The bioaccessibilities of the platinum group elements (PGE): Rh, Pd, and Pt; and the catalyzator poison, Pb, have been determined in particles derived from milled automotive catalytic converters using a physiologically based extraction test (PBET) that simulates, sequentially, the chemical conditions encountered in the human stomach and intestine. PGE accessibility, relative to total metal concentration, was generally less than a few percent, but increased in the stomach with decreasing pH (from 4 to 1) and/or increasing chloride concentration, and with decreasing particle concentration. In most cases, bioaccessibility increased from the acidic stomach to the neutral, carbonate-rich intestine. Bioaccessibility of Pb displayed similar pH and particle concentration dependencies to PGE in the stomach, but this metal exhibited significantly greater mobilization (up to 80%) overall and a reduction in accessibility from the stomach to intestine. Reaction kinetics of PGE dissolution in the stomach at pH 2.5 were modeled using a combined surface reaction-diffusion controlled mechanism with rate constants of 0.068, 0.031, and 0.015 (microg L(-1))(-1) h(-1) for Rh, Pd, and Pt, respectively. For Pb, however, mobilization proceeded via a different mechanism whose time-dependence was fitted with an empirical, logarithmic equation. Overall, PGE bioaccessibility appeared to be controlled by dissolution rates of metallic nanoparticles in the stomach, and solubility and kinetic constraints on inorganic species (chlorides, hydroxychlorides, and carbanatochlorides) and undefined organic complexes formed in the simulated gastrointestinal tract. Further studies are required to elucidate any effects engendered by the long-term oral exposure of small quantities of these species.