Rapid prediction of total petroleum hydrocarbons concentration in contaminated soil using vis-NIR spectroscopy and regression techniques

Visible and near infrared spectrometry (vis-NIRS) coupled with data mining techniques can offer fast and cost-effective quantitative measurement of total petroleum hydrocarbons (TPH) in contaminated soils. Literature showed however significant differences in the performance on the vis-NIRS between linear and non-linear calibration methods. This study compared the performance of linear partial least squares regression (PLSR) with a nonlinear random forest (RF) regression for the calibration of vis-NIRS when analysing TPH in soils. 88 soil samples (3 uncontaminated and 85 contaminated) collected from three sites located in the Niger Delta were scanned using an analytical spectral device (ASD) spectrophotometer (350-2500 nm) in diffuse reflectance mode. Sequential ultrasonic solvent extraction-gas chromatography (SUSE-GC) was used as reference quantification method for TPH which equal to the sum of aliphatic and aromatic fractions ranging between C-10 and C-35. Prior to model development, spectra were subjected to pre-processing including noise cut, maximum normalization, first derivative and smoothing. Then 65 samples were selected as calibration set and the remaining 20 samples as validation set. Both vis-NIR spectrometry and gas chromatography profiles of the 85 soil sampleswere subjected to RF and PLSR with leave-one-out cross-validation (LOOCV) for the calibration models. Results showed that RF calibration model with a coefficient of determination (R-2) of 0.85, a root means square error of prediction (RMSEP) 68.43 mg kg(-1), and a residual prediction deviation (RPD) of 2.61 outperformed PLSR (R-2 = 0.63, RMSEP = 107.54 mg kg(-1) and RDP = 2.55) in cross-validation. These results indicate that RF modelling approach is accounting for the nonlinearity of the soil spectral responses hence, providing significantly higher prediction accuracy compared to the linear PLSR. It is recommended to adopt the vis-NIRS coupled with RF modelling approach as a portable and cost effective method for the rapid quantification of TPH in soils. (c) 2017 Elsevier B.V. All rights reserved.