The determination of toxic metals in the biological samples of human beings is an important clinical screening procedure. This study aimed to assess the possible influence of environmental exposure on production workers (PW) and quality control workers (QCW) of a steel mill, all male subjects aged 25-55 years. In this investigation, the concentrations of Pb, Cd, Ni and Cr were determined in biological samples (blood, urine and scalp hair samples) from these steel mill workers in relation to controlled unexposed healthy subjects of the same age group. After pre-treatment with nitric acid-hydrogen peroxide, the samples were digested via a microwave oven, and for comparison purposes, the same samples were digested by the conventional wet acid digestion method. The samples digested were subjected to graphite furnace atomic absorption spectrometry (GFAAS). To assess the reliability of these methods, critical factors, such as detection limit(s), calibration range(s), accuracy and precision, were studied. Quality control for these procedures was established with certified sample of human hair, urine and whole blood. The results indicate that the level of lead, cadmium and nickel in scalp hair, blood and urine samples were significantly higher in both groups of exposed workers (QW and PW) than those of the controls. The possible connection of these elements with the etiology of disease is discussed. The results also show the need for immediate improvements in workplace ventilation and industrial hygiene practices.