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Hyperspectral data acquired from field-based platforms present new challenges for their analysis, particularly for complex vertical surfaces exposed to large changes in the geometry and intensity of illumination. The use of hyperspectral data to map rock types on a vertical mine face is demonstrated, with a view to providing real-time information for automated mining applications. The performance of two classification techniques, namely, spectral angle mapper (SAM) and support vector machines (SVMs), is compared rigorously using a spectral library acquired under various conditions of illumination. SAM and SVM are then applied to a mine face, and results are compared with geological boundaries mapped in the field. Effects of changing conditions of illumination, including shadow, were investigated by applying SAM and SVM to imagery acquired at different times of the day. As expected, classification of the spectral libraries showed that, on average, SVM gave superior results for SAM, although SAM performed better where spectra were acquired under conditions of shadow. In contrast, when applied to hypserspectral imagery of a mine face, SVM did not perform as well as SAM. Shadow, through its impact upon spectral curve shape and albedo, had a profound impact on classification using SAM and SVM.