The exchange of [Co(NH3)6]3+ from its vermiculite complex has been carried out with a number of inorganic and alkyl quaternary ammonium ions of varying ionic sizes. The distribution and selectivity coefficients of the desorbing ions increase in the order: Li<Na<NH4<K<Rb<H<Cs for the monovalent, Ca<Mg for the bivalent and (C2H5)4N<(CH3)4N≪CTA (cetyl trimethyl ammonium) <CP (cetyl pyridinium) for the organic ions. The ΔG° values of some of the cation exchange reactions have been calculated by an equation of Kielland (1935).

A technique has been developed for obtaining reproducible viscometric data on dilute clay suspensions using the recently developed capillary viscometer of Maron, Krieger and Sisko. Aging and type of mixing have important effects on the viscosity of the dispersions. At-tapulgite, hectorite, and Wyoming bentonite exhibit non-Newtonian behavior at all concentrations studied. The effect of temperature on the reduced fluidities of suspensions of the three clays is negligible. In this respect they agree with the behavior predicted for suspensions of rigid, noninteracting particles.

Diagenesis of the Holocene-Pleistocene volcanogenic sediments of the Mexican Basin produced, in strata of gravel and sand, 1H2O- and 2H2O-smectite, kaolinite, R3-2H2O-smectite (0.75)-kaolinite, R1-2H2O-smectite (0.75)-kaolinite, R3-kaolinite (0.75)-2H2O-smectite and R1-1H2O-smectite (0.75)-kaolinite. Smectite platelets were formed from volcanic glass by loss of Si4+. Partially-formed platelets have Si4+ between 4.55−4.10 a.p.f.u., Mg+Mn and the interlayer charge are relatively uniform while VIAl+Fe3++Ti varies between 0.98 and 1.63 a.p.f.u. Almost fully transformed platelets have Si4+ of 4.08−4.04 a.p.f.u.; Mg+Mn and the interlayer charge decrease proportionally to increasing VIAl+Fe3++Ti. Smectite-kaolinite mixed layers have octahedral occupancies of 2.01–2.15 a.p.f.u., IVAl3+ 0.09–0.55 a.p.f.u. and interlayer charges about half that of smectite; structural formulae corresponding to smectite (0.75–0.80)-kaolinite indicate octahedral occupancy of 2.50 a.p.f.u., tetrahedral replacement 0–0.31 a.p.f.u., and interlayer charge 0.24–0.51 equivalents, some indicating interstratifications of beidellite. Kaolinite is presumed to have formed from K-feldspar; smectite-kaolinite interstratifications sustain the transformation of kaolinite to smectite in an increasingly siliceous high-cation environment. In the mudstones of low-hydraulic conductivity and practically stagnant alkaline fluids, glass was transformed to 2H2O-smectite lamellae of IVAl between 0 and 0.47 a.p.f.u., octahedral occupancy 1.70–2.00 a.p.f.u. and interlayer charge of 0.23–1.21 equivalents, some corresponding to beidellite. The interlayer charge increases with IVAl and decreasing occupancy of the octahedral sheet; the abundance of Mg+Mn is inverse to that of VIAl+Fe3++Ti.

Clay suspensions containing 1H2O- and 2H2O-smectite, kaolinite and R3-2H2O-smectite (0.75)-kaolinite lead to low-energy edge-to-edge particle associations, non-Newtonian pseudoplastic behavior, and maximum apparent viscosity of 180 Pa s at 0.008 s−1 followed by rapid descent. Clay fractions with slightly larger 2H2O-smectite contents and smaller kaolinite contents reach maximum viscosity of 3611 Pa s at a shear rate of 0.0018 s−1 and of 3300 Pa s at 0.0024 s−1. They denote two high-energy face-to-face particle associations, followed by slow descent of the apparent viscosity under viscous flow. Suspensions change from elastic to viscous behavior at shear stresses of 1.03 and 5.91 Pa, respectively. Clay suspension vibrated at a frequency of 1 Hz develops a shear storage dynamic modulus greater than the shear dynamic loss modulus or the energy is preferentially stored, whereas at 5 Hz more energy is dissipated than stored.

Batch data for the sorption of Eu and Th on pelagic sediments may be represented by equations of the form: ln M = A ln Cs + B/T + D, where M = concentration of sorbate on sediment, Cs = concentration of sorbate in solution, T = absolute temperature, and A, B, and D = constants. Thermodynamic interpretation of this equation leads to an expression for the true thermodynamic equilibrium constant of K = m/CsA and for the enthalpy change, ΔH, of d ln(M/CsA)/d(1/T) = −ΔH/R, where R = universal gas constant.

Experimentally, the sorption of Eu onto clay-rich sediments was very rapid in the first few seconds and slowed over an interval of minutes to hours. Rate curves were similar in shape to those of α-iron hydroxide, rather than of the oxalate-extracted residual sediment, indicating the importance of oxyhydroxide-like phases in the uptake of Eu onto red-clay sediments. For clay-rich sediments, numerical modeling reproduced the general features of a series of diffusion experiments. To a first approximation, the penetration of Eu into a sediment proceeded by saturation of the sediment to the depth of penetration and produced a sharp drop-off in sorbed + dissolved Eu concentration at the diffusion front. Higher partition coefficients (Kp) resulted in greater sorbed + dissolved concentrations, but reduced penetration. For calcareous sediments, however, Eu concentrations at the surface were much higher than at depth, presumably due to the formation of an insoluble carbonate.

The alteration of bentonite under alkaline conditions and the subsequent changes in properties such as permeability and self-sealing ability should be evaluated for the performance assessment of radioactive waste repositories. As the period of evaluation for alterations is extremely long, natural analog (NA) studies that can observe long-term phenomena similar to the system of radioactive waste repositories have significant advantages. However, locations that can be set up as NA study sites with significant similarity are limited and should be pursued by localizing analog systems. This literature review summarized studies reporting secondary phases formed at low temperatures (<100°C) under a broader range of natural sites which are chemically similar to the alkaline conditions expected at bentonite in radioactive waste repositories, including near pyrometamorphic rocks, near ophiolites, and in alkaline saline lakes. This review provides insights into the species, formation conditions, and stability of secondary phases that could be formed during cement–bentonite interactions and the timescale for mineralogical transitions from a metastable to a stable phase. The findings could be useful for selecting secondary phases to be considered in reactive transport modeling for predicting cement–bentonite interactions in radioactive waste repositories.

The sustainability of high-level radioactive waste repositories situated in fractured crystalline rocks depends on the stability of bentonite liners, and this can pose a problem in certain groundwater conditions that favor the formation of colloids from backfill materials that are prone to erosion. The influence of different environments on the structure of Gaomiaozi bentonite (GMZ) and GMZ colloids (GMZC) is presented here. Different hydrated interlayer structures of bulk and colloidal forms of this bentonite from small-angle X-ray scattering (SAXS) data are demonstrated. Analysis of the scattering data showed that GMZ had three interlayer water structures: dehydrated (0W), monohydrated (1W), and bi-hydrated (2W). The colloids readily agglomerated at acidic pH (pH <5) but showed resistance to agglomeration in an alkaline condition (pH >7). The effect of Na+, K+, Mg2+, and Ca2+ on the lamellar structure and agglomerate morphology of GMZC particles was investigated. In general, the tendency of colloids to agglomerate was greater in the presence of divalent metal cations compared with monovalent metal cations. High concentrations (10–5 to 10–3 mol L–1) of divalent ions imparted order into the stacked lamellar structure after the saturation of the interlayer. In contrast, monovalent ions reduced the tendency of the particles to aggregate, leading to an abundance of colloidal nanoparticles prone to erosion. This work helps to better understand the structural characteristics of GMZC in the groundwater environment, and provides a valuable reference for the evaluation of nuclide migration in the deep geological disposal of high-level radioactive wastes.

Contamination of surface and groundwater with glyphosate, used widely on crops to control weeds, can cause severe environmental damage. Processes for glyphosate removal from water bodies have been developed, but few are effective and all are expensive. This objective of the present study was to investigate the use of a layered double oxide as a potentially effective and inexpensive material to remove glyphosate from water. Equilibrium, kinetics, and adsorption mechanisms were evaluated, in addition to the effects of competing anions and temperature on glyphosate adsorption. Up to 95% of glyphosate was removed from a synthetic solution in 50 min by Zn2Al-LDO (layered double oxide in Zn/Al ratio of 2:1) at pH 10. The adsorption isotherms were type L and the Langmuir model best fitted the experimental data, with a qmax value of 191.96 μg mg–1 at 25°C. The XRD pattern did not support the hypothesis of intercalation of glyphosate anions, whereas Fourier-transform infrared and solid-state 13C and 31P magic angle spinning nuclear magnetic resonance confirmed the adsorption of glyphosate anions on the Zn2Al-LDO surface, through carboxylate and phosphonate moiety interactions with end-on and side-on modes. The degree of removal of glyphosate increased with increasing temperature and decreased with increasing concentration of competing anions, with carbonate anions having the most prominent effect on the inhibition of glyphosate adsorption. The adsorption kinetics fitted a pseudo-first order law. Moreover, the intraparticle diffusion model suggested that the adsorption process depends on the formation and thickness of the film at the solution/solid interface.

Edible clays are consumed by diverse groups of people, especially of African descent, living in Africa and abroad, in a behavior known as geophagy. The clays are used topically as an emollient and drying agent and internally to control diarrhea. Scientific information concerning the chemical constituents and toxicity of edible clays is scarce. The aims of the present study, therefore, were to ascertain the chemical composition of white edible clays (WEC) and gray edible clays (GEC); to determine their toxicity profiles using analytical chemical methods; to test the acute and sub-acute toxicity of edible clays in their natural form as consumed; and to compare the raw and processed clays, and also to compare the latter to a proprietary drug known as ‘Mist kaolin’ (Moko®) which contains some clay along with other chemicals. Atomic absorption spectroscopy (AAS) and gas chromatography/mass spectrometry (GC/MS) were used to determine the elements present. White female Wistar mice and rats were used for the acute and sub-acute toxicity analyses, respectively. The results from AAS showed the presence of heavy metals and metalloids in both GEC and WEC, and the GC/MS revealed the presence of contaminants such as indomethacin and ethyl benzene, but quantities were below human toxicity levels. Doses of 100–500 mg/kg of either clay type could be harmful to the digestive system, but all of the tests revealed that edible clay is not toxic to humans unless very large amounts (500–1000 mg/kg of body weight) are consumed.