The surface charges and the zeta potential of a Na-montmorillonite (Na-mont) and two pillared montmorillonite (MP1 and MP2) samples with different aluminum contents were determined by Potentiometric titrations and electrophoretic measurements. At pH >9 the two pillared montmorillonite samples showed zeta potentials similar to those of Na-mont, but at pH <8, the negative zeta potential shifted to lower negative values as the aluminum content increased. Sample MP1, which had a greater Al content, showed an isoelectric point (IEP) of 5.0–5.5. Titration curves obtained by acid-base Potentiometrie titration for sample MP1 showed a well-defined cross-over point at pH = 5.0, whereas this point was not observed for sample MP2 in the pH range studied. The results indicate, in principle, that both techniques can be used to characterize surface charges in this type of material. An attempt was also made to relate the data obtained from electrophoretic mobility and Potentiometrie titrations.

Mica domains have received less attention in the literature than smectite quasi-crystals. This study was conducted to determine whether mica crystals form domains in suspension, the conditions in which those domains exist, and the distribution of adsorbed Na and Ca ions in the domains. Particle size distributions and electrophoretic mobilities (EM) of Silver Hill illite in suspension densities of 0.5 g liter−1 were determined by photon correlation spectroscopy (PCS). Solutions at salt concentration from 2 to 10 mmolc liter−1, sodium adsorption ratio (SAR) from 0 to ∞ (mmol liter−1)0.5, and pH values 5, 7, and 9 were used to prepare the clay suspensions. The particle size of Silver Hill illite suspensions showed a bimodal distribution. Through PCS measurements at low angles, the second peak of the bimodal distribution of the illite was found to be associated with the rotational movement of the b-dimension of the particles. Illite domains broke down in the range of SAR 10 to 15 (mmol liter−1)0.5 equivalent to exchangeable sodium percentages (ESP) of 13 to 18. Illite thus demonstrates a similar stability to smectites that require ESP ≈ 15 to disaggregate quasi-crystals. The EM of the illite particles increased drastically when the SAR increased from 2 to 10 (mmol liter−1)0.5. This increase in EM could not be explained exclusively by the change in the particle size. Cation demixing is required to explain the increase of the zeta potential at the shear plane. The EM of the Silver Hill illite was doubled when the pH increased from 5 to 9 at SAR > 15, but no pH effect was found when SAR < 15. The effect of pH on the EM at SAR values > 15 can be understood if we consider that at SAR > 15 most of the particles are single platelets. The relative importance of variable charge on single platelets or crystals is apparently greater than on domains because the pH affected the mobility of the individual crystals but not the mobility of the domains. The combination of particle size distribution and EM data gives additional information about the zero point of charge of the variable charge, also called point of zero net proton charge (PZNPC) of the clay. For Silver Hill illite, we estimate a PZNPC value between 5 and 7.

Noncrystalline aluminosilicates termed allophane and imogolite are common constituents of spodosols, soils derived from volcanic ash, and many inceptisols. The surface charge characteristics of their synthetic analogues may be used to better understand their ion retention properties. In this study, we determined the point of zero salt effect (PZSE) by potentiometric titration of allophanes with Al/Si ratios of 1.12, 1.52, and 2.04 and of imogolite with an Al/Si ratio of 2.02. We also used microelectrophoresis to determine the point of zero charge (PZC) at the particle shear plane for the same materials in CI solutions of Li, Na, Cs, and tetramethyl ammonium. The PZSE decreased with decreasing Al/Si ratio for the allophanes, but the imogolite PZSE was much lower than that of the allophane with 2.04 Al/Si. The PZC was always higher than the PZSE of the same material, especially for imogolite. The results are best explained if cations reside within the hollow tubes of imogolite. This conclusion is supported by a fluorescence study that showed that only quenchers smaller than the inner diameter of the imogolite tube could fully quench Ce-imogolite.

Clay particle aggregation affects a number of environmental processes, such as contaminant sorption/desorption, particle movement/deposition, and sediment structure and stability, yet factors that control clay aggregation are not well understood. This study was designed to investigate how microbial reduction of Fe(III) in clay structure, a common process in soils and sediments, affects clay-particle aggregation. Microbial Fe(III) reduction experiments were conducted with Shewanella putrefaciens CN32 in bicarbonate buffer with structural Fe (III) in nontronite as the sole electron acceptor, lactate as the sole electron donor, and AQDS as an electron shuttle. Four size fractions of nontronite (D5–D95 of 0.12–0.22 µm, 0.41–0.69 µm, 0.73–0.96 µm and 1.42–1.78 µm) were used to evaluate size-dependent aggregation kinetics. The extent of Fe(III) bioreduction and the amount of exopolysaccharide (EPS), a major biopolymer secreted by CN32 cells during Fe(III) bioreduction, were measured with chemical methods. Nontronite particle aggregation was determined by photon correlation spectroscopy and scanning electron microscopy. The maximum extent of Fe(III) bioreduction reached 36% and 24% for the smallest and the largest size fractions, respectively. Within the same time duration, the effective diameter, measured at 95% percentile (D95), increased by a factor of 43.7 and 7.7 for these two fractions, respectively. Because there was production of EPS by CN32 cells during Fe(III) reduction, it was difficult to assess the relative role of Fe(III) bioreduction and EPS bridging in particle aggregation. Thus, additional experiments were performed. Reduction of Fe(III) by dithionite was designed to examine the effect of Fe(III) reduction, and pure EPS isolated from CN32 cells was used to examine the effect of EPS. The data showed that both Fe(III) reduction and EPS were important in promoting clay mineral aggregation. In natural environments, the relative importance of these two factors may be dependent on local conditions. These results have important implications for understanding factors in controlling clay particle aggregation in natural environments.

A major issue for the oil sand industry is the settling of thin fine tailings (TFT) which are a byproduct of the oil sand extraction process. These tailings are deposited in large ponds and settling takes decades. The aim of the present study was to increase understanding of the role of specific ion types (monovalent/divalent) present in the water in flocculation behavior, and hence the settling of flotation fine tailings of the Athabasca oil sands (which consist predominantly of kaolinite). In this study, two series of measurements were conducted and compared: one with TFT and with varying pH and salinity, and another with kaolinite suspensions with varying pH, salinity, and volume fraction. The volume fraction of kaolinite and TFT used was in the range 0.01–1% volume fraction for any ionic strength or ion. In this range the electrophoretic mobility was constant indicating that there were no particle-particle interactions, a required condition for electrophoretic mobility measurements. Electrokinetic measurements were made as a function of concentration of salt added and pH. The flocculation behavior of both TFT and kaolinite can be linked to the electrokinetic mobility at high ionic strength. The electrophoretic mobility values and therefore the electrokinetic charge of the particles were smaller for divalent salt than for monovalent salt. As a consequence, both kaolinite and fine tailings should and do flocculate more quickly in the presence of a divalent electrolyte during settling-column experiments. The electrophoretic mobility of kaolinite and tailings in electrolytes containing a majority of monovalent ions (NaCl) decreased in absolute values with decreasing pH while their electrophoretic mobility in electrolytes containing a majority of divalent ions (MgCl2) did not depend on pH. The flocculation of the fine tailings in an electrolyte where divalent ions are predominant is therefore not expected to be influenced by pH.