Intercalated compounds of montmorillonite and poly-6-amide were prepared by heating mixtures of ɛ-caprolactam and 5, 10, 15 and 30 wt% of montmorillonite, cation-exchanged with NH3+(CH2)11COOH, at 250°C in a nitrogen atmosphere, and examined by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), gel permeation chromatography (GPC) and elemental analysis. ɛ-caprolactam was polymerized to poly-6-amide by the heat treatment. The mean number-average molecular weight decreased from 3·6 × 104 to 0·8 × 104 with increasing montmorillonite content. TEM showed that considerable swelling had taken place subsequent to polymerization and that the clay layers were uniformly distributed in the final clay/poly-6-amide products. Both XRD and TEM showed that the basal spacing of the compound increased from 51 Å to 210 Å with increasing polyamide content. The driving force for the swelling was considered to be a combination of the polymerization energy of ɛ-caprolactam and the attractive interaction between the interlayer cation and ɛ-caprolactam.

Synthetic 2-line and 6-line ferrihydrite and feroxyhite samples prepared from ferric salt solutions have been investigated by EXAFS spectroscopy. All these materials have been found to be short-range ordered, consisting of Fe octahedra linked by comers, edges, and faces. Their local structures are related to those of well-crystallized (oxyhydr)oxides, and the absence of hkl reflections in some samples is attributed to the small size of coherent scattering domains. The presence of face sharings indicates that these materials have structural similarities with hematite. Based on Fe-Fe distances and the analysis of the static disorder, it has been concluded that the local structure of feroxyhite is close to that of hematite, whereas ferrihydrite has common structural features with both hematite (αFe203) and cdβFeOOFI. The local structure of ferrihydrite thus differs from that of aqueous Fe polymers obtained by the partial hydrolysis of ferric nitrate and chloride solutions. Differences of local structures among hydrous Fe oxides and aqueous polymers have been interpreted on the basis of a room temperature stability phase diagram established for well-crystallized (oxyhydr)oxides.

The literature on the formation, structure and properties of allophane and imogolite is reviewed, with particular emphasis on the seminal contributions by Colin Farmer. Allophane and imogolite occur not only in volcanic-ash soils but also in other environments. The conditions required for the precipitation of allophane and imogolite are discussed. These include pH, availability of Al and Si, rainfall, leaching regime, and reactions with organic matter. Because of their excellent water storage and physical properties, allophanic soils can accumulate large amounts of biomass. In areas of high rainfall, these soils often occur under rain forest, and the soil organic matter derived from the forest biomass is stabilized by allophane and aluminium ions. Thus the turnover of soil organicmatter in allophanicsoils is slower than that in non-allophanicsoils. The organic matter appears to be derived from the microbial by-products of the plant material rather than from the plant material itself. The growth of young forests may be limited by nitrogen supply but growth of older forests tends to be P limited. Phosphorus is recycled through both inorganic and organic pathways, but it is also strongly sorbed by Al compounds including allophane. When crops are grown in allophanic soils, large amounts of labile P are required and, accordingly, these soils have to be managed to counteract the large P sorption capacity of allophane and other Al compounds, and to ensure an adequate supply of labile P. Because of their physical and chemical properties, allophanic soils are excellent filters of heavy metals and pathogens.

This paper summarizes recent results obtained on chemical modifications of smectites. These include replacement of exchangeable cations with protons, a process connected with smectite autotransformation – attack of protons on the layers and liberation of central atoms from the octahedral and tetrahedral sheets, causing modification of the acid sites on the particles. More severe modifications occur during dissolution in inorganic acids, when the layers are dissolved and threedimensional amorphous silica is formed. The negative charge on the smectite layers can be increased via reduction of structural Fe(III) to Fe(II) or decreased via fixation of small exchangeable cations, such as Li+, upon treatment at elevated temperatures. Heating for 24 h at different temperatures between 100 and 300ºC leads to a series of chemically similar materials of different charge, prepared from the same parent mineral. Such series are suitable for investigation of the effect of the layer charge on selected properties of smectites. Fe(II) can be partly stabilized in reduced smectites by Li fixation upon heating.

Intrastratal solution of detrital heavy minerals in North Sea Tertiary sandstones takes place in two different diagenetic settings, deep burial and acidic weathering. These are characterized by different orders of mineral stability: apatite, chloritoid, garnet, sphene and spinel are less stable in acidic weathering than in deep burial, whereas the reverse is true for andalusite, kyanite and sillimanite. Heavy-mineral dissolution patterns, therefore, do not follow one single order of stability but several, depending on the diagenetic environment in which the dissolution occurs. It seems from this that the relative order of stability for detrital heavy minerals is controlled by the chemistry of the interstitial waters, whereas the limits of persistence depend on pore-fluid temperature, rate of water throughput, and geological age. Because different diagenetic environments lead to differing orders of mineral stability, it may prove possible to elucidate certain aspects of the diagenetic history of a sandstone by heavy-mineral dissolution patterns.

This review focuses on the clay mineralogy of the most important Brazilian soils: the Latosols, which cover >60% of the country by area, and occur in association with other soils. They are typically deep, highly-weathered soils, dominated by low-activity 1:1 clay minerals and Fe and Al oxyhydroxides, with varying proportions of these minerals, depending on parent material and weathering intensity. They are usually of low fertility, although eutric types also occur. Latosols are generally correlated with Oxisols (American soil taxonomy) and Ferralsols (WRB system). Clay mineralogy is typically monotonous: kaolinite, gibbsite, hematite, goethite, maghemite and Ti minerals (mainly ilmenite and anatase) are the prominent mineral phases in the clay fraction. Some Latosols developing on basalt from southern Brazil contain significant amounts of hydroxyl-interlayed vermiculite. Among the pedogenic oxides the most frequent are goethite (α-FeOOH), indicated by yellowish colours (2.5Y–10YR; in the absence of hematite), and hematite (α-Fe2O3), which imbues reddish colors (2.5YR–5R), even when present in very minor amounts. Maghemite (γ-Fe2O3) is less frequent; it imparts a reddish-brown colour (5YR–2.5YR) and magnetic properties. Both goethite and hematite show Al-substitution, with a greater relative proportion in soil goethites. Hence, in similar drainage conditions, goethite is less prone to dissolution than hematite. Most reddish Latosols also contain maghemite, due to partial or complete oxidation of magnetite, which generally occurs naturally or is fire-induced. Magnetite and/or maghemite are associated with trace elements which are important in plant nutrition, such as Cu, Zn and Co. The contents of gibbsite in Latosols are extremely variable, from a complete absence in brown Latosols, to 54% in red Latosols from mafic rocks. Relatively large amounts of gibbsite are found in the clay fraction of these soils and this mineral is important in P sorption in deeply weathered Latosols in association with goethite and hematite. Even though most Latosols are dystrophic, some are eutrophic, revealing an unusually large base saturation in areas under ustic regimes where the parent material is particularly rich in bases, such as basalts. This eutrophic nature is attributed to the protecting role of micro-aggregates in ferric red Latosols, which retard baseleaching from the inner aggregate. At the other extreme, some Brazilian Latosols are acric and positively-charged in sub-surface horizons, as revealed by the relationship pH KCl > pH H2O. These acric Latosols are the result of long-term weathering and intensive leaching, during which pH tends to increase to values close to the zero point charge of Fe and Al oxides (between 6 and 7), greatly increasing P adsorption, which is mainly attributed to gibbsite, goethite and hematite. Soil kaolinites in Brazilian Latosols are mostly of low crystallinity, with Hughes and Brown indexes of between 6 and 15. In this review we have discussed the role of these clay-fraction minerals in soil genesis and fertility, highlighting the marked role of inheritance from deeply-weathered parent material. Latosols typically retain large amounts of Fe oxides, some of which are magnetic, with spontaneous magnetization >1 J T–1 kg–1. In this regard, reddish Latosols developed from mafic rocks are the most representative magnetic soils, and cover as much as 3.9% of Brazil. An overview of magnetic soils on four representative examples of mafic lithologies is presented, together with some aspects of their Fe-oxide mineralogy and related field and laboratory technqiues.

The unique properties of imogolite are closely related to its structure, which is a tube of 23–27 Å outer diameter and ∼10 Å inner diameter, with an AIOH outer surface and SiOH inner surface. Acid dispersions contain the long, positively-charged tubes as isolated units or small bundles, which form bulky gels in alkali, and flocculate with negatively-charged colloids, polyvalent anions, and long-chain anionic detergents. Sorption properties are associated with the 10 Å intra-tube pores and with inter-tube channels of variable dimensions. Surface acidity is less than that of layer-silicate clays. The chemical and mechanical stability, biological activity, film- and fibre-forming characteristics, and conditions of synthesis are reviewed, on the basis of both new and published findings. Areas of potential application are indicated.

Dissolution of feldspar and mica and precipitation of kaolinite require a through flow of meteoric water to remove cations such as Na+ and K+ and silica. Compaction driven pore-water flow is in most cases too slow to be significant in terms of transport of solids. The very low solubility of A1 suggests that precipitation of new authigenic clay minerals requires unstable Al-bearing precursor minerals. Chlorite may form diagenetically from smectite and from kaolinite when a source of Fe and Mg is present. In the North Sea Basin, the main phase of illite precipitation reducing the quality of Jurassic reservoirs occurs at depths close to 4 km (130-140°C) but the amount of illite depends on the presence of both kaolinite and K-feldspar. Clay mineral reactions in shales and sandstones are very important factors determining mechanical and chemical compaction and are thus critical for realistic basin modelling.

This paper describes the swelling properties of two highly compacted clays, natural, untreated Wyoming montmorillonite (MX80) and Fourges smectite (FoCa7), saturated with Na and Ca, respectively.

The initially compacted samples were hydrated by subjecting them to different suction pressures in a range between 100 MPa and 1 kPa. For each equilibrium state, the volume change (swelling) and water content (hydration) were measured. The samples were then studied by X-ray diffraction using a transmission device to determine interlayer distance and particle size, in order to clarify both the swelling and hydration mechanisms. The distances between clay layers ranged between 10 and 21.6 Å , i.e. corresponding to between 0 and 4 water layers. Upon hydration, the particle size decreased from 350 and 100 clay layers per particle to 10 layers per particle when the suction pressure decreased from 100 MPa to 1 kPa for MX80 and FoCa7, respectively. The first swelling stage is described as being an insertion of water molecules between the layers. Then a division of the initial particles into particles of smaller size with increasingly large inter-particle distances was observed. Observations by transmission electronic microscopy confirmed these results.

The influence of individual clay minerals on formation damage of reservoir sandstones is reviewed, mainly through the mechanism of fine particle dispersion and migration leading to the accumulation and blockage of pore throats and significant reduction of permeability. The minerals discussed belong to the smectite, kaolinite, illite and chlorite groups respectively. These minerals usually occur in an aggregate form in reservoir sandstones and the physicochemical properties of these aggregates are reviewed in order to reach a better understanding of the factors that lead to their dispersion in aqueous pore fluids. Particularly significant properties include the surface charge on both basal and edge faces of the clay minerals and how this varies with pH, external surface area of both swelling and non-swelling clays, porosity and pore size distribution in the micro- and meso-pore size range and overall aggregate morphology. For non-swelling clays, and perhaps even for swelling clays, dispersion is thought to be initiated at the micro- or meso-pore level, where the interaction between the pore solution and the charged clay surfaces exposed on adjacent sides of slit- or wedge-shaped pores brings about expansion of the diffuse double electric layer (DDL) and an increase in hydration pressure. Such expansion occurs only in dilute electrolyte solutions in contrast to the effect of concentrated solutions which would shrink the thickness of the DDL and so inhibit dispersion. Stable dispersions are formed, particularly where the solution pH exceeds the isoelectric pH of the mineral, which is often at alkali pH values, so that both basal face and edge surfaces are negatively charged and the particles repel each other. The osmotic swelling of smectitic clays to a gel-like form, so effectively blocking pores in situ, is often invoked as an explanation of formation damage in reservoir sandstones. Such swelling certainly occurs in dilute aqueous solutions under earth surface conditions but it is uncertain that stable smectitic gels could form at the temperatures and pressures associated with deeply buried reservoir sandstones.

Replacement of kaolinite by dickite has been observed to occur with increasing depth of burial in sandstones from three different basins on the Norwegian continental shelf. In the Garn Formation (Middle Jurassic) of Haltenbanken, samples from 1.4-2-7 km below the sea floor (110°C) contain kaolinite, whereas deeper than 3.2 km (130°C) mainly dickite is present. In the Statfjord Formation (Late Triassic-Early Jurassic) from Gullfaks and Gullfaks Sør Fields, transformation of kaolinite to dickite occurs at ~3.1 km below the sea floor (120°C) From the Stø and Nordmela Formations (Lower to Middle Jurassic) to the Troms Area, kaolin polytypes have been identified in only two shallow and two deep samples, but the results are consistent with the transformation depth determined in two other areas studied. These occurrences are significant because they allow the temperature of the kaolinite/dickite transformation to be established with greater confidence than had been possible previously. Also the observation of this transformation in all three areas so far examined indicates that it may be a general and predictable feature of kaolinbearing sandstones worldwide and therefore a potentially reliable paleogeothermometer. In most cases, the kaolinite occurs as relatively large vermicular crystals, whereas dickite forms more euhedral, blockier crystals. This morphological difference, together with the nature of the structural difference in octahedral occupancy between the kaolinite and dickite, suggests that the transformation occurs by dissolution and reprecipitation, rather then in the solid state.

IR spectroscopy has shown that adsorbed water is almost completely removed from ferrihydrite by evacuation at room temperature. Absorption bands at 3615 and 3430 cm−1 appearing thereafter are interpreted as arising from OH groups located respectively at the surface and deeper in the structure. These groups are readily converted to OD on treatment with D2O vapour and this has allowed the OH deformation vibration to be identified at 800 cm−1. It is proposed that OH groups in ferrihydrite are about half as numerous as those in akaganéite (β-FeOOH) and that they may occur in environments similar to those in this mineral. The formula for ferrihydrite proposed by earlier workers, 5 Fe2O3.9H2O, should thus be amended to Fe2O3. 2 FeOOH.2·6H2O in order to indicate the presence of structural OH groups. A re-appraisal of the ferrihydrite structure appears desirable.

Kaolinite was intercalated with n-hexylamine, n-octadecylamine and n-docosanamine, using methanol-kaolinite as the precursor. The intercalation compound with n-docosanamine presented the largest basal spacing for a kaolinite derivative thus far reported (64.2 Å). Five grafted derivatives of kaolinite were directly intercalated with n-hexyl- and n-octadecylamine. During intercalation, the grafted molecules rearrange from parallel to perpendicular orientation to the kaolinite surface, in order to maximize the interaction with the amine and minimize the interlayer expansion needed. The octadecylamine intercalation compounds were delaminated in toluene, accompanied by the deintercalation of the amine molecules. Thin kaolinite particles rolled into a halloysite-like morphology, but forming much smaller tubes, some of which possibly consist of single kaolinite layers. The delamination was more efficient with the grafted kaolinites than with raw kaolinite.

The chemical composition of about 500 diagenetic chlorites, determined by electron microprobe, has been studied in six different sedimentary sequences spanning conditions from early diagenesis to low-grade metamorphism, in the temperature range 40–330°C. The range of Fe/(Fe + Mg) is almost complete and is positively correlated with Al. Five sequences show the same compositional variation. In each, the most siliceous chlorites have the lowest R2+, substantially more octahedral than tetrahedral Al, and the lowest octahedral totals. Conversely, the least siliceous have the highest R2+, nearly equal octahedral and tetrahedral Al, and octahedral totals close to that for an ideal trioctahedral mineral. A dioctahedral substitution Si[]R2−2 (where [] represents a vacant octahedral site) which decreases with temperature, describes this variation. Low octahedral totals are, however, induced by the method of calculation and need not indicate vacancies; for published wet chemical analyses of metamorphic chlorites they may simply indicate oxidation of Fe. Intergrown dioctahedral phyllosilicates may partly account for apparent vacancies in diagenetic chlorites. Nevertheless, the correlation of composition with temperature and similarities to the temperature-related evolution of synthetic chlorites, suggest that diagenetic chlorites are compositionally distinct from, but metastable with respect to, fully trioctahedral metamorphic chlorites. Temperature-related trends are modified by bulk composition, complicating their potential use for low-temperature geothermometry.

The materials formed by dialysis of the precipitates formed by the reaction of NaOH with mixed Mg-Al solutions are described. In addition to aluminium and magnesium hydroxides, two hydrocarbonates having Mg/Al ratios of about 5 : 1 and 2 : 1 are formed, essentially pure, from solutions with Mg/Mg + Al molar ratios of 0.8 and 0.7, respectively. X-ray powder data shows that they have partially ordered hexagonal layer structures with unit layer dimensions a = 3.048 Å, layer thickness 7.60 Å for the Al-rich compound and a = 3.072 Å, layer thickness 7.92 Å for the Al-poor compound. X-ray and chemical data show that the new compounds resemble the minerals hydrotalcite and manasseite and also the compounds described as Mg-Al hydroxides by Feitknecht.

This present study provides an overview of the clay-mineral reactions involved in the chloritization process in a mixed-layer mineral series, and focuses on the properties of the resulting lowtemperature chlorites (formed at <220°C) in diagenetic and hydrothermal systems. According to the literature, most chlorite species occurring in low-temperature geological systems are derived fromspecific clay precursors except for direct precipitates from solution in veins. In addition, three main types of clay-mineral series have been associated with these chloritization processes: saponite-to-chlorite, berthierineto- chlorite and kaolinite-to-sudoite reactions. The conversion of saponite to chlorite results in the most common sequence of trioctahedral clay minerals related to the occurrence of Mg-Fe trioctahedral chlorite in a wide variety of hydrothermal and diagenetic to very low-grade metamorphism environments. Two models were proposed in the literature to describe the saponite-to-chlorite conversion through corrensite. The first model is a continuous transition model based on solid-state transformation (SST) mechanisms and is valid in rock-dominated systems (closed micro-systems with very low fluid-rock ratios). The second model is a stepwise transition model based on dissolution-crystallization mechanisms (DC) and is efficient in fluid-dominated systems (open systems with high fluid-rock ratio). The berthierine to Fechlorite transition results in a sequence of trioctahedral phases which are related to chloritization processes in iron-rich and reducing environments. This transformation is a cell-preserved phase transition dominated by a SST mechanismthat operates simultaneously in different domains of the parental mineral and may be considered as a polymorphic mineral reaction. Finally, the conversion of kaolinite to sudoite (Al-Mg ditrioctahedral chlorite) has not been documented like the other two aforementioned conversion series. Despite the scarcity of detailed investigations, the conversion of kaolinite to sudoite through tosudite is considered a stepwise mineral reaction that is dominated by a DC mechanism. From a compilation of literature data, it appears that several parameters of hydrothermal and diagenetic chlorites differ, including the minimal temperature, the textural and structural characteristics and the extents of compositional fields. In hydrothermal systems, discrete chlorite occurs at a minimal temperature near 200°C, regardless of its chemical composition. In diagenetic systems, discrete chlorite occurs at minimal temperatures that vary according to its crystal chemistry (100–120°C for Mg-chlorite as opposed to 40–120°C for Fe chlorite). The strong discrepancy between the lowest temperature at which Mg- and Fe-chlorite form in buried sediments and in geothermal systems should result from drastically different heating rates, heat-flow conditions and tectonism between basins at passivemargins and geothermal systems at active margins. The morphology, structure and compositional fields of the diagenetic Fe-rich chlorite may have been inherited from those of the berthierine precursor. All of the chlorite species formed through theDC mechanism have good geothermometry potential. However, the SST mechanism in which berthierine is transformed into chlorite could have unexplored consequences regarding the use of the chemistry (including stable isotope composition) of diagenetic Fe-chlorite for reconstructing the burial history of sediments. Further investigations regarding the formationmechanisms of mixed-layerminerals are required to provide us with insight to understand the chloritization process in low-temperature geological systems.

Visible to near-infrared (NIR) reflectance spectra and mid-IR transmittance spectra are presented here for a collection of dioctahedral smectites. Analysis of the structural OH vibrations is performed by comparing the NIR combination and overtone bands with fundamental stretching and bending absorption features in the mid-IR region. Second derivatives are used to determine the actual band centres, which are often shifted slightly by a spectral continuum in the reflectance or transmittance spectra. New bands have been identified near 4170 and 4000 cm–1 in the NIR spectra of nontronite with tetrahedral substitution. A related band is observed near 4100 cm–1 for montmorillonites with substantial tetrahedral and/or octahedral substitution. These bands are correlated with the mid-IR bands near 680 cm–1 for nontronite and near 630 cm–1 for montmorillonite. Comparison of the OH overtone and combination bands with the fundamental stretching and bending vibrations gives consistent results.

The more firmly held water which is directly co-ordinated to the exchangeable cations in smectites is clearly distinguished by infra-red spectroscopy from the more labile water in outer spheres of co-ordination. Li+, Ca2+ and Mg2+ retain both types of water to higher temperatures than do K+, Na+ and NH4+, and the former group give stable monohydrates in saponite which are probably not completely decomposed till 400–600°C. K-, Li- and Na-saponite rehydrate completely after heating, but NH4-, Mg- and Ca-saponite are irreversibly dehydrated at 600–700°C, by which temperature NH4+ is also decomposed. NH4-, Li- and Mg-montmorillonite fail to rehydrate after heating to 350°C, and changes in their spectra indicate interaction between the exchangeable cations and the lattice. Decomposition of NH4+ gives H-montmorillonite, but the products from Li- and Mg-montmorillonite are also acidic, and give spectra similar to that of H-montmorillonite. Na- and Ca-montmorillonite do not rehydrate after heating to 500–550°C, and K-montmorillonite rehydrates only partially in the range 350–550°C. Dehydration of saponite and montmorillonite at low temperatures causes changes in lattice vibrations which are reversed on rehydration. The spectra of the products of dehydroxylation of montmorillonite and saponite are slightly affected by the exchangeable cation originally present.

Poly(ethylene glycols) of molecular weights 200 to 20000 were strongly adsorbed on montmorillonite from aqueous solution. Free energies of adsorption calculated from the adsorption isotherms became more negative with increase in molecular weight and the entropy change became increasingly positive, probably due to a net desorption of water from the clay surface as the organic compound was adsorbed. The adsorption of the higher molecular weight polymers caused an increase in the interlamellar separation. The effect of the exchangeable cation on the adsorption followed the order Cs > Na > Ca > Al, indicating that the cation retained its hydration shell and did not form a direct association with the adsorbed organic molecules. Some evidence was obtained that 'water bridges' were formed between exchangeable calcium an aluminium ions and the ether groups of the polymers.

Subarkosic arenites of the Middle Jurassic Garn Formation are important hydrocarbon reservoirs in the Haltenbanken area. XRD and petrographic analyses of core samples from 11 wells show that a transition from incipient to extensive illitization in these sandstones is associated with a present burial depth of 3·7 km below the sea floor, corresponding to a formation temperature of 140°C. Illite has formed by reaction between K-feldspar and earlier diagenetic kaolinite and probably also by alteration of mica. Although several of the cores are filled with hydrocarbons that probably were in place before base-Eocene (57 Ma), there are no indications that illitization was inhibited by the presence of hydrocarbons in pore spaces. It is therefore suggested that 20–30% residual water saturation is sufficient for extensive illitization to occur by short-range diffusive transport in a compositionally closed system. There is an unresolved problem regarding both the timing and cause of illitization. On the one hand, the extent of illitization in the 11 wells correlates with variations in both present formation temperature and thermal maturity, implying that the present burial depth of 3·7 km below the seafloor coincides with a critical thermal threshold for illitization. According to this interpretation, the times of illitization in the different wells should correlate with variations in burial history and should in several cases be as young as 3 Ma, when deposition of one kilometer of glacially-derived sediment sharply increased temperatures throughout the Haltenbanken area. On the other hand, conventional K-Ar analyses of illite separates give dates ranging from 31–55 Ma. In general, these dates appear to be too old to fit the interpretation that the degree of illitization is a simple function of present temperature or thermal maturity. This inconsistency may reflect errors in the K-Ar dates due to a contamination problem.