The oxidation potential of dithionite (Na2S2O4) increases from 0.37 V to 0.73 V with increase in pH from 6 to 9, because hydroxyl is consumed during oxidation of dithionite. At the same time the amount of iron oxide dissolved in 15 minutes falls off (from 100 percent to less than 1 percent extracted) with increase in pH from 6 to 12 owing to solubility product relationships of iron oxides. An optimum pH for maximum reaction kinetics occurs at approximately pH 7.3. A buffer is needed to hold the pH at the optimum level because 4 moles of OH are used up in reaction with each mole of Na2S2O4 oxidized. Tests show that NaHCO3 effectively serves as a buffer in this application. Crystalline hematite dissolved in amounts of several hundred milligrams in 2 min. Crystalline goethite dissolved more slowly, but dissolved during the two or three 15 min treatments normally given for iron oxide removal from soils and clays.

A series of methods for the extraction of iron oxides from soils and clays was tested with soils high in free iron oxides and with nontronite and other iron-bearing clays. It was found that the bicarbonate-buffered Na2S2O4-citrate system was the most effective in removal of free iron oxides from latosolic soils, and the least destructive of iron silicate clays as indicated by least loss in cation exchange capacity after the iron oxide removal treatment. With soils the decrease was very little but with the very susceptible Woody district nontronite, the decrease was about 17 percent as contrasted to 35–80 percent with other methods.

Ion-exchange isotherms between hydrotalcite-like compounds (HT) of the NO3-, Cl-, and SO4- forms and F−, Cl− Br−, I−, OH−, SO42−, CO32−, and Naphthol Yellow S (NYS2−) ions were determined, and the spacing and the width of the 003 reflection were measured as a function of HT composition. The ion-exchange equilibrium constant for HTs of monovalent anions are in the sequence OH− > F− > Cl− > Br− > NO3− > I−, those for divalent anions are in the sequence CO32− > NYS2− > SO42−. The ion-exchange equilibrium constants tend to increase as the diameters of the anions decrease, and the crystallite size in the 001 direction tends to increase with anions having higher selectivity. The OH-form of HT has the smallest basal spacing and the largest crystallite size in the 001 direction.

Infrared (IR) spectroscopy has a long and successful history as an analytical technique and is used extensively (McKelvy et al., 1996; Stuart, 1996). It is mainly a complementary method to X-ray diffraction (XRD) and other methods used to investigate clays and clay minerals. It is an economical, rapid and common technique because a spectrum can be obtained in a few minutes and the instruments are sufficiently inexpensive as to be available in many laboratories. An IR spectrum can serve as a fingerprint for mineral identification, but it can also give unique information about the mineral structure, including the family of minerals to which the specimen belongs and the degree of regularity within the structure, the nature of isomorphic substituents, the distinction of molecular water from constitutional hydroxyl, and the presence of both crystalline and non-crystalline impurities (Farmel, 1979).

The basic salts of this system were prepared and their structures and physico-chemical properties were studies by electron microscopy, chemical analysis, X-ray powder diffraction, thermal analysis, i.r. absorption spectra, BET absorption, and acidity-basicity measurements. The salts were found to be new compounds analogous to hydrotalcite. They can be expressed by the formula; where M2+ and M3+ denote di- and trivalent cations, A− and A2− denote mono- and divalent anions, respectively, and y = z1 + 2z2; z1 ≫ z2.

The structures consist of positively charged Cd(OH)2-like basic layers and intermediate layers formed from anions and water molecules with the solid solution of divalent cation (M2+) and trivalent cation (M3+) being formed in the range of 0.6 < x/(x + y) < 0.9. The anions of Cl−, NO3− and ClO4− are easily substituted by CO32−. A large part of the NO3− makes a monodentate-type bond and the ClO4− a bridge-type bond.

Hydrotalcite solid solutions were prepared by coprecipitation followed by hydrothermal treatment between 150° and 250°C. Based on the structural formula [Mg1−xAlx(OH)2]x+[(CO3)x/2 • mH2O]x−, pure solid solutions were formed in the range A1/(A1 + Mg) = 0.2 to 0.33, where m = (1 − 3x/2). Maximum crystallite size was achieved by hydrothermal treatment between 180° and 200°C, with x = 0.337 to 0.429. Crystal strain was also minimized at these values of x. The adsorption capacity for Naphthol Yellow S increased as x increased and reached a maximum (1.56 × 10−6 moles/m2) when x = 0.287, a value eight times larger than that of Mg(OH)2. A weak endothermic DTA peak at about 350°C is probably due to the loss of structural water in the main layer of the structure. On calcination between 400° and 700°C, only periclase was detected, probably containing Al in solid solution. Hydration of the calcined product resulted in the reconstruction of the original hydrotalcite structure.

Investigations concerning selective sorption and fixation of K and similar cations by clay minerals and soil clays and the mechanisms of these reactions are reviewed. In particular, recent observations on selective sorption of these ions in dilute solutions by weathered micas and vermiculite in relation to the interlayer structures are discussed in detail. Also, implications of the resistance to weathering of small mica particles to cation selectivity by soils are described. Despite the increased understanding of sorption and fixation reactions, the following aspects remain unclear.

First, the mechanism of the collapse of alternate layers in vermiculite on K or Cs sorption has not been unequivocally established. Second, factors that impart stability to the central core of mica particles so that K extraction becomes progressively difficult are not known. Third, inability of Ca or Mg ions to expand interlayers of Cs-saturated vermiculite in contrast to K-saturated vermiculite is not completely understood.

Storage of ferrihydrite in aqueous suspensions at 24°C and pHs between 2.5 and 12 for as long as three years resulted in the formation of goethite and hematite. The proportions and crystallinity of these products varied widely with the pH. Maximum hematite was formed between pH 7 and 8, and maximum goethite at pH 4 and at pH 12. The crystallinity of both products, as indicated by X-ray powder diffraction line broadening and magnetic hyperfine field values and distribution widths, was poorer, the lower the proportion of the corresponding product in the mixture. The existence of two competitive formation processes is suggested: goethite is formed via solution, preferably from monovalent Fe(III) ions [Fe(OH)2+ and Fe(OH)4−], and hematite by internal rearrangement and dehydration within the ferrihydrite aggregates. This concept relates the proportions of goethite and hematite to the activity of the Fe(III) ion species in solution, and implies that conditions favorable for the formation of goethite are unfavorable for that of hematite and vice versa.

Under appropriate conditions, both surface areas and cation exchange capacities of clay minerals can be measured by absorption of methylene blue from aqueous solutions. The method has been applied to two kaolinites, one illite, and one montmorillonite, all initially saturated with Na+ ions. For Na-montmorillonite, the total area, internal plus external, is measured. For Ca-montmorillonite, entry of methylene blue molecules appears to be restricted by the much smaller expansion of the Ca- clay in water. X-ray diffraction data clarify the absorption behavior in Na- and Ca-montmorillonite, and in particular it is shown that two orientations of the methylene blue molecules are involved.

The crystal structure of Keokuk kaolinite, including all H atoms, was refined in space group C1 using low-temperature (1.5 K) neutron powder diffraction data (λ = 1.9102 Å) and Rietveld refinement/difference-Fourier methods to Rwp = 1.78%, reduced χ2 = 3.32. Unit-cell parameters are: a = 5.1535(3) Å, b = 8.9419(5) Å, c = 7.3906(4) Å, α = 91.926(2)°, β = 105.046(2)°, γ = 89.797(2)°, and V = 328.70(5) Å3. Unit-cell parameters show that most of the thermal contraction occurred along the [001] direction, apparently due to a decrease in the interlayer distance. The non-H structure is very similar to published C1 structures, considering the low temperature of data collection, but the H atom positions are distinct. The inner OH group is essentially in the plane of the layers, and the inner-surface OH groups make angles of 60°–73° with the (001) plane. Difference-Fourier maps show minor anisotropy of the inner-OH group in the [001] direction, but the inner-surface OH groups appear to have their largest vibrational (or positional disorder) component parallel to the layers. Although no data indicate a split position of any of the H sites in kaolinite, there is support for limited random positional disorder of the H atoms. However, these data provided no support for a space group symmetry lower than C1.

Subsurface samples of shales ranging in age from Pleistocene to Eocene obtained from five Gulf Coast oil wells were examined mineralogically and chemically to determine the nature and extent of burial diagenesis in pelitic sediments. Illite/montmorillonite dominates the mineralogy and undergoes a monotonic decrease in expandability from about 80 to a limit of 20 per cent montmorillonite layers with increasing depth. The interstratification changes from random to ordered at about 35 per cent expanded layers. Discrete illite and kaolinite phases are ubiquitous and judged detrital. The discrete illite (mica) content of the whole rock decreases with depth, while the kaolinite shows no systematic variation. Chlorite occurs in appreciable amounts in only one well and there only in samples from the shallow water facies. This chlorite is also considered detrital.

Whole rock chemical analyses show no systematic variation with depth except for a decrease in calcium and magnesium caused by solution of carbonate. In contrast, potassium increases progressively with depth in the clay-size fraction, indicating a redistribution of potassium within the rock. Detrital illite (mica) seems to break down with increasing depth, thereby supplying potassium for interlayer fixation in illite/montmorillonite as the proportion of illite layers increases. The diagenetic reaction is independent of the geologic age of the sediments and of stratigraphic boundaries. Temperature seems to be more important than pressure in governing the reaction.

Coefficients of permeability, calculated using Terzaghi’s theory of one-dimensional consolidation, are reported for smectite, illite, and kaolinite, in water, methyl and ethyl alcohol, benzene, and carbontetrachloride. When the pore fluid was water the clays were homoionized to either the sodium or calcium form and the pore water electrolyte concentration was varied. The coefficients of permeability are evaluated in terms of both mechanical and physico-chemical variables. It appears that the coefficients of permeability are mainly influenced by mechanical effects, particularly the distribution of void sizes and the tortuosity of the channels. The coefficient of permeability is maximized if the flow channels consist of many small channels and a relatively few large ones, through which the main flow occurs. Physico-chemical variables exert great influence on the coefficient of permeability through their influence on dispersion or aggregation of the clay particles.

Geological disposal is the preferred option for the final storage of high-level nuclear waste and spent nuclear fuel in most countries. The selected host rock may be different in individual national programs for radioactive-waste management and the engineered barrier systems that protect and isolate the waste may also differ, but almost all programs are considering an engineered barrier. Clay is used as a buffer that surrounds and protects the individual waste packages and/or as tunnel seal that seals off the disposal galleries from the shafts leading to the surface.

Bentonite and bentonite/sand mixtures are selected primarily because of their low hydraulic permeability in a saturated state. This ensures that diffusion will be the dominant transport mechanism in the barrier. Another key advantage is the swelling pressure, which ensures a self-sealing ability and closes gaps in the installed barrier and the excavation-damaged zone around the emplacement tunnels. Bentonite is a natural geological material that has been stable over timescales of millions of years and this is important as the barriers need to retain their properties for up to 106 y.

In order to be able to license a final repository for high-level radioactive waste, a solid understanding of how the barriers evolve with time is needed. This understanding is based on scientific knowledge about the processes and boundary conditions acting on the barriers in the repository. These are often divided into thermal, hydraulic, mechanical, and (bio)chemical processes. Examples of areas that need to be evaluated are the evolution of temperature in the repository during the early stage due to the decay heat in the waste, re-saturation of the bentonite blocks installed, build-up of swelling pressure on the containers and the surrounding rock, and degradation of the montmorillonite component in the bentonite. Another important area of development is the engineering aspects: how can the barriers be manufactured, subjected to quality control, and installed?

Geological disposal programs for radioactive waste have generated a large body of information on the safety-relevant properties of clays used as engineered barriers. The major relevant findings of the past 35 y are reviewed here.

Several clay-organic complexes were synthesized by placing quaternary ammonium cations on smectite by cation exchange. They were then examined for their ability to adsorb phenol and several of its chlorinated congeners. The organic cations used were: hexadecylpyridinium (HDPY+), hexadecyltri-methyl ammonium (HDTMA+), trimethylphenyl ammonium (TMPA), and tetramethylammonium (TMA+). The complexes containing long-chain alkyl (hexadecyl) groups were the most hydrophobic and adsorbed the phenols from water in proportion to their hydrophobicities, which increase with chlorine addition (phenol < chlorophenol < dichloropohenol < trichlorophenol). With n-hexane as the solvent, different adsorption was found which depended on the type and degree of solvent interactions with the compound and the clay-organic complex. Thus, the amount of adsorption of these phenols on clay-organic complexes was dependent on the relative energies of adsorbent-adsorbate and adsorbate-solvent interactions.

Methods previously used to distinguish between water adsorbed on external surfaces and in the interlamellar space of Na-montmorillonite during adsorption and desorption of water vapor have been extended to a set of homoionic Li-, Na-, K-, Rb- and Cs-montmorillonite. The textural and structural features have been investigated at different stages of hydration and dehydration using controlled-rate thermal analysis, nitrogen adsorption volumetry, water adsorption gravimetry, immersion microcalorimetry and X-ray powder diffraction under controlled humidity conditions. During hydration, the size of the quasi-crystals decreases from 33 layers to 8 layers for Na-montmorillonite and from 25 layers to 10 layers for K-montmorillonite, but remains stable around 8–11 layers for Cs-montmorillonite. Each homoionic species leads to a one-layer hydrate, which starts forming at specific values of water vapor relative pressure. Li-, Na- and K-montmorillonite can form a two-layer hydrate. By comparing experimental X-ray diffraction patterns with theoretically simulated ones, the evolution of structural characteristics of montmorillonites during hydration or desorption can be described. Using structural and textural data, it is shown that during adsorption: (1) the rate of filling of interlamellar space of the one layer hydrate increases with the relative pressure but decreases with the size of the cations; and (2) the different hydrated states are never homogeneous.

The Clay Minerals Society maintains a repository of Source Clays to provide scientists and researchers with a readily available supply of consistent materials so that research conducted by different groups can be correlated to identical material. These Source Clays include kaolinite, smectite, chlorite, vermiculite, illite, palygorskite and other minerals. As most of the Source Clays are naturally occurring materials, they typically contain minor to significant amounts of other mineral impurities. When conducting research using these samples, it is important that their mineral content be well characterized. It is also often desirable to remove these impurities to produce pure clay samples. For example, when studying the biological effects of a particular clay mineral, it is imperative that all contaminants (e.g. crystalline silica minerals) be removed from the clay in question so that experimental results can be attributed to the clay alone. If purification is required, the clays must be purified in a manner that does not significantly alter the physical or chemical properties of the samples. This chapter describes the X-ray diffraction (XRD) characteristics of a suite of Source Clays of The Clay Minerals Society and demonstrates methods of purification based on Stokes' law of settling in suspension that can be used to purify the clays.

An internal standard X-ray diffraction (XRD) analysis technique permits reproducible and accurate calculation of the mineral contents of rocks, including the major clay mineral families: Fe-rich chlorites + berthierine, Mg-rich chlorites, Fe-rich dioctahedral 2:1 clays and micas, Al-rich dioctahedral 2:1 clays and micas, and kaolinites. A single XRD pattern from an air-dried random specimen is used. Clays are quantified from their 060 reflections which are well resolved and insensitive to structural defects. Zincite is used as the internal standard instead of corundum, because its reflections are more conveniently located and stronger, allowing for a smaller amount of spike (10%). The grinding technique used produces powders free of grains coarser than 20 µm and suitable for obtaining random and rigid specimens.

Errors in accuracy are low, <2 wt. % deviation from actual values for individual minerals, as tested on artificial shale mixtures. No normalization is applied and thus, for natural rocks, the analysis is tested by the departure of the sum of the measured components from 100%. Our approach compares favorably with other quantitative analysis techniques, including a Rietveld-based technique.

The adsorption of uncharged polymers by clays is largely “entropy-driven.” Polymer conformation changes from a random coil in solution to an extended form at the surface in which adsorbed polymer segments or trains alternate with loops and tails extending away from the surface. Although the net interaction energy, ε, per segment-surface contact is small (~1 kT unit), the total energy of adsorption is large because the fraction of train segments, p, is commonly between 0.3 and 0.5. The adsorption isotherms are typically of the high-affinity type, and there is an apparent lack of desorption on dilution. Positively charged polymers (polycations) are adsorbed largely through electrostatic interactions between the cationic groups of the polymer and the negatively charged sites at the clay surface. Here ε ≫ 1 kT unit and p > 0.7, leading to an almost complete collapse of the polymer chain onto the surface. Indeed, beyond a given level of adsorption charge reversal can occur in that the clay-polycation system effectively behaves as an anion exchanger. Little adsorption occurs with negatively charged polymers (polyanions) due to initial charge repulsion between the polymer and the clay surface. Acid pH, a high ionic strength, and the presence of polyvalent cations in the system enhance and promote polyanion adsorption. Uncharged polymers and polycations can enter the interlayer space of expanding 2:1 type layer silicates but polyanions generally fail to intercalate.

The interactions of clays with biopolymers, such as proteins, nucleic acids, and polysaccharides, can be rationalized in similar terms. When intercalation occurs, the interlayer biopolymer is further stabilized against microbial (enzymatic) degradation giving rise to practical applications of clay-polymer complexes as flocculants and soil conditioners. Polyanions are effective as flocculants because of their large “grappling distance,” whereas uncharged polymers are better suited as soil conditioners because they can spread over adjacent clay/soil particle surfaces like a coat of paint.

Interlayer cations and moisture content greatly influence the molecular vibrations of H2O in montmorillonite as shown through reflectance spectroscopy in the infrared. The absorptions due to H2O have been studied in montmorillonites exchanged with H, Na, Ca, Mg and Fe3+ interlayer cations under variable moisture environments. Band assignments have been made for absorptions in the 3 µm region due to structural OH vibrations, symmetric and asymmetric H2O stretching vibrations and the H2O bending overtone. Changes in the energies of the absorptions due to H2O stretching vibrations were observed as the samples were dehydrated by reducing the atmospheric pressure. Absorptions near 3620 cm−1 and 3550 cm−1 have been assigned to water bound directly to cations (inner sphere) and surface-bonded H2O and absorptions near 3450 cm−1 and 3350 cm−1 have been assigned to additional adsorbed water molecules. Band assignments have been made for combination bands in the near-infrared as well. Absorptions near 1.41 μm and 1.91 μm are assigned to bound H2O combination bands, while the shoulders near 1.46μm and 1.97 μm are assigned to combinations of additional H2O molecules adsorbed in the interlayer regions and along grain surfaces.

We measured the visible to near-infrared (IR) spectra of 176 synthetic and natural samples of Fe oxides, oxyhydroxides and an oxyhydroxysulfate (here collectively called “Fe oxides”), and of 56 soil samples ranging widely in goethite/hematite and goethite/lepidocrocite ratios. The positions of the second-derivative minima, corresponding to crystal-field bands, varied substantially within each group of the Fe oxide minerals. Because of overlapping band positions, goethite, maghemite and schwertmannite could not be discriminated. Using the positions of the 4T1←6A1, 4T2←6A1, (4E;4A1)←6A1 and the electron pair transition (4T1+4T1)←(6A1+6A1), at least 80% of the pure akaganeite, feroxyhite, ferrihydrite, hematite and lepidocrocite samples could be correctly classified by discriminant functions. In soils containing mixtures of Fe oxides, however, only hematite and magnetite could be unequivocally discriminated from other Fe oxides. The characteristic features of hematite are the lower wavelengths of the 4T1 transition (848–906 nm) and the higher wavelengths of the electron pair transition (521–565 nm) as compared to the other Fe oxides (909–1022 nm and 479–499 nm, resp.). Magnetite could be identified by a unique band at 1500 nm due to Fe(II) to Fe(III) intervalence charge transfer. As the bands of goethite and hematite are well separated, the goethite/hematite ratio of soils not containing other Fe oxides could be reasonably predicted from the amplitude of the second-derivative bands. The detection limit of these 2 minerals in soils was below 5 g kg−1, which is about 1 order of magnitude lower than the detection limit for routine X-ray diffraction (XRD) analysis. This low detection limit, and the little time and effort involved in the measurements, make second-derivative diffuse reflectance spectroscopy a practical means of routinely determining goethite and hematite contents in soils. The identification of other accessory Fe oxide minerals in soils is, however, very restricted.