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.
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