Legacy of anthropogenic lead in urban soils: Co-occurrence with metal(loids) and fallout radionuclides, isotopic fingerprinting, and in vitro bioaccessibility.

Anthropogenic lead (Pb) in soils poses risks to human health, particularly to the neuropsychological development of exposed children. Delineating the sources and potential bioavailability of soil Pb, as well as its relationship with other contaminants is critical in mitigating potential human exposure. Here, we present an integrative geochemical analysis of total elemental concentrations, radionuclides of Cs and Pb, Pb isotopic compositions, and in vitro bioaccessibility of Pb in surface soils sampled from different locations near Durham, North Carolina. Elevated Pb (>400 mg/kg) was commonly observed in soils from urban areas (i.e., near residential house foundation and along urban streets), which co-occurred with other potentially toxic metal(loids) such as Zn, Cd, and Sb. In contrast, soils from city parks and suburban areas had systematically lower concentrations of metal(loids) that were comparable to geological background. The activities of Cs and excess Pb, coupled with their correlations with Pb and co-occurring metal(loids) were used to indicate the persistence and remobilization of historical atmospherically deposited contaminants. Coupled with total Pb concentrations, the soil Pb isotopic compositions further indicated that house foundation soils had significant input of legacy lead-based paint (mean = 1.1895 and 2.0618 for Pb/Pb and Pb/Pb, respectively), whereas urban streetside soils exhibited a clear mixed origin, dominantly of legacy leaded gasoline (1.2034 and 2.0416) and atmospheric deposition (1.2004-1.2055 and 2.0484-2.0525). The in vitro bioaccessibility of Pb in contaminated urban soils furthermore revealed that more than half of Pb in the contaminated soils was potentially bioavailable, whose Pb isotope ratios were identical to that of bulk soils, demonstrating the utility of using Pb isotopes for tracking human exposure to anthropogenic Pb in soils and house dust. Overall, this study demonstrated a holistic assessment for comprehensively understanding anthropogenic Pb in urban soils, including its co-occurrence with other toxic contaminants, dominant sources, and potential bioavailability upon human exposure.