We set up a microanalytical procedure for non-volatile ions by ion chromatography (IC) and for elements by energy-dispersive X-ray fluorescence (ED-XRF) and inductively coupled plasma optical emission spectroscopy (ICP-OES). We analysed NO3, SO4, NH4, Na, Mg, Ca, Fe, S, Zn, As, Cd, Cu, Mn, Ni, Pb, Sb, Se, Ti, and V. The use of complementary techniques yields reliable data for both trace and crustal elements, overcoming the analytical restrictions characteristic of the individual techniques. Some elements determined by two or by all three techniques can be used as data quality markers. The application of the procedure to a short PM2.5 monitoring campaign is also described, aimed to the identification of fireworks tracers.