The identification of highly toxic metals like Cd, Ni, Pb, Cr, Co or Cu in ambient particulate matter (PM) has garnered a lot of interest recently. Exposure to toxic metals, including carcinogenic ones, at levels above recommended limits, can significantly affect human health. Prolonged exposure to even trace amounts of toxic or essential metals can also have negative health impacts. In order to assess significant risks, it is crucial to govern the concentrations of bioavailable/bio-accessible metals that are available in PM. Estimating the total metal concentrations in PM is only an approximation of metal toxicity. This review provides an overview of various procedures for extracting soluble toxic metals from PM and the importance of chemical fractionation in risk assessment. It is observed that the environmental risk indices such as bioavailability index (BI), contamination factor (CF) and risk assessment code (RAC) are specifically influenced by the concentration of these metals in a particular fraction. Additionally, there is compelling evidence that health risks assessed using total metal concentrations may be overestimated, therefore, the metal toxicity assessment is more accurate and more sensitive to the concentration of the bioavailable/bio-accessible fraction than the total metal concentrations. Hence, chemical fractionation of toxic metals can serve as an effective tool for developing environmental protection laws and improving air quality monitoring programs for public health.
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