ABSTRACT
The oxidative dissolution of sulfide minerals, naturally present in the subsurface, is one of the major pathways of arsenic mobilization. This study investigates the release and fate of arsenic from arsenopyrite and löllingite oxidation under dynamic redox conditions. We performed multidimensional flow-through experiments focusing on the impact of chemical heterogeneity on arsenic mobilization and reactive transport. In the experimental setups the As-bearing sulfide minerals were embedded, with different concentrations and spatial distributions, into a sandy matrix under anoxic conditions. Oxic water flushed in the flow-through setups triggered the oxidative dissolution of the reactive minerals, the release of arsenic, as well as changes in pore water chemistry, surface-solution interactions and mineral precipitation. We developed a reactive transport model to quantitatively interpret the experimental results. The simulation outcomes showed that 40% of the arsenic released was reincorporated into a freshly precipitated iron-arsenate phase that created a coating on the mineral surface limiting the dissolution reactions. The faster dissolution rate of löllingite compared to arsenopyrite was responsible for sustaining the continuous release of As-contaminated plumes. The model also allowed shedding light on the spatial distribution, on the temporal dynamics, and on the interactions between arsenic sources (As-bearing minerals) and sinks (freshly formed secondary phases) in flow-through systems.
ABSTRACT
Low-permeability aquitards can significantly affect the transport, distribution, and persistence of contaminant plumes in subsurface systems. Although such low-permeability materials are often charged, the key role of charge-induced electrostatic processes during contaminant transport has not been extensively studied. This work presents a detailed investigation exploring the coupled effects of heterogeneous distribution of physical, chemical and electrostatic properties on reactive contaminant transport in field-scale groundwater systems including spatially distributed clay zones. We performed an extensive series of numerical experiments in three distinct heterogeneous sandy-clayey domains with different levels of complexity. The flow and reactive transport simulations were performed by explicitly resolving the complex velocity fields, the small-scale electrostatic processes, the compound-specific diffusive/dispersive fluxes and the chemical processes utilizing a multi-continua based reactive transport code (MMIT-Clay). In each particular domain, numerical experiments were performed focusing on both the forward and back diffusion through the sandy-clayey interfaces. The results illuminate the control of microscopic electrostatic mechanisms on macroscopic mass transfer. Coulombic interactions in the clay's diffuse layer can significantly accelerate or retard a particular species depending on its charge. Furthermore, the chemical heterogeneity plays a major role in mass storage and release during reactive transport. Neglecting such processes can lead to substantial over- or underestimation of the overall transport behavior, which underlines the need for integrated physical, chemical and electrostatic approaches to accurately describe mass transfer processes in systems including low-permeability inclusions.
