The lung bioaccessibility, i.e., the solubility in alveolar lung fluid of metals in particulate matter, has been recognized as an important parameter for health risk assessment, associated with the inhalation of airborne particles. The purpose of this study is to use an in vitro method to estimate the pulmonary bioaccessibility of toxic metals in different particle sizes, from a multi-influenced industrial emission area. The fine and ultrafine particles collected with cascade impactors in the chimneys and at different distances from a Fe–Mn smelter were extracted with a simulated alveolar fluid (Gamble solution). In addition, a four-step sequential extraction procedure was employed to approach the metal speciation. The bioaccessibility of metals ranged from almost insoluble for Fe (<1 %) to extremely soluble for Rb (>80 %). In terms of particle size, the trace element bioaccessibility is generally higher for the finer size fractions (submicron and ultrafine particles) than for the coarse one (>1 µm). These submicron particles have a very high number concentration and specific surface area, which confer them an important contact surface with the alveolar fluid, i.e., a higher bioaccessibility. Interestingly, the bioaccessibility of most metals clearly increases between the chimney stacks and the close environment of the studied Fe–Mn smelter, over a very short distance (800 m), possibly due to a mix with surrounding steelworks emissions. This increase is not observed over a greater distance from the smelter (2000 m), when industrial particles were mixed with urban aerosols, except for Fe, under more soluble forms in combustion particles.