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Luminescence of crystals of natural spodumene and natural diamond of the type IIa is studied upon excitation by a laser at a wavelength of 222 nm and by a subnanosecond avalanche electron beam (SAEB) formed in air at the atmospheric pressure. The photoluminescence spectra of spodumene and diamond are shown to exhibit additional bands, which are absent upon SAEB excitation. It is demonstrated that SAEB excitation allows one to analyse various crystals under normal conditions without using any vacuum equipment. (interaction of laser radiation with matter)