Accurate and detailed spatial soil information about within-field variability is essential for variable-rate applications of farm resources. Soil total nitrogen (TN) and total carbon (TC) are important fertility parameters that can be measured with on-line (mobile) visible and near infrared (vis-NIR) spectroscopy. This study compares the performance of local farm scale calibrations with those based on the spiking of selected local samples from both fields into an European dataset for TN and TC estimation using three modelling techniques, namely gradient boosted machines (GBM), artificial neural networks (ANNs) and random forests (RF). The on-line measurements were carried out using a mobile, fiber type, vis-NIR spectrophotometer (305–2200 nm) (AgroSpec from tec5, Germany), during which soil spectra were recorded in diffuse reflectance mode from two fields in the UK. After spectra pre-processing, the entire datasets were then divided into calibration (75%) and prediction (25%) sets, and calibration models for TN and TC were developed using GBM, ANN and RF with leave-one-out cross-validation. Results of cross-validation showed that the effect of spiking of local samples collected from a field into an European dataset when combined with RF has resulted in the highest coefficients of determination (R²) values of 0.97 and 0.98, the lowest root mean square error (RMSE) of 0.01% and 0.10%, and the highest residual prediction deviations (RPD) of 5.58 and 7.54, for TN and TC, respectively. Results for laboratory and on-line predictions generally followed the same trend as for cross-validation in one field, where the spiked European dataset-based RF calibration models outperformed the corresponding GBM and ANN models. In the second field ANN has replaced RF in being the best performing. However, the local field calibrations provided lower R² and RPD in most cases. Therefore, from a cost-effective point of view, it is recommended to adopt the spiked European dataset-based RF/ANN calibration models for successful prediction of TN and TC under on-line measurement conditions.

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 (350-2500nm) 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 C10 and C35. 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 samples were 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 (R2) of 0.85, a root means square error of prediction (RMSEP) 68.43mgkg-1, and a residual prediction deviation (RPD) of 2.61 outperformed PLSR (R2=0.63, RMSEP=107.54mgkg-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.

It is well-documented in the visible and near-infrared reflectance spectroscopy (VNIRS) studies that soil moisture content (SMC) negatively affects the prediction accuracy of soil attributes. This work was undertaken to remove the negative effect of SMC on the on-line prediction of soil organic carbon (SOC). A mobile VNIR spectrophotometer with a spectral range of 305–1700 nm and spectral resolution of 1 nm (CompactSpec, Tec5 Technology, Germany) was used for the spectral measurements at four farms in Flanders, Belgium. A total of 381 fresh soil samples were collected and divided into a calibration set (264) and a validation set (117). The validation samples were processed (air-dried and grind) and scanned with the same spectrophotometer in the laboratory. Three SMC correction methods, namely, external parameter orthogonalization (EPO), piecewise direct standardization (PDS), and orthogonal signal correction (OSC) were used to correct the on-line fresh spectra based-on its corresponding laboratory spectra. Then, the Cubist machine learning method was used to develop calibration models of SOC using the on-line spectra (after correction) of the calibration set. Results indicated that the EPO-Cubist outperformed the PDS-Cubist and the OSC-Cubist, with considerable improvements in the prediction results of SOC (coefficient of determination (R²) = 0.76, ratio of performance to deviation (RPD) = 2.08, and root mean square error of prediction (RMSEP) = 0.12%), compared with the corresponding uncorrected on-line spectra (R² = 0.55, RPD = 1.24, and RMSEP = 0.20%). It can be concluded that SOC can be accurately predicted on-line using the Cubist machine learning method, after removing the negative effect of SMC with the EPO method.