Abstract: The bioaccessibility of metal(loid)s in ambient particulate matter (PM) has been recently used to represent the risk of inhalation exposure. Nevertheless, different methodological factors affect the bioaccessibility values; among these, the type and composition of surrogate biological fluids and the liquid to solid ratio have been revealed to be the most important. To better understand how these methodological aspects affect the bioaccessibility, a reference material corresponding to urban dust (SRM1648a) was contacted with synthetic biological fluids commonly used in the literature representing surrogate fluids that may interact with fine (Gamble's solutions, artificial lysosomal fluid (ALF)) and coarse particles (gastric fluid), for liquid to solid (L/S) ratios ranging from 500 to 20,000. Visual MINTEQ 3.1. was used to enhance the discussion on how the solubility of metals in the leaching solution depends on the composition of the simulated fluids and the speciation of metals. The results obtained indicate that a small change in the composition of Gamble's solution (the presence of glycine) may increase significantly the bioaccessibility at a L/S ratio of 5,000. The highest bioaccessibility of most of the studied metal(loid)s at a L/S ratio of 5,000 was found for ALF fluid. The study of the effect of the L/S ratio showed that metal(loid)s bioaccessibility in Gamble's fluid increased logarithmically with increasing L/S ratio, while it remained practically constant in ALF and gastric fluid. This different behavior is explained assuming that the leaching of metal(loid)s in Gamble's solution is solubility-controlled, while in ALF and gastric fluid is availability-controlled.

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