This study examines Arsenic, mercury and selenium levels in human hair, nail and blood samples collected from Wassa West District, a mining impacted site in contrast with Akatsi and its environs, a non-mining impacted site using INAA facility at Ghana Research Reactor-1 (GHARR-1), Kwabenya, Accra. Other elements determined alongside the elements of interest were Na, K, Ca, Al, Mg, Mn, V, Cl, I, Br, Au, La, Cu, Zn, Sr, Ni, and Ag. An alternative method was developed for the Preconcentration Neutron Activation Analysis using dithizone/CHCl3 mixture as the chelating agent for very low levels of mercury and arsenic in human blood. Factors that affect dithizone complexation such as pH, and concentration were investigated. Selenium levels in all the matrices were determined by Hydride Generation Atomic Absorption Spectrophotometric (HGAAS) technique. Speciation of Se(IV) and Se(VI) was carried out on selected blood samples using HNO3/H2O2 as digestion reagent. The precision of the analytical methods used were evaluated by Schewart control chart for internal quality assessment purposes.