Mobilization and speciation of arsenic from hydrothermally altered rock containing calcite and pyrite under anoxic conditions

The effects of water residence time and anoxic conditions on the mobilization and speciation of As in a calcite- and pyrite-bearing altered rock excavated during a road-tunnel project has been evaluated using batch and column laboratory experiments. Higher infiltration rates (i.e., shorter water residence times) enhanced the leaching of As due to the higher pH values of the effluents and more rapid transport of dissolved As through the columns. The concentration of As in the effluent also increased under anoxic conditions regardless of the water residence time. This enhanced leaching of As under anoxic conditions could be attributed to a significant pH increase and decreased Fe oxyhydroxide/oxide precipitation compared to similar experiments done under ambient conditions. Processes that controlled the evolution of pH and the temporal release mechanisms of As under anoxic conditions were identical to those previously observed under ambient conditions: the dissolution of soluble phases, pyrite oxidation, co-precipitation and/or adsorption/desorption reactions. Speciation of As in the column experiments could partly be attributed to the pH-dependent adsorption of As species onto Fe oxyhydroxide/oxide precipitates. Moreover, apparent equilibrium of the total As and As[III] concentrations was delayed under anoxic conditions in both batch and column experiments.

► As leaching is dependent on the water residence time under anoxic conditions. ► Higher pH and reduced Fe-oxyhydroxide/oxide precipitation enhanced As leaching. ► As[V] predominates close to apparent equilibrium even under anoxic conditions. ► Speciation of As is partly attributed to pH dependent adsorption. ► Anoxic As release mechanisms include dissolution, oxidation and adsorption.