In vitro and in silico bioaccessibility of urban dusts contaminated by multiple legacy sources of lead (Pb)

Lead contamination from gasoline, paint, pesticides, and smelting have unique chemical structures. Recent investigations into Pb speciation in urban soils and dusts from multiple sources have revealed emerging forms which differ from the initial sources. This results from reactions with soil constituents leading to transformation to new forms for which the bioaccessibilities remain uninvestigated. We investigated the in vitro and in silico bioaccessibility of these emerging forms in three physiologically relevant milieux: artificial lysosomal fluid (ALF), simulated epithelial lung fluid (SELF), and simulated gastric fluid (SGF). Species were validated using extended X-ray absorption fine structure spectroscopy. Results highlight diverse bioaccessibilities which are form and compartmentally-dependent. In ALF the bioaccessibility trend was humate-bound Pb (86%) > hydrocerussite (79%) > Fe oxide-bound Pb (47%) > galena (10%) > pyromorphite (4%) > Mn oxide-bound Pb (2%). Humate-bound Pb, hydrocerussite, Fe and Mn oxide-bound Pb were 100% bioaccessible in SGF while pyromorphite and galena were 26%, and 8%, respectively. Bioaccessibility in SELF was very low (< 1%) and significantly lower than ALF and SGF (p < 0.001). In silico bioaccessibilities modeled using equilibrium solubilities in extraction solutions were in good agreement with empirical measurements. These emerging forms of Pb have a wide range of bioaccessibilities that can influence their toxicity and impact on human health.