Iron ore tailings are mainly composed of SiO2 and iron, whose content determines the potential reuse strategy of the tailings. Compared with the traditional wet chemistry approach, spectroscopy has proven its superior effectiveness in characterizing and predicting minerals, such as iron oxides, clay, and SiO2. This study aims to estimate the content of SiO2 and TFe in iron ore tailings based on visible–near infrared (VIS–NIR, 350–2500 nm) and thermal infrared (TIR, 8–14 μm) spectroscopy. The outer product analysis (OPA) method is used to combine VIS–NIR and TIR spectral domains, from which an outer product matrix of fusion data can be generated. The study area is the iron ore tailing dam from Waitoushan, which is one of the super-large iron deposits in the Anshan–Benxi iron cluster of northeastern China. The spectral analysis results demonstrated the following: (1) The reflectance feature at 1163–2499 nm in the VIS–NIR range correlates with TFe and the emissivity feature at 8–9.4 and 10.7–12 μm in the TIR range correlates with SiO2. (2) Compared with the original absorbance spectra, the correlation coefficients of fusion spectra improve from 0.66 to 0.87 for TFe and from 0.64 to 0.84 for SiO2. (3) The partial least squares regression, random forest (RF), and extreme learning machine exploiting particle swarm optimization modeling methods are established for SiO2 and TFe estimation. The prediction accuracy results indicate that the prediction model with OPA-fused spectra performs significantly better than with individual VIS–NIR and TIR spectra. The RF model with input-fused spectra provides the highest accuracy with the coefficients of determination of 0.95 and 0.91, root mean square errors of 0.97% and 0.96%, and ratios of performance to interquartile distance of 6.49 and 2.31 for SiO2 and TFe content estimation, respectively. These outcomes provide a theoretical basis and technical support for tailing composition estimation using spectroscopy.
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