Abstract

In this study, the critical coagulation concentration (CCC) for FEBEX bentonite colloids is determined by colloid coagulation studies under variation of pH, electrolyte concentration, and fulvic acid (GoHy-573FA) content. For CaCl2 electrolyte solution, a pH-independent Ca-CCC of 1 mmol L−1 is found. In the case of NaCl background electrolyte, a pH-dependent Na-CCC can be determined with 15 ± 5 mmol L−1 at pH 6, 20 ± 5 mmol L−1 at pH 7, 200 ± 50 mmol L−1 at pH 8, 250 ± 50 mmol L−1 at pH 9, and 350 ± 100 mmol L−1 at pH 10, respectively. The addition of 1 mg L−1 dissolved organic carbon in the form of fulvic acid (FA) increases the Ca-CCC to 2 mmol L−1. An association of FA with FEBEX bentonite colloids as surface coating can clearly be identified by scanning transmission X-ray microscopy (STXM). The experimental bentonite stability results are described by means of an extended DLVO (Derjaguin–Landau–Verwey–Overbeek) approach summing up hydration forces, short-range Born repulsion, van der Waals attraction, and electrical double layer repulsion. The measured zeta (ζ)-potential of the bentonite colloids is applied as platelet face electrokinetic potential and the edge electrokinetic potential is estimated by the combination of silica and alumina ζ-potential data in the ratio given by the FEBEX bentonite structural formula. Adjusting the montmorillonite face electrokinetic potential by a maximum of ±15.9 mV is sufficient to successfully reproduce the measured stability ratios. Due to the uncertainty in the ζ-potential measurement, only semiquantitative calculations of the stability ratio can be given.

Highlights

  • In many concepts for deep geological disposal of high-level nuclear waste in crystalline host rocks, the waste is emplaced inside a metal canister surrounded by a bentonite buffer [1,2]

  • Using CaCl2 as the background electrolyte solution at pH 8, the fastest observed coagulation was at a concentration of ≥33 mmol L−1

  • The results show that the general trend of stability ratio variations is qualitatively predicted, but the calculated stability ratios WDLVO under or overpredict the measured colloid stability Wmeasured, sometimes by orders of magnitude

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Summary

Introduction

In many concepts for deep geological disposal of high-level nuclear waste in crystalline host rocks, the waste is emplaced inside a metal canister surrounded by a bentonite buffer [1,2]. The bentonite acts, inter alia, as a hydrogeological barrier delaying the contact of the canister with formation water and retarding the radionuclide release to the geosphere by means of its high sorption capacity and a diffusion-controlled transport. In the colloid and radionuclide retardation (CRR) experiment performed at the Grimsel Test Site (GTS, Switzerland; Phase V), colloid-mediated transport of trivalent and tetravalent radionuclides (Am(III), Pu(IV), Th(IV)) was found to be occurring in the migration (MI) shear zone under the given hydraulic conditions [12,13]. In the successive colloid formation and migration experiment (CFM), huge geotechnical effort was undertaken to hydraulically isolate the MI shear zone from the artificial hydraulic gradient due to the GTS tunnel construction. After several conservative and “homologue” tracer tests, radioactive tracer tests were performed [14,15,16]

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