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Recent developments of Laser-Induced Breakdown Spectroscopy (LIBS) are devoted to the real-time and in situ detection of chemical (C) and biological (B) pollutants. The aim of the present work is to present and assess the abilities of an innovative field-transportable system based on LIBS to detect and ideally classify the different forms of C and B contaminations. In this paper, we focused on the detection of particulate matter. Multielemental model and Bacillus-based real bacterial aerosols are studied in terms of elemental sensitivity, statistical sampling strategy and classification purposes by means of the LIBS. The capabilities of the LIBS system to detect and discriminate a set of aerosols were assessed with satisfaction. Very rich atomic spectral information is contained in only one spectrum. Through statistical multivariate methods such as Principal Component Analysis, a distinction between the natural and surrounding environmental background and the "contamination" would be possible.