Chemical resilience of clay rich barrier materials to redox-oscillating conditions and implications for contaminant mobility

Document available in extended abstract form only. The mineralogical composition of argillaceous barrier materials is often considered to be static, and therefore, that interactions with contaminants and nutrients may be well constrained. Typically, solid/aqueous partition coefficients (Kd values) are obtained empirically to determine the proportion of contaminant immobilised by the solid phase for individual barrier material/contaminant combinations at defined contaminant loadings and pH. These values may then be used as indicators of potential contaminant mobility around waste storage facilities following the eventual failure of engineered barriers (1). While Kd values are a useful tool to modellers estimating contaminant mobility through porous media at thermodynamic equilibrium, over time and under dynamic biogeochemical conditions, matrix mineralogy, and therefore Kd values, are liable to change (2). Near surface environments implicated in back-filled or excavated storage solutions, currently proposed for low-level long-lived waste (LL-LLW), will result in more dynamic redox conditions than those predicted in deep, anoxic geological storage conditions (2). Such dynamic conditions are similar to those experienced in pluvial, fluvial or phreatic influenced soils and are likely to be far from thermodynamic equilibrium (3). Cyclic redox conditions of varying periodicity are likely to occur around near surface repositories due to a combination of microbial activity and variations in substrate saturation caused by changes to groundwater level and rates of pluvial infiltration. Upon saturation of near surface substrates reducing conditions occur rapidly due to slow inward diffusion of oxygen from the surface and rapid oxygen consumption by aerobic heterotrophic bacteria gaining energy from the mineralisation of organic matter (4, 5). Subsequent to the exhaustion of residual oxygen, anaerobic metabolism dominates in such environments resulting in the depletion of nitrate and sulphate in addition to the reductive dissolution of manganese and iron oxide minerals and an increase in CO2 partial pressure. Whilst some authors demonstrate that such cyclic redox conditions may alter the properties of clay barrier materials due to illitisation of smectite clays (6, 7), the dynamic chemical conditions occurring during redox cycling may also result in the dissolution and re-precipitation of metal oxides, sulphides and carbonates. The balance of these minerals, even if present at sub-per cent levels as impurities has the potential to dramatically alter contaminant mobility. Many inorganic contaminants often associated with LL-LLW including Sb, Cr, As, Hg and U are also highly sensitive to changes in redox conditions which may result in changes to their speciation, toxicity and mobility (8, 9). We demonstrate through the combination of redox-stat batch-reactor experiments and thermodynamic modelling that periodic and cumulative changes to matrix mineralogy, contaminant speciation and mineral surface properties occur following periodic cycles of reduction and oxidation. These changes result in both short term (intra-cycle) and long-term (inter-cycle) changes to Kd values for a range of redox sensitive contaminants associated with LL-LLW including arsenic, chromium, selenium, mercury and uranium (Table 1 and Figures 1 and 2). During a series of laboratory experiments argillaceous substrates were subjected to successive cycles of oxidising and reducing conditions with Eh oscillating between -215 and +340 mV induced via both abiotic and microbial methods. Chemically induced cycles of oxidation and reduction were achieved via a combination of gas sparging (nitrogen vs compressed air) and the addition of a synthetic reduced humic substance analogue (AH2DS2-). Microbially induced cycles of oxidation and reduction were achieved using gas sparging (nitrogen vs compressed air) to stimulate different metabolic pathways of a natively present microbial community. We demonstrate that naturally occurring redox oscillations may result in l ong term immobilisation of contaminants in the solid phase in addition to short term variations in mobility. (authors)