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Applied Optics

Applied Optics


  • Editor: Joseph N. Mait
  • Vol. 51, Iss. 7 — Mar. 1, 2012
  • pp: B213–B222

Correlation of limestone beds using laser-induced breakdown spectroscopy and chemometric analysis

Nancy J. McMillan, Carlos Montoya, and Warren H. Chesner  »View Author Affiliations

Applied Optics, Vol. 51, Issue 7, pp. B213-B222 (2012)

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Correlation of limestone beds is commonly based on a variety of features, including the age of the bed, the fossil assemblage, internal sedimentary structures, and the relationship to other units in the stratigraphy. This study uses laser-induced breakdown spectroscopy (LIBS) to correlate 16 limestone beds from Kansas, USA, using three multivariate techniques: (1) soft independent modeling of class analogy (SIMCA) classification, (2) a partial least squares regression, 1 variable (PLS-1) model in which the spectra are regressed against a matrix of the indicator variables 1 through 16, and (3) a matching algorithm that consists of a sequence of binary PLS-1 models. Each gravel-sized limestone particle was analyzed by one LIBS shot; ten spectra were averaged into a single spectrum for chemometric analysis. The entire spectrum (198–969 nm wavelength) is used for multivariate analysis; the only preprocessing is averaging. The SIMCA and PLS-1 models fail to discriminate among the beds, which are chemically similar. In contrast, the matching algorithm has a success rate of 95% to 96%, using half of the spectra to train the model and the other half of the spectra to validate it. However, 100% success can be accomplished by accepting the classification of the majority of spectra for a given bed as the correct classification. This study indicates that LIBS can be applied to complex geologic correlation problems and provide rapid, accurate results.

© 2012 Optical Society of America

OCIS Codes
(160.0160) Materials : Materials
(300.6365) Spectroscopy : Spectroscopy, laser induced breakdown

Original Manuscript: October 5, 2011
Revised Manuscript: December 31, 2011
Manuscript Accepted: January 25, 2012
Published: March 1, 2012

Nancy J. McMillan, Carlos Montoya, and Warren H. Chesner, "Correlation of limestone beds using laser-induced breakdown spectroscopy and chemometric analysis," Appl. Opt. 51, B213-B222 (2012)

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  1. R. S. Harmon, F. C. DeLucia, C. E. McManus, N. J. McMillan, R. F. Jenkins, M. E. Walsh, and A. Miziolek, “Laser-induced breakdown spectroscopy: an emerging chemical sensor technology for real-time field-portable, geochemical, mineralogical, and environmental applications,” Appl. Geochem. 21, 730–747 (2006). [CrossRef]
  2. K. Novotný, J. Kaiser, M. Galiová, V. Konečná, Novotný, M. Liśka, V. Kanický, and V. Otruba, “Mapping of different structures on a large area of granite sample using laser-ablation based analytical techniques, an exploratory study,” Spectrochim. Acta B 63, 1139–1144 (2008). [CrossRef]
  3. R. Barbini, F. Colao, V. Lazic, R. Fantoni, A. Paluci, and M. Angelone, “On board LIBS analysis of marine sediments collected during the XVI Italian campaign in Antarctica,” Spectrochim. Acta B 57, 1203–1218 (2002). [CrossRef]
  4. J. R. Thompson, R. C. Wiens, J. E. Barefield, D. T. Vaniman, H. E. Newsom, and S. M. Clegg, “Remote laser-induced breakdown spectroscopy analyses of Dar al Gani 476 and Zagami Martian meteorites,” J. Geophys. Res. 111, doi:10.1029/2005JE002578 (2006). [CrossRef]
  5. A. De Giacomo, M. Del’Aglio, O. De Pascale, S. Longo, and M. Capitelli, “Laser induced breakdown spectroscopy on meteorites,” Spectrochim. Acta B 62, 1606–1611 (2007). [CrossRef]
  6. M. Dell’Aglio, A. De Giocomo, R. Gauduiso, O. De Pascale, G. S. Senesi, and S. Longo, “Laser induced breakdown spectroscopy applications to meteorites: chemical analysis and composition profiles,” Geochim. Cosmochim. Acta 74, 7329–7339 (2010). [CrossRef]
  7. F. Colao, R. Fantoni, V. Lazic, A. Paolini, F. Fabbri, G. G. Ori, L. Marinangeli, and A. Baliva, “Investigation of LIBS feasibility for in situ planetary exploration: an analysis on Martian rock analogues,” Planet. Space Sci. 52, 117–123 (2004). [CrossRef]
  8. B. Sallé, D. A. Cremers, S. Maurice, R. C. Wiens, and P. Fichet, “Evaluation of a compact spectrograph for in-situ and stand-off laser-induced breakdown spectroscopy analyses of geological samples on Mars missions,” Spectrochim. Acta B 60, 805–815 (2005). [CrossRef]
  9. B. Sallé, J.-L. Lacour, P. Mauchien, P. Fichet, S. Maurice, and G. Manhès, “Comparative student of different methodologies for quantitative rock analysis by laser-induced breakdown spectroscopy in a simulated Martian atmosphere,” Spectrochim. Acta B 61, 301–313 (2006). [CrossRef]
  10. D. Derome, M. Cathelineau, M. Cuney, C. Fabre, and T. Lhomme, “Mixing of sodic and calcic brines and uranium deposition at McArthur River, Saskatchewan, Canada: a Raman and laser-induced breakdown spectroscopic study of fluid inclusions,” Econ. Geol. 100, 1529–1545 (2005).
  11. D. Derome, M. Cathelineau, C. Fabre, M.-C. Boiron, D. Banks, T. Lhomme, and M. Cuney, “Paleo-fluid composition determined from individual fluid inclusions by Raman and LIBS: applications to mid-Proterozoic evaporitic Na-Ca brines (Alligator Rivers Uranium Field, Northern Territories Australia),” Chem. Geol. 237, 240–254 (2007). [CrossRef]
  12. C. Fabre, M. C. Coiron, J. Dubessey, A. Chabiron, B. Charoy, and T. M. Crespo, “Advances in lithium analysis in solids by means of laser-induced breakdown spectroscopy: an exploratory study,” Geochim. Cosmochim. Acta 66, 1401–1407 (2002). [CrossRef]
  13. M. Z. Martin, N. Labbé, N. André, S. D. Wullschleger, R. D. Harris, and M. H. Ebinger, “Novel multivariate analysis for soil carbon measurements using laser-induced breakdown spectroscopy,” Soil Sci. Soc. Am. J. 74, 87–93 (2010). [CrossRef]
  14. M. D. Dyar, J. M. Tucker, S. Humphries, S. M. Clegg, R. C. Wiens, and M. D. Lane, “Strategies for Mars remote laser-induced breakdown spectroscopy analysis of sulfur in geological samples,” Spectrochim. Acta B 66, 39–56 (2011). [CrossRef]
  15. J.-B. Sirven, B. Bousquet, L. Canioni, and L. Sarger, “Laser-induced breakdown spectroscopy of composite samples: comparison of advanced chemometrics methods,” Anal. Chem. 78, 1462–1469 (2006). [CrossRef]
  16. D. L. Death, A. P. Cunningham, and L. J. Pollard, “Multi-element and mineralogical analysis of mineral ores using laser-induced breakdown spectroscopy and chemometric analysis,” Spectrochim. Acta B 63, 763–769 (2008). [CrossRef]
  17. D. L. Death, A. P. Cunningham, and L. J. Pollard, “Multi-element analysis of iron ore pellets by laser-induced breakdown spectroscopy and principal components regression,” Spectrochim. Acta B 64, 1048–1058 (2009). [CrossRef]
  18. S. M. Clegg, E. Sklute, M. D. Dyar, J. E. Barefield, and R. C. Wiens, “Multivariate analysis of remote laser-induced breakdown spectroscopy spectra using partial least squares, principal component analysis, and related techniques,” Spectrochim. Acta B 64, 79–88 (2009). [CrossRef]
  19. J. M. Tucker, M. D. Dyar, M. W. Schaefer, S. M. Clegg, and R. C. Wiens, “Optimization of laser-induced breakdown spectroscopy for rapid geochemical analysis,” Chem. Geol. 277, 137–148 (2010). [CrossRef]
  20. M. D. Dyar, M. L. Carmosino, J. M. Tucker, E. A. Brown, S. M. Clegg, R. C. Wiens, J. E. Barefield, J. S. Delaney, G. M. Ashley, and S. G. Driese, “Remote laser-induced breakdown spectroscopy analysis of East African Rift sedimentary samples under Mars conditions,” Chem. Geol., doi:10.10163/j.chemgeo.2011.11.019 (2011). [CrossRef]
  21. C. A. Smith, M. A. Martine, D. K. Veirs, and D. A. Cremers, “Pu-239/Pu-240 isotope ratios determined using high resolution emission spectroscopy in a laser-induced plasma,” Spectrochim. Acta B 57, 929–937 (2002). [CrossRef]
  22. R. E. Russo, A. A. Bol’shakov, X. Mao, C. P. McKay, D. L. Perry, and O. Sorkhabi, “Laser ablation molecular isotopic spectrometry,” Spectrochim. Acta B 66, 99–104 (2011). [CrossRef]
  23. F. R. Doucet, G. Lithgow, R. Kosierb, P. Bouchard, and M. Sabsabi, “Determination of isotope ratios using laser-induced breakdown spectroscopy in ambient air at atmospheric pressure for nuclear forensics,” J. Anal. At. Spectrom. 26, 536–541 (2011). [CrossRef]
  24. K. L. Maxwell and M. K. Hudson, “Spectral study of metallic molecular bands in hybrid rocket plumes,” J. Pyrotech. 21, 59–69 (2005).
  25. K. A. Yetter, “Determining provenance of corundum using laser-induced breakdown spectroscopy (LIBS) and chemometric analysis,” M. S. thesis (New Mexico State University, 2011).
  26. I. B. Gornushkin, A. Ruíz-Medina, J. M. Anzano, B. W. Smith, and J. D. Winefordner, “Identification of particulate materials by correlation analysis using a microscopy laser induced breakdown spectrometer,” J. Anal. At. Spectrom. 15, 581–586(2000). [CrossRef]
  27. J. J. Remus, J. L. Gottfried, R. S. Harmon, A. Draucker, D. Baron, and R. Yohe, “Archeological applications of laser-induced breakdown spectroscopy: an example from the Coso Volcanic Field, California, using advanced statistical signal processing analysis,” Appl. Opt. 49, C120–C131. [CrossRef]
  28. N. J. McMillan, R. S. Harmon, F. C. De Lucia, and A. W. Miziolek, “Laser-induced breakdown spectroscopy analysis of minerals: carbonate and silicates,” Spectrochim. Acta B 62, 1528–1536 (2007). [CrossRef]
  29. R. S. Harmon, J. Remus, N. J. McMillan, C. McManus, L. Collins, J. L. Gottfried, F. C. De Lucia, and A. W. Miziolek, “LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals,” Appl. Geochem. 24, 1125–1141 (2009). [CrossRef]
  30. J. L. Gottfried, R. S. Harmon, F. C. De Lucia, and A. W. Miziolek, “Multivariate analysis of laser-induced breakdown spectroscopy chemical signature for geomaterial classification,” Spectrochim. Acta B 64, 1009–1019 (2009). [CrossRef]
  31. N. L. Lanza, R. C. Wiens, S. M. Clegg, A. M. Ollila, S. D. Humphries, H. E. Newsom, and J. E. BarefieldChemCam Team, “Calibrating the ChemCam laser-induced breakdown spectroscopy instrument for carbonate minerals on Mars,” Appl. Opt. 49, C211–C217. [CrossRef]
  32. J.-B. Sirven, B. Sallé, P. Mauchien, J.-L. Lacour, S. Maurice, and G. Manhès, “Feasibility study of rock identification at the surface of Mars by remote laser-induced breakdown spectroscopy and three chemometric methods,” J. Anal. At. Spectrom. 22, 1471–1480 (2007). [CrossRef]
  33. D. E. Zeller, “The stratigraphic succession in Kansas,” Bull. Kans. Geol. Sur. 189, 81 (1968).
  34. R. A. Multari, D. A. Cremers, J. M. Dupre, and J. E. Gustafson, “The use of laser-induced breakdown spectroscopy (LIBS) for distinguishing between bacterial pathogen species and strains,” Appl. Spectrosc. 64, 750–759 (2010). [CrossRef]
  35. D. A. Cremers and L. J. Radziemski, Handbook of Laser-Induced Breakdown Spectroscopy (Wiley, 2006).
  36. S. Wold, “Pattern recognition by means of disjoint principal components models,” Pattern Recogn. 8, 127–139(1976). [CrossRef]
  37. S. Wold, M. Sjöström, and L. Eriksson, “PLS-regression: a basic tool of chemometrics,” Chemom. Intell. Lab. Syst. 58, 109–130 (2001). [CrossRef]

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