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Studies regarding the role of geochemical processes in urban environmental matrices (UEM) and their influence on respiratory bioaccessibility in humans are scarce in humid tropical regions, especially in Brazil. Contaminated UEM are potentially hazardous to humans if particles <10 μm in diameter are inhaled and reach the tracheobronchial region. In this study, we evaluated samples collected in Brazilian UEMs with a large environmental liability left by former mining industries and in a city with strong industrial expansion. UEM samples were classified into soil, sediment and mine tailings according to the characteristics of the collection sites. The respiratory bioaccessibility of potentially harmful elements (PHE) was evaluated using artificial lysosomal fluid (ALF, pH 4.5), and the BCR-sequential extraction was performed to evaluate how the respiratory bioaccessibility of the PHE was related to the solid phase partitioning. The bioaccessible fraction (BAF) ranged from 54 to 98% for Cd; 21-89% for Cu; 46-140% for Pb, 35-88% for Mn and; 41-84% for Zn. The average BAF of the elements decreased in the following order: Soil: Cd > Pb > Mn > Zn > Cu; Tailing: Pb > Cd > Zn > Mn > Cu; and Sediments: Pb > Mn > Cd > Zn > Cu. BCR-fractions were useful to predict the PHE bioaccessibility (R 2  = 0.79-0.98), thus suggesting that particle geochemistry and mineralogy can influence PHE behaviour in the pulmonary fluid. Therefore, this approach provides a combination of quantitative and qualitative data, which allows us to carry out a more realistic assessment of the current situation of the potentially contaminated site and possible alternatives for decision making by the stakeholders., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The Caco-2 cell line is derived from a human colon adenocarcinoma and is generally used in toxicity assays. The ingestion of soil or dust is a significant route of human exposure to potential harmful elements (PHE), and assays of bioaccessibility or bioavailability can be used to measure the potential hazard posed by exposure to toxic substances. The in vitro digestion (UBM method) and Caco-2 cell model were used to investigate the bioaccessibility and absorption by intestinal cells of the PHE in four matrices (two urban soils and two soils with lead (Pb)-mining tailings) along with the guidance material for bioaccessibility measurements, BGS 102. The gastrointestinal (GI) compartment was simulated, and the resulting material added to Caco-2 cells. In the GI, the average bioaccessibility was 24% for cadmium (Cd), 17% for copper (Cu), 0.2% for Pb, 44% for manganese (Mn) and 6% for zinc (Zn). The poor reproducibility was attributed to the pH (6.3) and the highly complex GI fluid that formed PHE precipitates and complexes. In 2 h, Caco-2 cells absorbed 0.2 ng mg -1 of cellular protein for Cd, 13.4 ng mg -1 for Cu, 5 ng mg -1 for Mn and 31.7 µg mg -1 for Zn. Lead absorption was lower than the limit of quantification (< 2 µg L -1 ). Cd was presented in the cell monolayer and could interfere in the intracellular accumulation of Cu, Mn and Zn. The use of in vitro assays allowed for an estimation of the absorption of Cd, Cu, Mn and Zn from environmental matrices to be made, and except for Mn, it had a positive correlation with bioaccessible concentration, suggesting a common association of these elements in the cellular environment.