Skip to main content
Log in

Application of laser-induced breakdown spectroscopy (LIBS) coupled with PCA for rapid classification of soil samples in geothermal areas

  • Research Paper
  • Published:
Analytical and Bioanalytical Chemistry Aims and scope Submit manuscript

Abstract

The Manuguru geothermal area, located in the Telangana state, is one of the least explored geothermal fields in India. In this study, characterization of the soil samples is carried out by laser-induced breakdown spectroscopy (LIBS) coupled with analytical spectral-dependent principal component analysis. A total of 20 soil samples were collected both from near the thermal discharges as well as away from the thermal manifestations. LIBS spectra were recorded for all the collected soil samples and principal component analysis (PCA) was applied to easily identify the emission lines majorly responsible for variety classification of the soil samples. In this submission, a modified PCA was developed which is based on the spectral truncation method to reduce the huge number of spectral data obtained from LIBS. The PCA bi-plot on the LIBS data reveals the presence of two different clusters. One cluster represents the soil samples collected from the close vicinity of the thermal manifestations whereas the other cluster contains the soil samples collected away from the thermal sprouts. PCA performed on the chemical dataset of the soil samples also reveals the same clustering of the soil samples. Both LIBS and chemical analysis data shows that soil samples near the thermal waters are found to be enriched in B, Sr, Cs, Rb, Fe, Co, Al, Si, Ti, Ru, Mn, Mg, Cu, and Eu concentrations compared to the soil samples located away from thermal manifestations. This study demonstrates the potential use of LIBS coupled with PCA as a tool for variety discrimination of soil samples in a geothermal area. LIBS is shown to be a viable real-time elemental characterization technology for these samples, avoiding the rigorous dissolution required by other analytical techniques.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  1. Awan MA, Ahmed SH, Aslam MR, Qazi IA, Baig MA. Determination of heavy metals in ambient air particulate matter using laser-induced breakdown spectroscopy. Arab J Sci Eng. 2013;38:1655–61.

    Article  CAS  Google Scholar 

  2. Badday MA, Bidin N, Rizvi ZH, Hosseinian R. Determination of environmental safety level with laser-induced breakdown spectroscopy technique. Chem Ecol. 2015;31:379–87.

    Article  CAS  Google Scholar 

  3. Boucher TF, Ozanne MV, Carmosino ML, Dyar MD, Mahadevan S, Breves EA, et al. A study of machine learning regression methods for major elemental analysis of rocks using laser-induced breakdown spectroscopy. Spectrochim Acta B. 2015;107:1–10.

    Article  CAS  Google Scholar 

  4. Caneve L, Diamanti A, Grimaldi F, Palleschi G, Spizzichino V, Valentini F. Analysis of fresco by laser induced breakdown spectroscopy. Spectrochim Acta B. 2010;65:702–6.

    Article  CAS  Google Scholar 

  5. Clegg SM, Sklute E, Dyar MD, Barefield JE, Wiens RC. Multivariate analysis of remote laser-induced breakdown spectroscopy spectra using partial least squares, principal component analysis, and related techniques. Spectrochim Acta B. 2009;64:79–88.

    Article  CAS  Google Scholar 

  6. Clegg SM, Wiens R, Misra AK, Sharma SK, Lambert J, Bender S, et al. Planetary geochemical investigations using Raman and laser-induced breakdown spectroscopy. ApplSpectrosc. 2014;68(9):925–36. https://doi.org/10.1366/13-07386.

    Article  CAS  Google Scholar 

  7. Cousin A, Forni O, Maurice S, Gasnault O, Fabre C, Sautter V, et al. Laser induced breakdown spectroscopy library for the Martian environment. Spectrochim. Acta Part B. 2011;66:805–14.

    Article  CAS  Google Scholar 

  8. Davis JC. Statistics and data analysis in geology. New York: John Wiley& Sons Inc; 1986.

    Google Scholar 

  9. De Lucia FC Jr, Gottfried JL, Munson CA, Miziolek AW. Double pulse laser induced breakdown spectroscopy of explosives: initial study towards improved discrimination. Spectrochim. Acta Part B. 2007;62:1399–404.

    Article  CAS  Google Scholar 

  10. De Lucia FC, Samuels AJ, Harmon RS, Walters RA, McNesby KL, LaPointe A, et al. Laser-induced breakdown spectroscopy (LIBS): a promising versatile chemical sensor technology for hazardous material detection. IEEE Sensors J. 2005;5:681–9.

    Article  CAS  Google Scholar 

  11. Diedrich J, Rehse SJ, Palchaudhuri S. Pathogenic Escherichia coli strain discrimination using laser-induced breakdown spectroscopy. J Appl Phys. 2007;102:014702. https://doi.org/10.1063/1.2752784.

    Article  CAS  Google Scholar 

  12. Fang SC. Sorption and transformation of mercury vapor by dry soil. Environ Sci Technol. 1978;12:285–8.

    Article  CAS  Google Scholar 

  13. Fink H, Panne U, Niessner R. Process analysis of recycled thermoplasts from consumer electronics by laser-induced plasma spectroscopy. Anal Chem. 2002;74:4334–42.

    Article  CAS  PubMed  Google Scholar 

  14. Gottfried JL, De Lucia FC Jr, Munson CA, Miziolek AW. Double-pulse standoff laser-induced breakdown spectroscopy for versatile hazardous materials detection. Spectrochim Acta B. 2007;62:1405–11.

    Article  CAS  Google Scholar 

  15. Gottfried JL, Harmon RS, De Lucia FC Jr, Miziolek AW. Multivariate analysis of laser-induced breakdown spectroscopy chemical signatures for geomaterial classification. SpectrochimicaActa B. 2009;64:1009–19.

    Article  CAS  Google Scholar 

  16. Harmon RS, Remus J, McMillan NJ, McManus C, Collins L, Gottfried JL Jr, et al. LIBS analysis of geomaterials: geochemical fingerprinting for the rapid analysis and discrimination of minerals. Appl Geochem. 2009;24:1125–41.

    Article  CAS  Google Scholar 

  17. Jung EC, Lee DH, Yun JI, Kim JG, Yeon JW, Song K. Quantitative determination of uranium and europium in glass matrix by laser-induced breakdown spectroscopy. Spectrochim Acta B At Spectrosc. 2011;66(9–10):761–4.

    Article  CAS  Google Scholar 

  18. Kaasalainen H, Stefánsson A. The chemistry of trace elements in surface geothermal waters and steam, Iceland. Chem Geol. 2012;330–331:60–85.

    Article  CAS  Google Scholar 

  19. Kaiser J, Novotny K, Martin MZ, Hrdlicka A, Malina R, Hartl M, et al. Trace elemental analysis by laser-induced breakdown spectroscopy-biological applications. Surf Sci Rep. 2012;67:233–43.

    Article  CAS  Google Scholar 

  20. Knight AK, Scherbarth NL, Cremers DA, Ferris MJ. Characterization of laser induced breakdown spectroscopy (LIBS) for application to space exploration. Appl Spectrosc. 2000;54:331–40.

    Article  CAS  Google Scholar 

  21. Kumar A, Singhal RK, Rout S, Ravi PM. Spatial geochemical variation of major and trace elements in the marine sediments of Mumbai Harbor Bay. Environ Earth Sci. 2013. https://doi.org/10.1007/s12665-013-2366-3.

  22. Landa ER. The retention of metallic mercury vapour by soils. Geochim Cosmochim Acta. 1978;42:1407–11.

    Article  CAS  Google Scholar 

  23. Mowery MD, Sing R, Kirsch J, Razaghi A, Bechard S, Reed RA. Rapid at-line analysis of coating thickness and uniformity on tablets using laser induced breakdown spectroscopy. J Pharm Biomed Anal. 2002;28:935–43. https://doi.org/10.1016/S0731-7085(01)00705-1.

    Article  CAS  PubMed  Google Scholar 

  24. Myakalwar AK, Sreedhar S, Barmanb I, Dingari NC, Rao VS, Kiran PP, et al. Laser-induced breakdown spectroscopy-based investigation and classification of pharmaceutical tablets using multivariate chemometric analysis. Talanta. 2011;87:53–9.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  25. Nicholson K. Geothermal fluids: chemistry and exploration techniques, ISBN 3-540-56017-3. Berlin: Springer-Verlag; 1993. p. 209–10.

    Book  Google Scholar 

  26. Phelps DW, Buseck PR. Natural concentration of Hg in the Yellowstone and Coso geothermal fields, vol. 2: Geotherm.ResourcesCouncilTrans; 1978. p. 521–2.

  27. Phelps D, Buseck PR. Distribution of soil mercury and the development of soil mercuryanomalies in the Yellowstone geothermal area, Wyoming. Econ Geol. 1980;75:730–41.

    Article  CAS  Google Scholar 

  28. Sallé B, Lacour JL, Vors E, Fichet P, Maurice S, Cremers DA, et al. Laser induced breakdown spectroscopy for Mars surface analysis: capabilities at stand-off distances and detection of chlorine and sulfur elements. Spectrochim Acta B. 2004;59:1413–22.

    Article  CAS  Google Scholar 

  29. Sallé B, Lacour JL, Mauchien P, Fichet P, Maurice S, Manhès G. Comparative study of different methodologies for quantitative rock analysis by laser-induced breakdown spectroscopy in a simulated Martian atmosphere. Spectrochim Acta B. 2006;61:301–13.

    Article  CAS  Google Scholar 

  30. Sarkar A, Mishra RK, Kaushik CP, Wattal PK, Alamelu D, Aggarwal SK. Analysis of barium borosilicate glass matrix for uranium determination by using ns-IR-LIBS in air and Ar atmosphere. RadiochimicaActa. 2014;102(9):805–12.

    CAS  Google Scholar 

  31. Shakeri A, Ghoreyshinia S, Mehrabi B, Delavari M. Rare earth elements geochemistry in springs from Taftan geothermal area SE Iran. J Volcanol Geotherm Res. 2015;304:49–61.

    Article  CAS  Google Scholar 

  32. Shen XK, Lu YF. Detection of uranium in solids by using laser-induced breakdown spectroscopy combined with laser-induced fluorescence. Appl Opt. 2008;47(11):1810–5.

    Article  CAS  PubMed  Google Scholar 

  33. Singh M, Karki V, Mishra RK, Kumar A, Kaushik CP, Mao X, et al. Analytical spectral dependent partial least squares regression: a study of nuclear waste glass from thorium based fuel using LIBS. J Anal At Spectrom. 2015;30:2507–15.

    Article  CAS  Google Scholar 

  34. Sirven JB, Bousquet B, Canioni L, Sarger L, Tellier S, Gautier MP, et al. Qualitative and quantitative investigation of chromium-polluted soils by laser-induced breakdown spectroscopy combined with neural networks analysis. Anal Bioanal Chem. 2006;385:256–62.

    Article  CAS  PubMed  Google Scholar 

  35. Sirven JB, Sallé B, Mauchien P, Lacour JL, Maurice S, Manhès G. Feasibility study of rock identification at the surface of Mars by remote laser-induced breakdown spectroscopy and three chemometric methods. J Anal At Spectrom. 2007;22:1471–80.

    Article  CAS  Google Scholar 

  36. Snyder GH. Methods for silicon analysis in plants, soils, and fertilizers. Stud Plant Sci. 2001;8:185–96.

    Article  CAS  Google Scholar 

  37. Tirumalesh K, Ramakumar KL, Chidambaram S, Pethaperumal S, Singh G. Rare earth elements distribution in clay zones of sedimentary formation, Pondicherry, south India. J Radioanal Nucl Chem. 2012;294:303–8.

    Article  CAS  Google Scholar 

  38. Unnikrishnan VK, Choudhari KS, Kulkarni SD, Nayak R, Karthaa VB, Santhosh C. Analytical predictive capabilities of laser induced breakdown spectroscopy (LIBS) with principal component analysis (PCA) for plastic classification. RSC Adv. 2013;3:25872–80.

    Article  CAS  Google Scholar 

  39. White DE. Mercury and base-metal deposits with associated thermal and mineral waters. In: Barnes HL, editor. Geochemistry of hydrothermal ore deposits. New York: Holt, Rinehart and Winston; 1967. p. 575–631.

    Google Scholar 

  40. Yu KQ, Zhao YR, Liu F, Yong H. Laser-induced breakdown spectroscopy coupled with multivariate chemometrics for variety discrimination of soil. Sci Rep. 2016;6:27574. https://doi.org/10.1038/srep27574.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  41. Yueh FY, Zheng HB, Singh JP, Burgess S. Preliminary evaluation of laser-induced breakdown spectroscopy for tissue classification. Spectrochim Acta B. 2009;64:1059–67.

    Article  CAS  Google Scholar 

  42. Zhang T, Wu S, Dong J, Wei J, Wang K, Tang H, et al. Quantitative and classification analysis of slag samples by laser induced breakdown spectroscopy (LIBS) coupled with support vector machine (SVM) and partial least square (PLS) methods. J Anal Atom Spectrom. 2015;30:368–74.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors (SC and UKS) wish to acknowledge Dr. P.K. Pujari, AD, RC&I group and the officers of GSI for their help and encouragement during the study. The authors (MS and AS) are thankful to Dr. S. Kannan, Head, FCD, for their constant support and encouragement in the LIBS work. The authors greatly acknowledge the in-depth and insightful reviews of two anonymous reviewers which have immensely contributed to the improvement of the quality of the manuscript.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Sitangshu Chatterjee or Arnab Sarkar.

Ethics declarations

Conflict of interest

The authors declare that there is no conflict of interest.

Additional information

Publisher’s note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chatterjee, S., Singh, M., Biswal, B.P. et al. Application of laser-induced breakdown spectroscopy (LIBS) coupled with PCA for rapid classification of soil samples in geothermal areas. Anal Bioanal Chem 411, 2855–2866 (2019). https://doi.org/10.1007/s00216-019-01731-3

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00216-019-01731-3

Keywords

Navigation