Analytical and Bioanalytical Chemistry

, Volume 400, Issue 10, pp 3261–3271 | Cite as

A PLS model based on dominant factor for coal analysis using laser-induced breakdown spectroscopy

  • Jie Feng
  • Zhe Wang
  • Logan West
  • Zheng Li
  • Weidou Ni
Original Paper


Thirty-three bituminous coal samples were utilized to test the application of laser-induced breakdown spectroscopy technique for coal elemental concentration measurement in the air. The heterogeneity of the samples and the pyrolysis or combustion of coal during the laser–sample interaction processes were analyzed to be the main reason for large fluctuation of detected spectra and low calibration quality. Compared with the generally applied normalization with the whole spectral area, normalization with segmental spectral area was found to largely improve the measurement precision and accuracy. The concentrations of major element C in coal were determined by a novel partial least squares (PLS) model based on dominant factor. Dominant C concentration information was taken from the carbon characteristic line intensity since it contains the most-related information, even if not accurately. This dominant factor model was further improved by inducting non-linear relation by partially modeling the inter-element interference effect. The residuals were further corrected by PLS with the full spectrum information. With the physical-principle-based dominant factor to calculate the main quantitative information and to partially explicitly include the non-linear relation, the proposed PLS model avoids the overuse of unrelated noise to some extent and becomes more robust over a wider C concentration range. Results show that RMSEP in the proposed PLS model decreased to 4.47% from 5.52% for the conventional PLS with full spectrum input, while R 2 remained as high as 0.999, and RMSEC&P was reduced from 3.60% to 2.92%, showing the overall improvement of the proposed PLS model.


Laser-induced breakdown spectroscopy Bituminous coal Dominant factor Partial least squares 



The authors acknowledge the financial support from the governmental “863” project (NO. 20091860346) and “973” project (NO. 2010CB227006).

Supplementary material

216_2011_4865_MOESM1_ESM.pdf (1.5 mb)
ESM 1 (PDF 1497 kb)


  1. 1.
    Bustamante MF, Rinaldi CA, Ferrero JC (2002) Laser induced breakdown spectroscopy characterization of Ca in a soil depth profile. Spectrochim Acta B 57:303–309CrossRefGoogle Scholar
  2. 2.
    Maravelaki-Kalaitzaki P, Anglos D, Kilikoglou V, Zafiropulos V (2001) Compositional characterization of encrustation on marble with laser induced breakdown spectroscopy. Spectrochim Acta B 56:887–903CrossRefGoogle Scholar
  3. 3.
    Rials TG, Kelley SS, So CL (2002) Use of advanced spectroscopic techniques for predicting the mechanical properties of wood composites. Wood Fiber Sci 34:398–407Google Scholar
  4. 4.
    Pandhija S, Rai AK (2008) Laser-induced breakdown spectroscopy: a versatile tool for monitoring traces in materials. Pramana J Phys 70:553–563CrossRefGoogle Scholar
  5. 5.
    Gomba JM, D’Angelo C, Bertuccelli D, Bertuccelli G (2001) Spectroscopic characterization of laser-induced breakdown in aluminum-lithium alloy samples for quantitative determination of traces. Spectrochim Acta B 56:695–705CrossRefGoogle Scholar
  6. 6.
    Lee WB, Wu JY, Lee YI, Sneddon J (2004) Recent applications of laser-induced breakdown spectrometry: a review of material approaches. Appl Spectrosc Rev 39:27–97CrossRefGoogle Scholar
  7. 7.
    Li J, Lu J, Lin Z, Gong S, Xie C, Chang L, Yang L, Li P (2009) Effects of experimental parameters on elemental analysis of coal by laser-induced breakdown spectroscopy. Opt Laser Technol 41:907–913CrossRefGoogle Scholar
  8. 8.
    Taschuk MT, Tsui YY, Fedosejevs R (2006) Detection and mapping of latent fingerprints by laser-induced breakdown spectroscopy. Appl Spectrosc 60:1322–1327CrossRefGoogle Scholar
  9. 9.
    Beldjilali S, Borivent D, Mercadier L, Mothe E, Clair G, Hermann J (2010) Evaluation of minor element concentrations in potatoes using laser-induced breakdown spectroscopy. Spectrochim Acta B 65:727–733CrossRefGoogle Scholar
  10. 10.
    Feng J, Wang Z, Li Z, Ni W (2010) Study to reduce laser-induced breakdown spectroscopy measurement uncertainty using plasma characteristic parameters. Spectrochim Acta B 65:549–556CrossRefGoogle Scholar
  11. 11.
    Zhang L, Dong L, Dou H, Yin W, Jia S (2008) Laser-induced breakdown spectroscopy for determination of the organic oxygen content in anthracite coal under atmospheric conditions. Appl Spectrosc 62:458–463CrossRefGoogle Scholar
  12. 12.
    Yin W, Zhang L, Dong L, Ma W, Jia S (2009) Design of a laser-induced breakdown spectroscopy system for on-line quality analysis of pulverized coal in power plants. Appl Spectrosc 63:865–872CrossRefGoogle Scholar
  13. 13.
    Wallis FJ, Chadwick BL, Morrison RJS (2000) Analysis of lignite using laser-induced breakdown spectroscopy. Appl Spectrosc 54:1231–1235CrossRefGoogle Scholar
  14. 14.
    Body D, Chadwick BL (2001) Optimization of the spectral data processing in a LIBS simultaneous elemental analysis system. Spectrochim Acta B 56:725–736CrossRefGoogle Scholar
  15. 15.
    Blevins LG, Shaddix CR, Sickafoose SM, Walsh PM (2003) Laser-induced breakdown spectroscopy at high temperatures in industrial boilers and furnaces. Appl Opt 42:6107–6118CrossRefGoogle Scholar
  16. 16.
    Ctvrtnickova T, Mateo MP, Yanez A, Nicolas G (2010) Laser induced breakdown spectroscopy application for ash characterization for a coal fired power plant. Spectrochim Acta B 65:734–737CrossRefGoogle Scholar
  17. 17.
    Ctvrtnickova T, Mateo MP, Yanez A, Nicolas G (2009) Characterization of coal fly ash components by laser-induced breakdown spectroscopy. Spectrochim Acta B 64:1093–1097CrossRefGoogle Scholar
  18. 18.
    Gaft M, Sapir-Sofer I, Modiano H, Stana R (2007) Laser induced breakdown spectroscopy for bulk minerals online analyses. Spectrochim Acta B 62:1496–1503CrossRefGoogle Scholar
  19. 19.
    Gaft M, Dvir E, Modiano H, Schone U (2008) Laser induced breakdown spectroscopy machine for online ash analyses in coal. Spectrochim Acta B 63:1177–1182CrossRefGoogle Scholar
  20. 20.
    Mateo MP, Nicolas G, Yanez A (2007) Characterization of inorganic species in coal by laser-induced breakdown spectroscopy using UV and IR radiations. Appl Surf Sci 254:868–872CrossRefGoogle Scholar
  21. 21.
    Romero CE, De Saro R, Craparo J, Weisberg A, Moreno R, Yao Z (2010) Laser-induced breakdown spectroscopy for coal characterization and assessing slagging propensity. Energy Fuels 24:510–517CrossRefGoogle Scholar
  22. 22.
    Noda M, Deguchi Y, Iwasaki S, Yoshikawa N (2002) Detection of carbon content in a high-temperature and high-pressure environment using laser-induced breakdown spectroscopy. Spectrochim Acta B 57:701–709CrossRefGoogle Scholar
  23. 23.
    Burakov VS, Tarasenko NV, Nedelko MI, Kononov VA, Vasilev NN, Isakov SN (2009) Analysis of lead and sulfur in environmental samples by double pulse laser induced breakdown spectroscopy. Spectrochim Acta B 64:141–146CrossRefGoogle Scholar
  24. 24.
    Yu L, Lu J, Xie C, Chen W, Wu G, Shen K, Feng W (2005) Analysis of pulverized coal by laser-induced breakdown spectroscopy. Plasma Sci Technol 7:3041–3044CrossRefGoogle Scholar
  25. 25.
    Clegg SM, Sklute E, Dyar MD, Barefield JE, Wiens RC (2009) Multivariate analysis of remote laser-induced breakdown spectroscopy spectra using partial least squares, principal component analysis, and related techniques. Spectrochim Acta B 64:79–88CrossRefGoogle Scholar
  26. 26.
    Fink H, Panne U, Niessner R (2002) Process analysis of recycled thermoplasts from consumer electronics by laser-induced plasma spectroscopy. Anal Chem 74:4334–4342CrossRefGoogle Scholar
  27. 27.
    Sirven JB, Bousquet B, Canioni L, Sarger L (2006) Laser-induced breakdown spectroscopy of composite samples: comparison of advanced chemometrics methods. Anal Chem 78:1462–1469CrossRefGoogle Scholar
  28. 28.
    Amador-Hernandez J, Garcia-Ayuso LE, Fernandez-Romero JM, Luque De Castro MD (2000) Partial least squares regression for problem solving in precious metal analysis by laser induced breakdown spectrometry. J Anal At Spectrom 15:587–593CrossRefGoogle Scholar
  29. 29.
    Freedman A, Iannarilli FJ, Wormhoudt JC (2005) Aluminum alloy analysis using microchip-laser induced breakdown spectroscopy. Spectrochim Acta B 60:1076–1082CrossRefGoogle Scholar
  30. 30.
    Braga JWB, Trevizan LC, Nunes LC, Rufini IA, Santos D, Krug FJ (2010) Comparison of univariate and multivariate calibration for the determination of micronutrients in pellets of plant materials by laser induced breakdown spectrometry. Spectrochim Acta B 65:66–74CrossRefGoogle Scholar
  31. 31.
    Miziolek AW, Palleschi V, Schechter I (2006) Laser induced breakdown spectroscopy. Cambridge University Press, Cambridge, UKCrossRefGoogle Scholar
  32. 32.
    Wold S, Sjostrom M, Eriksson L (2001) PLS-regression: a basic tool of chemometrics. Chemom Intell Lab Syst 58:109–130CrossRefGoogle Scholar
  33. 33.
    Wang Z, Feng J, Li L, Ni W, Li Z (2010) A novel multivariate model based on dominant factor for laser-induced breakdown spectroscopy measurements, arXiv:1012.2735v1 [physics.optics]Google Scholar
  34. 34.
    Aragon C, Aguilera JA, Penalba F (1999) Improvements in quantitative analysis of steel composition by laser-induced breakdown spectroscopy at atmospheric pressure using an infrared Nd: YAG laser. Appl Spectrosc 53:1259–1267CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Jie Feng
    • 1
  • Zhe Wang
    • 1
  • Logan West
    • 1
  • Zheng Li
    • 1
  • Weidou Ni
    • 1
  1. 1.State Key Lab of Power Systems, Department of Thermal Engineering, Tsinghua-BP Clean Energy CenterTsinghua UniversityBeijingChina

Personalised recommendations