We report on instrumentation-related challenges of applying graphite furnace atomic absorption spectroscopy (GF-AAS) and inductively coupled plasma mass spectrometry (ICP-MS). We show that a significant amount of polyatomic species derived from silicon sample solution in the plasma, such as SiO, SiOH, SiOH 2·SiOH 3, SiO 2, SiO 2H, SiO 2H 2 and SiO 2H 3, can hamper the detection limits of many elements of interest. This paper describes a method for eliminating these polyatomic ions. We discuss the advantages and disadvantages of vapor phase decomposition method (VPD), drop etching method (DE) and drop sandwich-etching method (DSE) for the recovery of metal impurities from a silicon wafer surface. We report the application of the DSE method for the evaluation of near-surface metal impurities, used for gettering studies. We describe the direct acid bulk decomposition (DABD) and the room temperature acid vapor phase decomposition method (RT-AVPD) for the determination of metal impurities in bulk silicon. Finally, we report concentration of trace metal contamination in several chemical reagent solutions.