Abstract
Polycyclic aromatic hydrocarbons (PAHs) are currently of great concern due to their potential carcinogenicity. The standard methods of identification and quantification of PAHs are costly and time–consuming. Laser–induced fluorescence (LIF) spectroscopy can overcome these limitations and make it possible to simultaneously identify and quantify several PAHs without the aid of chemical pre-processing steps. LIF system and multivariate chemometric analysis, especially the partial least square (PLS) regression method, have been employed to investigate the potential correlations between LIF data and soil properties, especially their physical composition and moisture content, and confirm the capability for the detection of PAHs in soils, using the soil samples artificially comprised of sand and silt/clay. Phenanthrene and pyrene were selected as representative PAHs. The diffuse reflectance has also been recorded to investigate the capability to normalize the LIF data. Data analysis, through a multivariate chemometric analysis, showed significant statistical correlations between the LIF intensity and the PAH concentrations in soil samples. The LIF intensity has been shown to depend on the sample properties, with the diffuse reflectance at 532 nm also depending on these factors. It has been demonstrated that the errors induced by the physical composition could be reduced by dividing the LIF intensity by the diffuse reflectance at 532 nm. The LIF concentration data were compared with those measured by high performance liquid chromatography (HPLC), with values of correlation coefficient (R) of 0.96 and 0.90 for phenanthrene and pyrene, respectively. The results obtained through a data analysis algorithm, based on the linear mixture model and the normalization by diffuse reflectance, demonstrated that the PAHs in artificial soil samples could be discriminated and quantified by LIF spectroscopy.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Andressen, P. and Strube, G.: 1994, Optical Measurement: Laser-Induced Fluorescence,in F. Mayinger (ed.), Springer-Verlag, New York, 243 pp.
Beach, D., Shotwell, A. and Essue, P.: 1993, Applications of Lasers and Laser Systems, PTR Prentice Hall, New Jersey, 97 pp.
Beltran, J., Ferrer, R. and Guiteras, J.: 1998, 'Multivariate calibration of polycyclic hydrocarbon mixtures from excitation-emission fluorescence spectra', Anal. Chim. Acta 373, 311–319.
Billa, E., Pastou, A., Monties, B., Romero, J. and Koukios, E.: 2000, ' Multivariate chemometric analysis of the fluorescence spectra of eucalyptus wood', Ind. Crops Prod. 11, 187–196.
Bublitz, J., Dickenhausen, M. Grätz, M., Todt, S. and Schade, W.: 1995, 'Fiber-optic laser-induced fluorescence probe for the detection of environmental pollutants', Appl. Optics 34, 3223–3233.
Bünting, U. and Karlitscheck, P.: 1998, 'Mathematical model for optimum fibre optic probe design and characterization', Spectrochim. Acta A54, 1369–1374.
Bünting, U., Lewitzka, F. and Karlitschek, P.: 1999, 'Mathematical model of a laser-induced fluo-rescence fiber-optic sensor head for trace detection of pollutants in soil', Appl. Spectrosc. 53, 49–56.
Deming, S. and Morgan, S.: 1973, 'Simplex optimization of variables in analytical chemistry', Anal. Chem. 45, 278–283.
Harvey, R.: 1991, Polycyclic Aromatic Hydrocarbons: Chemistry and Carcinogenicity, Cambridge University Press, Cambridge.
Karlitschek, P. and Hillrichs, G.: 1997, 'Active and passive Q-switching of a diode pumped Nd:KGW-laser', Appl. Phys. B 64, 21–24.
Karlitschek, P., Lewitzka, F., Bünting, U., Niederkrüger, M. and Marowsky, G.: 1998, 'Detection of aromatic pollutants in the environment by using UV-laser-induced fluorescence', Appl. Phys. B 67, 497–504.
Knorr, F. and Harris, J.: 1981, ' Resolution of multicomponent fluorescence spectra by an emission wavelength-decay time data matrix', Anal. Chem. 53, 272–276.
Ko, E.J., Lee, C. K., Kim, Y. J. and Kim, K. W., 2003. 'Monitoring of PAHs-contaminated soils using laser-induced fluorescence (LIF)', Environ. Technol. 24, 1157–1164.
Kostecki, P. and Calabrese, E.: 1992, Contaminated Soils: Diesel Fuel Contamination,Lewis Publishers, Boca Raton.
Kramer, R.: 1998, Chemometric Techniques for Quantitative Analysis, Marcel Dekker, New York, 131 pp.
Kumke, M., Löhmannsröben, H. and Roch, T.: 1995, ' Fluorescence spectroscopy of polynuclear aromatic compounds in environmental monitoring', J. Fluorescence 5, 139–153.
Lewitzka, F., Bünting, U., Karlitschek, P., Niederkrüger, M. and Marowsky, G.: 1999, 'Quantitative analysis of aromatic molecules in water by laser induced fluorescence spectroscopy and multi-variate calibration techniques', SPIE Proc. 3821, 331–338.
Lewitzka, F. and Niessner, R.: 1995, 'Application of time resolved fluorescence spectroscopy on the analysis of PAH-coated aerosols', Aerosol Sci. Technol. 23, 454–464.
Löhmannsröben, H. and Roch, T.: 2000, 'In situ laser-induced fluorescence (LIF) analysis of petroleum product-contaminated samples', J. Environ. Monit. 2, 17–22.
Löhmannsröben, H. and Schober, L.: 1999, 'Combination of laser-induced fluorescence and diffuse-reflectance spectroscopy for the in situ analysis of diesel-fuel-contaminated soils', Appl. Optics 38, 1404–1410.
Martens, H. and Naes T.: 1998, Multivariate Calibration: Multivariate Calibration Based on the Linear Mixture Model,Wiley, 116 pp.
Nikolau, K. and Mouvier, P.: 1984, ' sources and chemical reactivity of polynuclear aromatic hydro-carbons in the atmosphere-A critical review', Sci. Total Environ. 32, 103–132.
Panne, U., Lewitzka, F. and Niessner, R.: 1992, 'Fibre optical sensors for detection of atmospheric and hydrospheric polycyclic aromatic hydrocarbons', Analysis 20, 533–542.
Rudnick, S. and Chen, R.: 1998, 'Laser-induced fluorescence of pyrene and other polycyclic aromatic hydrocarbons (PAH) in seawaater', Talanta 47, 907–919.
Skoog, D. A. and Leary, J. J.: 1971, Principles of Instrumental Analysis, 4th edn., Saunders College Publishing, Orando, 7 pp.
U. S. EPA: 1995, 'Site Characterization Analysis Penetrometer System: Innovative Technology Evaluation Report', EPA/540/R-95/520.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Lee, C.K., Ko, E.J., Kim, K.W. et al. Partial Least Square Regression Method for the Detection of Polycyclic Aromatic Hydrocarbons in the Soil Environment Using Laser-Induced Fluorescence Spectroscopy. Water, Air, & Soil Pollution 158, 261–275 (2004). https://doi.org/10.1023/B:WATE.0000044858.39836.e2
Issue Date:
DOI: https://doi.org/10.1023/B:WATE.0000044858.39836.e2