The hydroxyl stretching region of two montmorillonites (SWy-1, Crook County, Wyoming, USA, and JP, Jelšový Potok, Slovakia) and a ferruginous smectite (SWa-1, Grant County, Washington, USA) have been analysed using decomposition and curve-fitting. The positions and integrated intensities of component bands were correlated with the nearest cationic environment of the OH groups, and the populations of the octahedral sheet were calculated. The differences between the octahedral coefficients obtained and those from chemical analyses were 0.07 or less. This method provides reasonable contents of octahedral cations for the smectites with various iron contents, containing no other admixtures absorbing in the 3700-3500 cm–1 region. The cation distribution was found to be not completely disordered. Though some preferential pairing has been observed, no general rule could be established.

Analysis of the near-infrared (NIR) spectral bands of phyllosilicates, together with the mid-infrared bands, enables testing and confirmation of band assignments for the structural OH vibrations. Spectral analyses of selected smectites and serpentine-kaolin minerals are presented here. The results of this study indicate that dioctahedral smectites may contain both in-plane and out-of-plane OH-bending vibrations, as suggested by Farmer (1974). In-plane bands occur near 800 ­ 915 cm–1, while the weaker out-of-plane vibrations occur near 600 ­ 700 cm–1 and are enhanced in dioctahedral smectites when the structure is disrupted by substitutions. Analysis of the OH-stretching vibrations and their NIR overtone bands is also presented for both smectites and serpentine-kaolin minerals. These overtones are more straightforward for serpentines than for kaolinite, and a strong overtone associated with the kaolinite OH-stretching band at 3620 cm–1 is found that supports its assignment as an OH-stretching band.

A magnetic iron oxide is a common constituent of ferruginous concretions in highly weathered Australian soils and is generally associated with varying proportions of hematite and occasionally with goethite. The X-ray diffraction pattern and the low Fe (11) contents (4-15% of total Fe) of this magnetic phase identify it as maghemite which was further confirmed by IR and DTA. This maghemite is only slightly soluble in dithionite but readily in 1:1 HCl or oxalic acid. From the Fe (11) contents and mineralogical associations in soil concretions, conditions for maghemite formation under near pedogenic conditions are suggested.

The reductive dissolution by Na-dithionite of 28 synthetic goethites and 26 hematites having widely different crystal morphologies, specific surfaces and aluminium substitution levels has been investigated. For both minerals the initial dissolution rate per unit of surface area decreased with aluminium substitution. At similar aluminium substitution and specific surface, goethites and hematites showed similar dissolution rates. These results suggest that preferential, reductive dissolution of hematite in some natural environments, such as soils or sediments, might be due to the generally lower aluminium substitution of this mineral compared to goethite.

Spanish montmorillonites from Frente Archidona were used to demonstrate the determination of charge density, CEC and, in mixtures, the montmorillonite content by the aikylammonium method. Special attention is directed to heterogeneous montmorillonites and the determination of the charge density distribution. Some problems which arise by application of the method are discussed: relations between layer charge and cation densities, particle size corrections, microstructures and unsymmetric charge distributions in the interlayer spaces.

The Triassic Sherwood Sandstone Group comprises a complex of continental red beds deposited by a major fluvial system flowing dominantly down a northerly inclined palaeoslope. Sedimentation took place in several distinct, tectonically active basins with varying maximum burial depths, ranging from shallow (<1 km) to deep (>3 km). Despite proximal to distal variations in stream type, a distinct suite of early diagenetic events can be recognized throughout all the depositional basins, which is related to the depositional environment. These events are best preserved in those basins with shallow burial histories, and show many similarities to the processes recorded from modern red beds of the Sonoran Desert, Baja California, although a more advanced grade of diagenesis has been reached in the Sherwood Sandstone. On the margins of the Irish Sea Basin in Cumbria, where burial was shallow, these early diagenetic textures are well preserved. The detrital grains underwent changes aimed at reaching equilibrium with the near-surface chemical environment. Unstable silicates were dissolved or replaced and the released ions were capable of precipitating authigenic phases, typically mixed-layer illite-smectite, K-feldspar, non-ferroan carbonates and hematite. Lateral variations in the early diagnetic assemblages reflect chemical and spatiotemporal changes ofinterbasin depositional and diagenetic environments. Deeply buried equivalents in the Irish Sea reached a maximum burial depth in excess of 3 km towards the end of the Mesozoic. Superimposed on the early diagenetic fabric are a series of depth-related changes. In the absence of early cements, compaction reduced porosity to low levels. Mixed-layer illite-smectites were converted to highly crystalline illites with low Fe and Mg contents. Early framework-preserving non-ferroan carbonates were extensively dissolved, generating widespread secondary porosity. Late pore-filling carbonate cements comprise ferroan dolomites and ankerites with compositions up to Ca(Ca0·02Mg0·43Fe0·53Mn0·02). Following late Mesozoic burial, inversion of the Triassic basins resulted in the re-exposure of basin margin sequences and shallow burial basins. Modern groundwaters are typically very dilute, with essentially neutral pH, and are capable of dissolving carbonate, sulphate and halite cements. In the Wessex Basin, however, the Triassic sandstones of the South Devon aquifer have been extensively modified by the percolation of post-inversion acidic groundwaters. These low-pH waters have resulted in the in situ breakdown of feldspar to produce abundant authigenic kandite, widespread dissolution of carbonate cements and removal of early-formed iron oxide cements. In contrast, the concealed, deeply buried eastern margin of the Wessex Basin exhibits a diagenetic evolution resultant of deep burial and has no development of authigenic kandite.

Some of the many problems associated with the acquisition and interpretation of K-Ar isotope data for authigenic illites in porous sandstone lithologies are discussed. Difficulties arise from a lack of critical awareness of the assumptions made in deriving a K-Ar age of illite formation. Calculations are presented which imply that where sustained reservoir temperatures are high (> 150°C), erroneously low K-Ar ages could result from diffusive Ar loss. Very low levels of detrital contamination with other K-bearing minerals cause further difficulties. Even non-K-bearing contaminants may have a marked effect on apparent ages of illite ‘separates’. However, if considerable care is exercised during separation, the contamination problem is not intractable. The potential of the K-Ar technique to specify temporal development of the characteristics of reservoir rocks suggests that analytical refinements and basic experimental parameters are worth pursuit. Hypothetical examples of depth-age profiles are discussed in the context of their relevance to the timing and nature of hydrocarbon charging of reservoirs.

The intercalation of several highly polar organic compounds into kaolinite and the formation of interlamellar complexes has been examined by X-ray diffraction. Some compounds intercalate directly into kaolinite, while others can only be intercalated by the displacement of a previously intercalated compound. The formation of the complexes is strongly dependent on the properties of the organic compound, and generally a large dipole moment favours the formation of a complex. A large dipole moment may however cause extensive association in the liquid state and this decreases the rate of intercalation. The addition of water to highly associated compounds increases the rate of intercalation by breaking up the structure of the associated liquid, and the rate passes through a maximum with increasing water content. Thus the rate of intercalation is found to depend on the extent of association in the liquid or solution, the temperature and the molecular size. The d(001) spacings of the complexes are given and the orientation and packing of the intercalated molecules in relation to the Δ - values is discussed.

Well-cuttings and core samples from four Gulf Coast areas have been examined by high-resolution scanning-transmission electron microscopy and other techniques to detail the chemical, mineralogical and textural changes during diagenesis. Wells in each of the four areas exhibit a distinct smectite-to-illite (S-I) transition, but the estimated depths for the transition vary significantly: 5600 to 8800 ft for the onset of the transition, and 7500 to 13 600 ft for the completion (70–80% illite). Calculated temperatures also vary significantly: 58° to 92°C for the onset, and 88° to 142°C for the completion. No pattern is evident for characteristic temperatures of the S-I transition. These data suggest that it is inappropriate to use the S-I transition for determining absolute diagenetic temperatures in geological settings similar to Gulf Coast sequences. TEM data imply the presence of two distinctly different kinds of domains, interpreted as smectite (with some mixed-layer component?) and illite. Initially, smectite domains dominate and contain subparallel layers of variable thickness. As the transition proceeds, abundant dislocations provide avenues for diffusion of both necessary reactants (K and Al) and products (Na, Si, Fe, Mg); illite packets grow within a shrinking matrix of smectite. Variable temperatures for the transition may be due to several factors, including chemical heterogeneity of the original smectite, variation in water/rock ratio, porosity differences, diverse chemical character of available fluids, and the particular physical environment for diagenesis. It is suggested that actual depths and temperatures for the transition are primarily a function of kinetic factors associated with a reaction for which at least one of the principal phases is metastable; the transition therefore is highly dependent on local geological factors.

It is surprising how reluctant many clay mineralogists have been to attribute the small cation exchange capacity of kaolinite to a correspondingly small isomorphous replacement. After all, only one silicon in 400 need be replaced by aluminium to give an exchange capacity of 2 m.e./100 gm., and it is very difficult to prove or disprove so small a replacement by chemical analysis.

Clay mineralogical differences between eight soils in South Island, New Zealand, are related to differences in climate, vegetation, and formation time. Alteration of chlorite follows the sequence chlorite→interlayered hydrousmica→chlorite-swelling chlorite→chlorite-vermiculite, with increased weathering leading to the destruction of the chloritic layers. Mica (muscovite) follows two alteration sequences depending on the overlying vegetation. Under tussock grassland the sequence is mica→mica-vermiculite→mica-beidellite→beidellite. This sequence is also followed under beech forest, together with the sequence of mica→vermiculite→beidellite, with pedogenic chlorite forming when the pH is > 4·5. All but one of the interstratified products (the interlayered hydrous mica) appear to be based on a 1:1 regular interlayering of the two components.

Batch reactor experiments were performed at 35°C and 80°C to determine the effect of high molar KOH solutions on the mineralogy and solution chemistry of two different smectites. The Ceca smectite is a nearly pure montmorillonite, and the Ibeco clay has a significant component of 35% beidellitic charge. Each reactor was charged with 1 g of <2 mm fraction smectite and 80, 160, 240 ml of 0.1–4 M KOH solution. In these experiments, the changes in solution composition and mineralogy were monitored as a function of time.

In the experiments, at all temperatures and under all chemical conditions, the smectite appears to change in diffracting domain size, which decreases with time. This probably reflects a change in crystal shape. The structures then become more illite rich and the diffracting domain continues to decrease.

The extraction of naturally occurring free iron oxides from soils and clays with oxalate solutions is distinctly photosensitive. Apparently wave-lengths around 366 mµ, the near ultra-violet region, are the most efficient; this radiation is predominant in the emission of a medium-pressure mercury arc lamp. A qualitative consideration of the dissolution process indicates that in all probability electron transfer from solute to solid via intermediary C2O4− is involved. Such a mechanism may explain the attack of near-neutral oxalate solutions upon natural ferric oxides and the decomposition of the quite resistant hematite in slightly acid media, when irradiated. The reaction appears to be autocatalytic. Electron transfer utilizing thermal electrons may also explain the attack of dithionite ions upon ferric oxides, which was shown to proceed in media above neutrality. Finally, a detailed description of the method is given, including the application for estimating free iron oxides in particle-size fractions obtained during the course of mechanical analysis.

Iron(II)-containing minerals are potential inorganic nitrate reductants in soils and sediments. Specifically, synthetic green rust (Fe4IIFeIII2(OH)12SO4.yH2O, GR) reduces nitrate to ammonium. The reaction of GR with two different nitrate salts, NaNO3 and Ba(NO3)2, has been compared. The reaction stoichiometry and the reaction order with respect to Fe(II) in GR does not change in the examined temperature range (15-50°C) irrespective of the nitrate salt used. Activation energies of 83.9±7.6 kJ mol-1 and 90.5±6.9 kJ mol-1 have been determined for the reaction of GR with NaNO3 and Ba(NO3)2, respectively. However, for the latter reaction the rate of reaction is increased 40 times. Based on X-ray and M6ssbauer investigations, this acceleration of the reaction rates is attributed to the forced exchange of sulphate with nitrate in GR interlayers caused by precipitation of BaSO4 outside the GR particles, a reaction which does not occur in the presence of NaNO3. This difference in anion exchange behaviour is confirmed by anion exchange experiments with the redox-inactive GR-analogue, pyroaurite. A reaction model initiated by nitrate electrostatically bound at positively charged sites of GR is proposed.

In this study, the influence of pH, electrolyte concentration and type of ionic species (such as LiCl, NaCl, KCl, RbCl, CsCl, CaCl2, AlCl3) on the electrokinetic properties (zeta potential and electrokinetic charge density) of montmorillonite has been quantified. The zeta potential of montmorillonite particles did not change significantly with change in pH. The valencies of the ions have proven to have a great influence on the electrokinetic behaviour of the suspension. There is a gradual decrease in the zeta potential (from —24 mV to —12 mV) with increase in monovalent electrolyte concentration (from 10-4 M to 10-1 M). At any monovalent electrolyte concentration, the magnitude of the zeta potential increased with the electrolytes in the order Li+ > Na+ > K+ > Rb+ > Cs+. The zeta potential of the montmorillonite minerals in CaCl2 solutions illustrated the same behaviour as the monovalent cations. Less negative values were obtained for the CaCl2 electrolyte (∼–10 mV) due to the greater valence of the ions. A sign reversal was observed at an AlCl3 concentration of 5 x 10-4 M, and, at greater concentrations, zeta potential values had a positive sign (∼20 mV).

The electrokinetic charge density of montmorillonite showed similar trends of variation in mono and divalent electrolyte solutions. Up to concentrations of ∼10-3 M, it remained practically constant at ∼0.5 x 10-3Cm-2, while for greater electrolyte concentrations the negative charge produced more negative values (–16 x 10-3Cm-2). The electrokinetic charge density of montmorillonite particles was constant at low AlCl3 concentrations, but at certain concentrations it increased rapidly and changed sign to positive.

Theories concerning the optical properties of cationic dyes adsorbed on clay surfaces are analysed in detail. An investigation of the aggregation of methylene blue (MB) in montmorillonite dispersions is conducted using visible (VIS) spectroscopy. The effects of the dye/ clay ratio and of the swelling properties of the montmorillonite substrate on dye aggregation are compared in terms of the effect of clay layer charge. The observed influence on dye aggregation was almost negligible for both swelling and dye loading. The layer charge of the silicate determines the extent and the type of dye aggregation in freshly prepared MB/montmorillonite dispersions. Observed spectral changes with time indicate a rearrangement and redistribution of dye H-aggregates (band close to 570 nm) to monomers (660 nm), dimers (605 nm) and J-aggregates (760 nm). Dye aggregates are probably already formed during dye cation migration in the vicinity of clay colloid particles. The extent and the type of initially formed species are probably affected by the electric double layer of clay layers. After reaching the clay surface, dye cation assemblies are rearranged and decompose as described above. Reaching chemical equilibrium, dye cations adjust the distribution of the layer charge, in order that each cation could balance the charge due to one unequivalent substitution.

Depending on the preparation temperature and the origin of the raw mineral, the products obtained by thermal activation of kaolinite lead, by hydrothermal treatment with sodium hydroxide at 102°C, either to zeolite 4A, or to cubic zeolite P, or to a mixture of cubic and tetragonal zeolite P. The change in the type of zeolite obtained was explained on the basis of a radical change of the zeolite nucleation process due to either the presence of soluble potassium or high silica content resulting from dehydration of muscovite (an impurity in the raw-kaolinite), or from “segregation” associated with the first step of the metakaolinite to mullite transformation. These phenomena occur at a lower calcination temperature with poorly-crystallized kaolinite, and iron in such a sample promotes a sensitive decrease in the formation rate of zeolite crystals. Such results could be used to characterize the crystallinity of kaolinites.

Transmission electron microscopic (TEM) examination of the <0·1-µm fraction of montmorillonite and regularly interstratified illite-smectite (I-S) shows that these clays, when dried from suspension, consist primarily of particles 10 Å and 20 Å thick respectively. However, X-ray diffraction (XRD) examination of sedimented aggregates of montmorillonite indicate that the effective number of unit cells that are diffracting coherently is ∼9. This discrepancy can be reconciled by postulating an interparticle diffraction effect from the sedimented aggregates of oriented particles. The interfaces of these particles are capable of adsorbing water, ethylene glycol etc. so that on this basis smectite is composed of elementary silicate particles 10 Å thick, and regularly interstratified I-S is primarily composed of elementary ‘illite’ particles 20 Å thick, values which are in agreement with the TEM observations. This concept is confirmed experimentally by XRD examination of sedimented aggregates from mixed suspensions of both materials; the resulting patterns are identical to those of randomly interstratified illite and smectite layers, which indicates that the layer sequence examined by XRD has been entirely rearranged. It is concluded that the use of XRD peak breadth to determine mean crystal thickness cannot be reliably applied to these systems. Standard XRD data from sedimented aggregates may not be able to distinguish between true interstratification and interparticle diffraction effects of intimate physical mixtures.

Clay mineral associations of Palaeocene and Eocene age, with special attention to the late Palaeocene thermal maximum, have been examined in ten sections from the Tethys (Egypt, Israel, Tunisia, Spain and Kazakhstan) and Atlantic (England). A widespread abundance of kaolinite in marine sediments at all locations suggests a warm and humid climate with high rainfall in the Tethys region during the early Palaeocene. In the coastal basins along the southern margin (Israel and southern Tunisia), kaolinite disappears gradually giving way to palygorskite and sepiolite, suggesting the progressive development of arid climatic conditions in this part of the Tethys from the late Palaeocene to the early Eocene. Remarkably, kaolinite increases strongly throughout most of the Tethys during the late Palaeocene thermal maximum (LPTM) reflecting an episode of humidity and warmth and coincident with a global maximum warmth of seawaters inferred from oxygen isotopic data.

β-FeOOH (akaganéite) was prepared by slow hydrolysis of an FeCl3 solution. X-ray diffraction measurements gave refined unit-cell parameters of a=10·535 Å, c=3·030 Å.

Two doublets with δ(Fe)=0·39, ΔEQ=0·95, and δ=0·38, ΔEQ=0·55 mm s−1, respectively, can be fitted to the Mössbauer spectrum taken at room temperature.

Magnetically split Mössbauer spectra were registered at 135 and 4°K. These can be resolved into at least three superimposed sextets, corresponding to different Fe3+ sites in the β-FeOOH structure. At 4°K a three sextet model gives parameters of δ=0·36, ΔEQ=0·90, Hi=473; δ=0·35, ΔEQ=0·30, Hi=479; and δ=0·37, ΔEQ=−0·05 mm s−1, Hi=486kOe, respectively.

The complexity of the Mössbauer spectra of β-FeOOH limits the usefulness of this method as a tool for the identification of akaganéite in composite natural samples.