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Laser-induced breakdown spectroscopy (LIBS) is an analytical technique real-time geochemical analysis that is being developed for portable use outside of the laboratory. In this study, statistical signal processing and classification techniques were applied to single-shot, broadband LIBS spectra, comprising measured plasma light intensities between 200 and 960 nm, for a suite of 157 garnets of different composition from 92 locations worldwide. Partial least squares discriminant analysis was applied to sets of 25 LIBS spectra for each garnet sample and used to classify the garnet samples based on composition and geographic origin. Careful consideration was given to the cross-validation procedure to ensure that the classification algorithm is robust to unseen data. The results indicate that broadband LIBS analysis can be used to discriminate garnets of different composition and has the potential to discern geographic origin. © 2010

A broad suite of geological materials was studied a using a handheld laser‐induced breakdown spectroscopy (LIBS) instrument. Because LIBS is simultaneously sensitive to all elements, the full broadband emission spectrum recorded from a single laser shot provides a ‘chemical fingerprint’ of any material – solid, liquid or gas. The distinguishing chemical characteristics of the samples analysed were identified through principal component analysis (PCA), which demonstrates how this technique for statistical analysis can be used to identify spectral differences between similar sample types based on minor and trace constituents. Partial least squares discriminant analysis (PLSDA) was used to distinguish and classify the materials, with excellent discrimination achieved for all sample types. This study illustrates through four examples (carbonate minerals and rocks, the oxide mineral pair columbite–tantalite, the silicate mineral garnet and native gold) how portable, handheld LIBS analysers can be used for real‐time chemical analysis under simulated field conditions for element or mineral identification, plus such applications as stratigraphic correlation, provenance determination and natural resource exploration.