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In present study, an in-vitro physiologically based extraction test has been applied for extraction of bio-accessible trace metal fractions in airborne particulate matter (APM) samples collected from different urban sites in Austria and Pakistan using the leaching agents H2O, sodium chloride, ammonium acetate, ammonium citrate, synthetic gastric juice and artificial lung fluids. Obtained extracts were then measured using an ETV-ICP-OES procedure which allowed highly sensitive measurement of dissolved analytes even in the presence of leaching agents. Derived results indicated that the investigated leaching agents extract different amounts of trace metals. In general, leaching agents with organic nature yielded comparatively greater extractable and thus bio-accessible trace metal fractions to that of simple solvents like H2O or aqueous NaCl solution. With water, only 26.3±4.0% of Cd was found to be bio-accessible whereas 88.4±24.8 of Cd was obtained as bio-accessible fraction with the use of synthetic gastric juice. The concentrations of bio-accessible metal fractions varied from 0.4 ng m−3 (Cd) to 714 ng m−3 (Zn) and 0.3 ng m−3 (Cd) to 190 ng m−3 (Zn) for PM10 samples collected from Karachi (Pakistan) and Graz (Austria) respectively.