Influence of clay minerals on pH and major cation concentrations in acid-leached sands: Column experiments and reactive-transport modeling.

A series of laboratory experiments are conducted to simulate the acidification and subsequent recovery of a sand aquifer exploited by in situ recovery (ISR) mining. A sulfuric acid solution (pH 2) is first injected into a column packed with sand from the Zoovch Ovoo uranium roll front deposit (Mongolia). Solutions representative of local groundwater or enriched in cations (Na+, Mg2+) are then circulated through the column to simulate the inflow of aquifer water. pH and major ion concentrations (Na+, Cl-, SO42-, Ca2+, Mg2+, K+) measured at the column outlet reproduce the overall evolution of porewater chemistry observed in the field. The presence of minor quantities of swelling clay minerals (≈6 wt% smectite) is shown to exert an important influence on the behavior of inorganic cations, particularly H+, via ion-exchange reactions. Numerical models that consider ion-exchange on smectite as the sole solid-solution interaction are able to reproduce variations in pH and cation concentrations in the column experiments. This highlights the importance of clay minerals in controlling H+ mobility and demonstrates that sand from the studied aquifer can be described to a first order as an ion-exchanger. The present study confirms the key role of clay minerals in controlling water chemistry in acidic environments through ion-exchange processes. In a context of managing the long-term environmental footprint of industrial and mining activities (ISR, acid mine drainage…), this work will bring insights for modeling choices and identification of key parameters to help operators to define their production and/or remediation strategies.

Role of zeolite content on the sorption properties of analcime-rich rocks from the Abinky Formation (Niger).

The Abinky formation, composed of analcimolites (i.e., rocks with <70 wt% analcime), underlies Tchirezrine II, which hosts the Imouraren (Niger) uranium deposit. A potential mining project is under consideration to recover U by in situ acid leaching. Analcimolites are uncommon rocks, and assessing their ion-exchange properties is the first step to understand and predict the mobility of aqueous species in these formations. The objective of this study is then to understand the link between the Cation Exchange Capacities (CEC) of analcimolites as a function of their analcime content and associated crystal chemistry. Mineral quantification was performed by Rietveld refinement constrained by local chemical analysis with scanning electron microscopy coupled with Energy Dispersive Spectrometry. CEC were obtained at neutral pH by performing NH4+-for-Na+ exchange (CECNa/NH4), and Na+/H+ ion exchange experiments were performed with 4 analcimolites. Results showed that the analcime crystal chemistry deduced from Rietveld refinement was in good agreement with that obtained from SEM analysis (1.99 < Si/Al < 2.53). The results showed that all samples had a positive correlation between CECNa/NH4 and analcime content until ~30 meq/100 g for a sample containing ~85wt%Riet. of analcime, and that ~6 % of the total amounts of Na+ present in the analcime could be exchanged by NH4+ and H+. Based on Si and Al aqueous measurements, results showed that exchange with Na+ is the main process consuming H+ during Na+/H+ exchange when pH > 3.5. These experimental data were then interpreted by considering a single site equal to the CECNa/NH4 value, specific for each analcimolite, and a selectivity coefficient equal to log KNa/H = 1.3 (Gaines Thomas convention) being equal for all samples investigated. Finally, these data were used to assess the role played by Na+/H+ exchange in the pH evolution of the pore water of an analcime-rich rock subjected to dynamic acidification.

Competitive ion-exchange reactions of Pb(II) (Pb2+/PbCl+) and Ra(II) (Ra2+) on smectites: Experiments, modeling, and implication for 226Ra(II)/210Pb(II) disequilibrium in the environment.

In this study, new experimental data for the adsorption of lead onto a swelling clay mineral with a tetrahedral charge (beidellite) at the ultratrace level (<10-10 M) are presented. The data were interpreted using an ion-exchange multisite model that considers the sorption of major cations (including H+), which always compete with trace elements for sorption onto mineral surfaces in natural environments. The ability of the proposed model to predict experimental Kd values under various conditions of ionic strength (fixed by NaCl solutions) and aqueous cation compositions (including Pb2+ and PbCl+) was tested. The proposed model was applied to experimental data previously published for other types of swelling clay minerals, and the results were compared with the results obtained using previously published models. The preferential adsorption of chloride ion pairs, as well as the effect of the swelling clay crystal chemistry on lead adsorption, were assessed. Finally, the selective adsorption behavior of 226Ra compared to 210Pb was demonstrated, which has implications for the study of many environmental processes using isotope partitioning.