Relationship of arsenic speciation and bioavailability in mine wastes for human health risk assessment

Abstract

X-ray absorption near-edge spectroscopy (XANES) was used for arsenic speciation in mine processing and waste samples from two mines in northern Australia. XANES fitting of model compound spectra to samples was used, in combination with in vitro bioaccessibility data for the pure compounds, to predict bioaccessibility of each mine waste sample (Pearson’s correlation R² = 0.756, n = 51). The XANES fitting data for a smaller set of the samples (n = 12) were compared with in vivo bioavailability and in vitro bioaccessibility data. The bioavailability of arsenic (As) in the mine wastes, which is dependent, at least in part, on its oxidation state, was found to be <14 % (0.9–13.5 %) for arsenite (AsIII) and <17 % (3.5–16.4) for arsenate (Asν). Arsenic bioaccessibility in the mine wastes ranged from 8–36 % in the stomach to 1–16 % in the intestinal phase, indicating that a small portion of the total As concentration in the mine waste was available for absorption. A significant correlation showed that bioaccessibility can be used as a predictor of bioavailability. The XANES results support that bioavailability and bioaccessibility results were very similar and show a strong association with the presence of ferric arsenate and As sulfides. It can be concluded that, when soil intake is adjusted for bioaccessibility, the potential health risk estimate to local residents exposed to the mine waste was significantly lower than that estimated based on a 100 % bioavailability often employed for the risk assessment.