Mechanisms and health implications of toxicity increment from arsenate-containing iron minerals through in vitro gastrointestinal digestion.

Inadvertent oral ingestion is an important exposure pathway of arsenic (As) containing soil and dust. Previous researches evidenced health risk of bioaccessible As from soil and dust, but it is unclear about As mobilization mechanisms in health implications from As exposure. In this study, we investigated As release behaviors and the solid-liquid interface reactions toward As(V)-containing iron minerals in simulated gastrointestinal bio-fluids. The maximum As release amount was 0.57 mg/L from As-containing goethite and 0.82 mg/L from As-containing hematite at 9 h, and the As bioaccessibility was 10.8% and 21.6%, respectively. The higher exposure risk from hematite-sorbed As in gastrointestinal fluid was found even though goethite initially contained more arsenate than hematite. Mechanism analysis revealed that As release was mainly coupled with acid dissolution and reductive dissolution of iron minerals. Proteases enhanced As mobilization and thus increased As bioaccessibility. The As(V) released and simultaneously transformed to high toxic As(III) by gastric pepsin, while As(V) reduction in intestine was triggered by pancreatin and freshly formed Fe(II) in gastric digests. CaCl2 reduced As bioaccessibility, indicating that calcium-rich food or drugs may be effective dietary strategies to reduce As toxicity. The results deepened our understanding of the As release mechanisms associated with iron minerals in the simulated gastrointestinal tract and supplied a dietary strategy to alleviate the health risk of incidental As intake.

Release mechanism and interactions of cadmium and arsenic co-contaminated ferrihydrite by simulated in-vitro digestion assays.

Cadmium (Cd) and arsenic (As) co-contamination is widespread and threatens human health, therefore it is important to investigate the bioavailability of Cd and As co-exposure. Currently, the interactions of Cd and As by in vitro assays are unknown. In this work, we studied the concurrent Cd-As release behaviors and interactions with in vitro simulated gastric bio-fluid assays. The studies demonstrated that As bioaccessibility (2.04 to 0.18 ± 0.03%) decreased with Cd addition compared to the As(V) single system, while Cd bioaccessibility (11.02 to 39.08 ± 1.91%) increased with As addition compared to the Cd single system. Release of Cd and As is coupled to proton-promoted and reductive dissolution of ferrihydrite. The As(V) is released and reduced to As(Ⅲ) by pepsin. Pepsin formed soluble complexes with Cd and As. X-ray photoelectron spectroscopy showed that Cd and As formed Fe-As-Cd ternary complexes on ferrihydrite surfaces. The coordination intensity of As-O-Cd is lower than that of As-O-Fe, resulting in more Cd release from Fe-As-Cd ternary complexes. Our study deepens the understanding of health risks from Cd and As interactions during environmental co-exposure of multiple metal(loid)s.

Mobilization of arsenic from As-containing iron minerals under irrigation: Effects of exogenous substances, redox condition, and intermittent flow.

Irrigation activities can cause strong geochemical and hydrological fluctuations in the unsaturated zone, and affect arsenic (As) migration and transformation. The As geochemical cycle in the unsaturated zone is coupled with that of iron minerals through sorption-desorption, coprecipitation and redox processes. Dynamic batch experiments and wetting-drying cycling column experiments were conducted to evaluate As mobilization behaviors under the effects of exogenous substances, redox condition and intermittent flow. Our results show that As release under exogenous substances carried by irrigation (e.g., phosphate, carbonate, fulvic acid, humic acid, etc.) followed three trends with the types of exogenous inputs. Inorganic anions and organic matter resulted in opposite trends of arsenate release in different redox conditions. In anoxic environments, As(V) release was favored by the addition of phosphate and carbonate, while in oxic environments, the mobilization of As(V) was promoted by the addition of fulvic acid (FA). Further, intermittent irrigation promoted the reductive dissolution of Fe oxides and the mobilization of As. The addition of humic acid (HA) resulted in the mobilization of arsenate as As-Fe-HA ternary complexes. The mechanism of arsenic mobilization under irrigation has importance for prevention of arsenic exposure through soil to food chain transfer in typical high arsenic farmland.