Oral bioaccessibility and human health risk assessment of trace elements in agricultural soils impacted by acid mine drainage.

Cultivated soils around the historic mine site of Tharsis (Spain) contain elevated concentrations of As (up to 621 mg kg), Cu (752 mg kg) and Pb (2395 mg kg), exceeding the regional background levels and the statutory limits set for agricultural use. A site-specific health risk assessment of occupational and environmental exposures was conducted using an approach based on guidelines from regulatory agencies, refined by combining bioaccessibility and bioavailability data. Oral bioaccessibility, as determined by simulating the human digestion process in vitro (Unified BARGE Method), was largely related to total trace element concentrations in soil. Arsenic seemed to be evenly distributed among the gastric and gastro-intestinal phases (about 31%), whereas the bioaccessible fraction of pH-dependent metal cations, like Pb and Zn, was noticeably higher in the stomach (nearly 50%) than in the gastro-intestinal tract (less than 10%). Bioaccessibility assessed by single extraction with 0.43 M HNO3 was overestimated by a factor of 1.2-1.4 relative to that obtained from the BARGE method. Site-specific relative bioavailability (RBA) values of As (27.7%) and Pb (42.6%), predicted from bioaccessibility measurements through linear regression models, had little effect on the overall risk estimates. For the ingestion pathway, the RBA-adjusted cancer risk values (9.7E-05 to 2.0E-04) exceeded the regulatory threshold in all plots, and the hazard index re-calculated after adjustment of oral dose was also above the allowable limit, with values ranging from 2.5 to 4.8. However, no detrimental health effects are expected to occur through inhalation of soil particles in nearby residents.