Lead (Pb) bioaccessibility was assessed using 2 in vitro methods in 12 Pb-contaminated soils and compared to relative Pb bioavailability using an in vivo mouse model. In vitro Pb bioaccessibility, determined using the intestinal phase of the Solubility Bioaccessibility Research Consortium (SBRC) assay, strongly correlated with in vivo relative Pb bioavailability (R(2) = 0.88) following adjustment of Pb dissolution in the intestinal phase with the solubility of Pb acetate at pH 6.5 (i.e., relative Pb bioaccessibility). A strong correlation (R(2) = 0.78) was also observed for the relative bioaccessibility leaching procedure (RBALP), although the method overpredicted in vivo relative Pb bioavailability for soils where values were <40%. Statistical analysis of fit results from X-ray absorption near-edge structure (XANES) data for selected soils (n = 3) showed that Pb was strongly associated with Fe oxyhydroxide minerals or the soil organic fraction prior to in vitro analysis. XANES analysis of Pb speciation during the in vitro procedure demonstrated that Pb associated with Fe minerals and the organic fraction was predominantly solubilized in the gastric phase. However, during the intestinal phase of the in vitro procedure, Pb was strongly associated with formation of ferrihydrite which precipitated due to the pH (6.5) of the SBRC intestinal phase. Soils where Fe dissolution was limited had markedly higher concentrations of Pb in solution and hence exhibited greater relative bioavailability in the mouse model. This data suggests that coexistence of Fe in the intestinal phase plays an important role in reducing Pb bioaccessibility and relative bioavailability.
In this study, cadmium (Cd) relative bioavailability in contaminated (n = 5) and spiked (n = 2) soils was assessed using an in vivo mouse model following administration of feed containing soil or Cd acetate (reference material) over a 15 day exposure period. Cadmium relative bioavailability varied depending on whether the accumulation of Cd in the kidneys, liver, or kidney plus liver was used for relative bioavailability calculations. When kidney plus liver Cd concentrations were used, Cd relative bioavailability ranged from 10.1 to 92.1%. Cadmium relative bioavailability was higher (14.4-115.2%) when kidney Cd concentrations were used, whereas lower values (7.2-76.5%) were derived when liver Cd concentrations were employed in calculations. Following in vivo studies, four in vitro methodologies (SBRC, IVG, PBET, and DIN), encompassing both gastric and intestinal phases, were assessed for their ability to predict Cd relative bioavailability. Pearson correlations demonstrated a strong linear relationship between Cd relative bioavailability and Cd bioaccessibility (0.62-0.91), however, stronger in vivo-in vitro relationships were observed when Cd relative bioavailability was calculated using kidney plus liver Cd concentrations. Whereas all in vitro assays could predict Cd relative bioavailability with varying degrees of confidence (r(2) = 0.348-0.835), large y intercepts were calculated for a number of in vitro assays which is undesirable for in vivo-in vitro predictive models. However, determination of Cd bioaccessibility using the intestinal phase of the PBET assay resulted in a small y intercept (5.14; slope =1.091) and the best estimate of in vivo Cd relative bioavailability (r(2) = 0.835).
The effect of phosphate treatment on lead relative bioavailability (Pb RBA) was assessed in three distinct Pb-contaminated soils. Phosphoric acid (PA) or rock phosphate were added to smelter (PP2), nonferrous slag (SH15), and shooting range (SR01) impacted soils at a P:Pb molar ratio of 5:1. In all of the phosphate amended soils, Pb RBA decreased compared to that in untreated soils when assessed using an in vivo mouse model. Treatment effect ratios (i.e., the ratio of Pb RBA in treated soil divided by Pb RBA in untreated soil) ranged from 0.39 to 0.67, 0.48 to 0.90, and 0.03 to 0.19 for PP2, SH15, and SR01, respectively. The decrease in Pb RBA following phosphate amendment was attributed to the formation of poorly soluble Pb phosphates (i.e., chloropyromorphite, hydroxypyromorphite, and Pb phosphate) that were identified by X-ray absorption spectroscopy (XAS). However, a similar decrease in Pb RBA was also observed in untreated soils following the sequential gavage of phosphate amendments. This suggests that in vivo processes may also facilitate the formation of poorly soluble Pb phosphates, which decreases Pb absorption. Furthermore, XAS analysis of PA-treated PP2 indicated further in vivo changes in Pb speciation as it moved through the gastrointestinal tract, which resulted in the transformation of hydroxypyromorphite to chloropyromorphite.
In this study, PAH bioavailability was assessed in creosote-contaminated soil following bioremediation in order to determine potential human health exposure to residual PAHs from incidental soil ingestion. Following 1,000 days of enhanced natural attenuation (ENA), a residual PAH concentration of 871 ± 8 mg kg(-1) (∑16 USEPA priority PAHs in the <250 μm soil particle size fraction) was present in the soil. However, when bioavailability was assessed to elucidate potential human exposure using an in vivo mouse model, the upper-bound estimates of PAH absolute bioavailability were in excess of 65% irrespective of the molecular weight of the PAH. These results indicate that a significant proportion of the residual PAH fraction following ENA may be available for absorption following soil ingestion. In contrast, when PAH bioavailability was estimated/predicted using an in vitro surrogate assay (FOREhST assay) and fugacity modelling, PAH bioavailability was up to 2000 times lower compared to measured in vivo values depending on the methodology used.
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