Mobilization and speciation of arsenic from hydrothermally altered rock in laboratory column experiments under ambient conditions

This paper describes the mobilization and speciation of As found in hydrothermally altered rock under oxic column conditions. The altered rock sample was obtained from a tunnel project located in the Nakakoshi area of Hokkaido, Japan, whose geology is represented by slate, shale and sandstone. This area has undergone silicification, pyritization and argillic alteration resulting in As-enrichment of the rock. Results of the column experiments show that the infiltration rate, bulk density and rock bed thickness affected the duration of water residence, which in turn influenced the pH of the rock–water system. Coexisting ions most notably Ca²⁺ at amounts greater than ca. 50 mg/L retarded the mobilization of As. Mobilization of As from the rock with time occurred in two stages: stage 1 (weeks 1–20) with higher As leaching and stage 2 (weeks 20–76) characterized by nearly constant As release. In addition, pore water As concentrations revealed that the columns developed into two regions: the top half where most of the leaching occurred and the bottom part dominated by adsorption. Thus, the mechanism controlling the mobilization of As from the rock is a combination of one or more of the following processes: dissolution of soluble As-bearing fractions, pyrite oxidation and adsorption reactions. Arsenite (As[III]) was the dominant species in the effluent at the start of the experiment in columns with shorter water residence time and lower pH conditions (<8). On the other hand, arsenate (As[V]) was the major inorganic species released from the rock at higher pH (8–9.5) and when the system was close to equilibrium. Speciation of As with depth also indicated that As[III] disappeared around the bottom half of the columns, probably as a result of adsorption and/or oxidation. Arsenic speciation is partially controlled by the pH dependent adsorption of As species. The important adsorbent phases in the rock included Fe–Al oxides/oxyhydroxides, clay minerals and organic matter, which permitted the columns to attenuate additional As loadings including As[III]. Implications of these results on the design of a novel disposal method for these altered rocks include the enhancement of As adsorption through the addition of natural or artificial adsorbents and the utilization of a covering soil with low permeability to minimize rainwater infiltration into the rock.