Impact of Zinc(II) Chloride Contamination on Bentonites: Formation of Simonkolleite and Effects on Porosity and Chemical Composition

This study examines the formation of the clay mineral simonkolleite (Skl) in bentonites contaminated with zinc(II) chloride (ZnCl₂), a process that has been little documented in heterogeneous systems such as contaminated bentonites. We explain the contamination mechanisms and provide new insights into the mineralogical, structural, and physicochemical transformations occurring within these materials. The objective, explored for the first time, was to assess how the ZnCl₂-induced mineral phase formation influences the properties of bentonites used as sealing materials, particularly regarding changes in specific surface area and porosity. Three bentonites were analyzed: Ca-bentonite from Texas (STx-1b), Na-bentonite from Wyoming (SWy-3), and Ca-bentonite from Jelsovy Potok, Slovakia (BSvk). Treatment with ZnCl₂ solution led to ion exchange and the formation of up to ~30% simonkolleite, accompanied by a concurrent decrease in montmorillonite content by 9-30%. A suite of analytical techniques, including X-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), X-ray fluorescence (XRF), and energy-dispersive X-ray spectroscopy (EDS), was employed to characterize these transformations. The contamination mechanism of ZnCl₂ involves an ion exchange of Zn²⁺ within the montmorillonite structure, the partial degradation of specific montmorillonite phases, and the formation of a secondary phase, simonkolleite. These transformations caused a ~50% decrease in specific surface area and porosity as measured by the Brunauer-Emmett-Teller (BET) nitrogen adsorption and Barrett-Joyner-Halenda (BJH) methods. The findings raise concerns regarding the long-term performance of bentonite-based barriers. Further research should evaluate hydraulic conductivity, mechanical strength, and the design of modified bentonite materials with improved resistance to Zn-induced alterations.