Evaluation of Mid-Infrared and X-ray Fluorescence Data Fusion Approaches for Prediction of Soil Properties at the Field Scale.

Previous studies investigating multi-sensor fusion for the collection of soil information have shown variable improvements, and the underlying prediction mechanisms are not sufficiently understood for spectrally-active and -inactive properties. Our objective was to study prediction mechanisms and benefits of model fusion by measuring mid-infrared (MIR) and X-ray fluorescence (XRF) spectra, texture, total and labile organic carbon (OC) and nitrogen (N) content, pH, and cation exchange capacity (CEC) for n = 117 soils from an arable field in Germany. Partial least squares regression models underwent a three-fold training/testing procedure using MIR spectra or elemental concentrations derived from XRF spectra. Additionally, two sequential hybrid and two high-level fusion approaches were tested. For the studied field, MIR was superior for organic properties (ratio of prediction to interquartile distance of validation (RPIQV) for total OC = 7.7 and N = 5.0)), while XRF was superior for inorganic properties (RPIQV for clay = 3.4, silt = 3.0, and sand = 1.8). Even the optimal fusion approach brought little to no accuracy improvement for these properties. The high XRF accuracy for clay and silt is explained by the large number of elements with variable importance in the projection scores >1 (Fe ≈ Ni > Si ≈ Al ≈ Mg > Mn ≈ K ≈ Pb (clay only) ≈ Cr) with strong spearman correlations (±0.57 < rs < ±0.90) with clay and silt. For spectrally-inactive properties relying on indirect prediction mechanisms, the relative improvements from the optimal fusion approach compared to the best single spectrometer were marginal for pH (3.2% increase in RPIQV versus MIR alone) but more pronounced for labile OC (9.3% versus MIR) and CEC (12% versus XRF). Dominance of a suboptimal spectrometer in a fusion approach worsened performance compared to the best single spectrometer. Granger-Ramanathan averaging, which weights predictions according to accuracy in training, is therefore recommended as a robust approach to capturing the potential benefits of multiple sensors.

Accuracy and Reproducibility of Laboratory Diffuse Reflectance Measurements with Portable VNIR and MIR Spectrometers for Predictive Soil Organic Carbon Modeling.

Soil spectroscopy in the visible-to-near infrared (VNIR) and mid-infrared (MIR) is a cost-effective method to determine the soil organic carbon content (SOC) based on predictive spectral models calibrated to analytical-determined SOC reference data. The degree to which uncertainty in reference data and spectral measurements contributes to the estimated accuracy of VNIR and MIR predictions, however, is rarely addressed and remains unclear, in particular for current handheld MIR spectrometers. We thus evaluated the reproducibility of both the spectral reflectance measurements with portable VNIR and MIR spectrometers and the analytical dry combustion SOC reference method, with the aim to assess how varying spectral inputs and reference values impact the calibration and validation of predictive VNIR and MIR models. Soil reflectance spectra and SOC were measured in triplicate, the latter by different laboratories, for a set of 75 finely ground soil samples covering a wide range of parent materials and SOC contents. Predictive partial least-squares regression (PLSR) models were evaluated in a repeated, nested cross-validation approach with systematically varied spectral inputs and reference data, respectively. We found that SOC predictions from both VNIR and MIR spectra were equally highly reproducible on average and similar to the dry combustion method, but MIR spectra were more robust to calibration sample variation. The contributions of spectral variation (ΔRMSE < 0.4 g·kg−1) and reference SOC uncertainty (ΔRMSE < 0.3 g·kg−1) to spectral modeling errors were small compared to the difference between the VNIR and MIR spectral ranges (ΔRMSE ~1.4 g·kg−1 in favor of MIR). For reference SOC, uncertainty was limited to the case of biased reference data appearing in either the calibration or validation. Given better predictive accuracy, comparable spectral reproducibility and greater robustness against calibration sample selection, the portable MIR spectrometer was considered overall superior to the VNIR instrument for SOC analysis. Our results further indicate that random errors in SOC reference values are effectively compensated for during model calibration, while biased SOC calibration data propagates errors into model predictions. Reference data uncertainty is thus more likely to negatively impact the estimated validation accuracy in soil spectroscopy studies where archived data, e.g., from soil spectral libraries, are used for model building, but it should be negligible otherwise.

Comparison of Portable and Bench-Top Spectrometers for Mid-Infrared Diffuse Reflectance Measurements of Soils.

Mid-infrared (MIR) spectroscopy has received widespread interest as a method to complement traditional soil analysis. Recently available portable MIR spectrometers additionally offer potential for on-site applications, given sufficient spectral data quality. We therefore tested the performance of the Agilent 4300 Handheld FTIR (DRIFT spectra) in comparison to a Bruker Tensor 27 bench-top instrument in terms of (i) spectral quality and measurement noise quantified by wavelet analysis; (ii) accuracy of partial least squares (PLS) calibrations for soil organic carbon (SOC), total nitrogen (N), pH, clay and sand content with a repeated cross-validation analysis; and (iii) key spectral regions for these soil properties identified with a Monte Carlo spectral variable selection approach. Measurements and multivariate calibrations with the handheld device were as good as or slightly better than Bruker equipped with a DRIFT accessory, but not as accurate as with directional hemispherical reflectance (DHR) data collected with an integrating sphere. Variations in noise did not markedly affect the accuracy of multivariate PLS calibrations. Identified key spectral regions for PLS calibrations provided a good match between Agilent and Bruker DHR data, especially for SOC and N. Our findings suggest that portable FTIR instruments are a viable alternative for MIR measurements in the laboratory and offer great potential for on-site applications.