Process NIR spectrometer

31. Reed canary grass Briquette

32. Predict = determine quality ahead Humidity for briquette quality Other parameters (e.g. ash content, energy, CO 2 ) for energy production

33. Measure how? Location (how many? where?) How often? How detailed? Buckets? Single particles?

35. Content What is biomass? What is NIR spectroscopy? Examples What is calibration? Advanced topics

36. Calibration Concentration Spectral property Model

37. y Offset Slope  Calibration

38. Xy I K f b = + y = Xb + fy = Xb + f Multivariate calibration

39. Why calibrate? SpectrumConcentration Spectrum -measured in 1 min -no sample preparation -on-line possible -noninvasive -nondestructive Concentration -sample preparation -slow -expensive -waste chemicals -destructive

40. Methods of data analysis Multivariate calibration Classification Multivariate image analysis Multiway analysis Neural nets Genetic algorithms

41. Content What is biomass? What is NIR spectroscopy? Examples What is calibration? Advanced topics

42. High quality instrumentation Simplified instrumentation Experimental instrumentation Complexity Speed, Robustness Instrumentation

43. Imaging / Spectroscopy An image for each wavelength A spectrum for each pixel

47. Table : Wavelength bands in some airborne / satellite imaging systems Band/channelWavelength (nm) SPOT-XSLANDSAT-TMJERS-OPSAVIRIS 1500-590450-520520-600224 bands 2610-680520-600630-690every 10nm 3790-890630-690760-860390-2500 nm 4-760-900760-860* 5-1550-17501600-1710 6-10400-125002010-2120 7-2080-23502130-2250 8--2270-2400 * bands 3 and 4 are a stereo pair. SPOT-XS= (Système Probatoire d'Observation de la Terre) Image size 60x60 km; resolution 20x20 m. (Panchromatic = B/W resolution 10x10 m). LANDSAT-TM = (Thematic Mapper) Image size 185x172 km; resolution 30x30 m JERS-OPS = Japanese Earth ResourcesSatellite - Optical Sensor 75x75km; resolution 18.3x25.4 m. There is also 1.275 GHz radar. AVIRIS = (Airborne Visible/Infrared Imaging Spectrometer ) Typical 512x614 pixels and 20x20 m resolution.

48. Resolution Wavelength –reduction and selection Time –fast product streams –parallel measurements Space –0-D bulk analysis –1-D product streams –2-D images, microscopy –3-D tomography

49. What is new and exciting? Spatial resolution imaging in 2D, 3D Fast streams in 1D Polarisation etc. Simplified instrumentation Advanced data analysis Database / search / control / presentation

50. Books to read B. Osborne, T. Fearn & P. Hindle, Practical NIR Spectroscoy 2nd ed., Longman Scientific & Technical, Harlow, 1993, ISBN 0-582-09946-3 D. Burns & E. Ciurzak eds., Handbook of Near- Infrared Analysis 2nd ed., Marcel Dekker, New York, 200, ISBN 0-8247-0534-3 H. Siesler, Y. Ozaki, S. Kawata & H. Heise eds., Near-Infrared Spectroscopy, Wiley-VCH, Weinheim, 2002, ISBN 3-527-30149-6