When describing clay minerals of natural origin one often has to take into account the possibility that they contain other phases, e.g. iron oxides and hydroxides which may form a ‘coating’ on the clay mineral itself or occur as physically inseparable ultra-fine particles. These iron oxyhydroxides are sometimes difficult to detect by XRD as a consequence of their very small ‘domain volumes’ (Kodama et al., 1977). The iron oxyhydroxides are normally removed chemically prior to detailed characterization of the clay mineral. Removal of iron oxyhydroxide coatings facilitates dispersion and subsequent particle-size fractionation of minerals and soils and also enhances the parallel orientation, and therefore the intensity, of basal X-ray reflections of layer-silicates.

The Etive Formation of the Middle Jurassic Brent Group in part of the Northern North Sea comprises dominantly clean, fine- to medium-grained sands, deposited as part of a barrier-bar complex. The overlying Ness Formation was deposited on supra- or intertidal fiats, and comprises silty channel sands with silts, muds and thin coals. The sands of both Formations are mainly quartz-rich, with up to 12% by volume of feldspar, and variable proportions of clayey matrix. Early carbonate cementation preceded a phase of quartz overgrowth, which continued during burial. Later dissolution of unstable grains, dominantly feldspars, was followed by precipitation of pore-filling kaolinite and minor late-stage mineral phases. Better permeability of the Ness sands (up to 500 mD) relative to the Etive (mostly <10 mD) is mainly due to the effects of diagenesis on different lithofacies. Silty sands escaped intense quartz cementation and were thus more affected by acid groundwaters which improved permeability.

The data obtained on zeolites, kaolins, alunites, hydrated sulphates and soils by DTA-TG-EGA carried out under various experimental conditions are discussed. Among the main subjects dealt with are chabazite and phillipsite identification and their quantification by TG, clay mineral distribution in size fractions of kaolins, significance and use of thermoanalytical data from alunitic rocks, the influence of calcite and calcined kaolinite on the sulphate DTA curves, rates of decomposition of hydrated sulphates, and thermal analysis of soils in forensic studies.

L'argile blanche en provenance du sol ferrallitique dérivé de matériaux pyroclastiques de Vaté (Vanuatu) possède un rapport moléculaire SiO2/(Al2O3 + Fe2O3) proche de 2, est riche en fer (∼7% Fe2O3) et se présente sous forme de fines lamelles irrégulières et parfois froissées. Sous l'effet de tout traitement de déshydratation, l'espacement basal de cette argile passe progressivement de 10 Å vers 7 Å. Toutes ces caractéristiques permettraient son identification comme halloysite (10 Å) ferrifère hydratée. Cependant, les spectres de diffraction des rayons X de cette argile déshydratée puis déshydroxylée ne correspondent pas à ceux que l'on obtient pour une halloysite ‘normale’. Ils révèlent plutôt la présence d'un édifice interstratifié 1:1/2:1 où le minéral 2:1, présent à raison de 20% environ, est dioctaédrique. En outre, la CEC de ce matériau (∼44 mEq/100 g à pH 4) est anormalement élevée pour un minéral 1:1. Par spectroscopie Mössbauer, on établit que la quasi-totalité du fer présent dans cet échantillon doit être localisée en position octaédrique au sein d'un phyllosilicate. Comme ce fer est ferrique, son inclusion dans la couche octaédrique d'un minéral 1:1 ne pourrait justifier l'importante charge négative permanente que porte cette argile. En réalité, toutes les propriétés reconnues pour ce matériau justifient son identification comme minéral interstratififé de 80% environ d'halloysite et de 20% de smectite ferrifère. Certaines particularités des spectres d'infrarouge, notamment l'absence des bandes à 3560 et 820 cm−1 caractéristiques des vibrations d'élongation et de déformation des hydroxyles de la nontronite, suggèrent que la smectite ferrifère inclue dans l'édifice interstratifié pourrait être une hisingérite dioctaédrique.

Solid-state 29Si and 27Al NMR spectroscopy with magic-angle spinning was used to study two smectites, two illites and a vermiculite. 27Al NMR was able to directly observe the coordination of aluminium. 29Si NMR was sensitive to both the chemical nature of the interlayer species and the presence of aluminium in the tetrahedral sheet. Well-resolved resonances in the vermiculite at δ = −84·6, −88·7 and −92·9 (ppm relative to TMS) were assigned to Q3(2Al), Q3(1Al) and Q3(0Al) respectively. The smectites exhibited single resonances centred at δ = −93 (Q3(0Al)). The illites displayed broad resonances between δ = −80 and −105. The 29Si spectrum of a smectite complexed with alkylammonium cations showed a shielding of up to 1 ppm relative to the untreated sample.

Sepiolite is an Mg-silicate with fibrous morphology. Its structure consists of talc-like ribbons parallel to the fibre axis. Although the tetrahedral sheets are continuous, the apices in adjacent ribbons point in opposite directions, each ribbon alternating with an open channel along the fibre axis. Tetrahedral positions are normally filled with Si atoms. The width of the ribbons corresponds to eight octahedral positions, which are, normally occupied by Mg atoms, and the channel cross-section is 3·8 x 9·4 Å. This structure gives the mineral a high adsorptive capacity and molecular sieve capability. The ideal mineralogical formula is (OH2)4(OH)4Mg8Si12O30.8H2O (Brauner & Preisinger, 1956).

Activation of sepiolite by acid attack has been extensively studied (Fernández-Alvarez, 1972; Jiménez-López et al., 1978; Rodríguez-Reinoso et al., 1981). This note describes the changes undergone by sepiolite during dissolution of the octahedral Mg-sheet by HCl attack, silica gel being the end-product. This process was followed by IR spectroscopy, study of Mg-extraction kinetics, and morphological observations by SEM and TEM.

Emphasis is placed on the advantages of combining simultaneous thermal analysis methods (TG-DTA-DTG) with other complementary physico-chemical techniques for investigating synthesis and various properties of zeolites belonging to the pentasil family. TG and DTA give quantitative information on the dehydration and decomposition of organic guest molecules that interact with intermediate phases obtained during hydrothermal transformation of amorphous aluminosilicate gels into crystalline zeolites. In particular, weight losses (TG) and heat effects (DTA) due to the oxidative decomposition of tetrapropylammonium ions occluded in an intermediate phase have been related to the amount of zeolite ZSM-5 present. As a result, very small particles of this zeolite, amorphous to X-rays, could be detected in the early stages of the crystallization process. Isothermal sorption of small hydrocarbon molecules (n-hexane, 3-methyl-pentane) is used to probe the intracrystalline pore volume of zeolite ZSM-5. The total hydrocarbon uptake (TG) and the shape of the corresponding DTA peak are sensitive to steric modifications of the ZSM-5 channel system by various chemicals, while the sorption rates are better correlated to the extent of zeolite surface poisoning by boron or carbon. TG-DTA data provide an easy means of describing the filling and packing of n-hexane in ZSM-5 pore structure. Various steps characterizing isothermal competitive sorptions (nitrogen, ethylene, water) or catalytic conversions at high temperature (ethylene, methanol) over H-ZSM-5 are described. Finally, the progressive formation (removal) of carbonaceous residues resulting from these transformations are related to the actual rate of de-activation (re-activation) of a zeolitic material. In this respect, three different synthetic zeolites, namely mordenite, offretite and H-ZSM-5, which differ by their shape-selective properties and structure of their channel network, are investigated by TG.

La formación Fardes consiste en secuencias alternadas de turbiditas y hemipelagitas. Estos sedimentos han sido silicificados diagenéticamente y se presentan como estratos gruesos de color amarillo, que contienen jarosita y sideronatrita, inicialmente depositados en un medio reductor. Los niveles hemipelagíticos se pueden considerar por su composición quimica y mineralógica como bentonitas, compuestas principalmente de esmectitas, mica y cuarzo. En algunos casos se han encontrado asimismo, calcita, dolomita, halita y yeso. En la fracción <2 µm el mineral más abundante es la esmectita (48%) seguido por la palygorskita y la mica (28% y 32% respectivamente). La composición de la esmectita corresponde a los miembros ricos en Fe de la serie nontronita-beidellita; las micas son verdaderas moscovitas y la paligorskita tiene contenidos anormalmente altos de Fe y Al. Evidencias mineralógicas y geoquimicas indican que estas bentonitas son productos de alteración de rocas volcánicas, posiblemente, andesitas calcoalcalinas.

Rodrique et al. (1972) reported that kaolinite was formed at 200°C from gels with an A12O3/(A12O3 + SiO2) weight ratio ⩽0·315 and pH values ranging from 4·8 to 5·8. At this temperature and using a gel with an A12O3/(A12O3 + SiO2) weight ratio >0.315, boehmite and pseudoboehmite, were obtained at pH values of up to 5·8. The latter minerals were also observed in the products formed under similar conditions at 175°C.

Unlike the situation under acidic conditions, where gel composition is important, the gel/solution ratio becomes critical under alkaline conditions. When the gel/solution ratio is low, zeolites are produced from a gel with a weight ratio between 0·3 and 0·5 in the presence of NaOH at 130-170°C (De Kimpe, 1976). When the gel/solution ratio is high, kaolinite instead of zeolites is formed under similar conditions (De Kimpe, 1969, 1976). For an intermediate gel/solution ratio, smectite is produced from a gel with a weight ratio of 0.4 in the presence of NaOH at 175°C In the presence of KOH, however, kaolinite is the only crystalline product formed under similar pH and temperature conditions (De Kimpe et al., 1981).

The extent of diagenesis in Lower Jurassic shoreline sandstones of the Beatrice oilfield was controlled primarily by their detrital clay content. Sandstones rich in detrital clay had low depositional permeabilities; these show preservation of detrital feldspars to the present day and have no extensive diagenetic quartz overgrowths. Sandstones poor in detrital clay had high permeabilities and show large quartz overgrowths as part of a normal sub-arkosic diagenetic sequence. Such quartz occurs preferentially below, but not above, impermeable mudstones. These low- and high-permeability features suggest that pore-fluid flow was important during diagenesis. Fluid inclusions trapped in diagenetic quartz overgrowths formed between 68° and 94°C. This silica was probably supplied in solution from the temperature-driven illitization of smectitic clays surrounding these sandstones deeper in the basin. Fluid volumes from clay dewatering, from mechanical compaction, or from influx of overlying seawater were too small to transport diagenetic silica volumes. Silica-rich fluids were probably transported up-dip by convective cells within the sandstones and authigenic quartz precipitated as these fluids cooled. This episode of quartz diagenesis could have been completed within 1·6 × 106 yr if fluid velocities were 3·1 m/yr. Similar convective fluid flows could have transported the fluids responsible for secondary porosity development and the hydrocarbons expelled from mudstones later in the basin burial history.

The amount of Fe and Al extracted from soil by 0·1 M pyrophosphate (Fep, Alp) has long been used as a criterion in the designation of spodic horizons of podzols (Avery, 1973). Although Adams et al. (1980) showed that in a group of podzolic soils developed from Lower Palaeozoic sedimentary (LPS) rocks Fep was very closely correlated with the quantities of Fe eluviated and illuviated, such evidence validating the use of pyrophosphate is not generally available. Recently there has been renewed interest in the identification of forms of Fe and Al extracted by pyrophosphate in order that greater confidence might be gained in the use of Fep and Alp in soil classification (McKeague & Schuppli, 1982).

Our interest in pyrophosphate extraction was stimulated when Nto (1981) discovered that Fep was an excellent predictor of P sorption in soils developed from LPS rocks. Indeed, the level of predictability was not improved by the inclusion, in multiple regressions, of either Fe or Al extracted by any other of the commonly used selective extractants.

The electron microprobe has been used in petrographic research for almost 20 years and more recently as a tool for investigations of clay minerals. However, to the author's knowledge no information has been published concerning the reliability of such analyses―especially those of the alkali elements. Since the alkali contents of clays are often critical, e.g. in determining the smectite content of mixed-layered minerals, it is important to have some idea of the reliability of an analysis made using an electron microprobe.

Three variables can be controlled in electron microprobe analysis—time, beam-current intensity and beam size (the diameter of the beam which excites the sample). Exaggerated conditions of any one of these variables tend to diminish the signal received by the detectors for the alkali elements, especially sodium. As an example, the effect of varying two of these parameters on the intensity of sodium radiation for sodium-aluminumsilicon glass is shown in Fig. 1. The signal decreases (% loss Na) over a 200 s counting time. Beam intensity and beam diameter were varied in this example.

Reactions undergone by leadhillite from the type locality on heating to 1000°C have been followed by DTA, TG, DSC, evolved gas analysis, continuous-heating XRD and IR, and hot-stage microscopy. Intermediate decomposition products were identified by X-ray powder photography. At 80°C, biaxial leadhillite inverts to a uniaxial phase with properties similar to those of susannite, a naturally occurring polymorph of leadhillite, but this higher-temperature modification only partially reverts to the original structure on cooling (up to 24 hours at room temperature is required for complete reversion). Between 250 and 600°C the mineral undergoes two decomposition reactions: PbO.PbCO3 and PbO.PbSO4 form during the first reaction (PbCO3 may form in the initial stages) and 4PbO.PbSO4 during the second. α-2PbO.PbSO4 appears at 650°C due to solid-state reaction between the other lead oxysulphate products. Melting occurs above 850°C. The reaction products are discussed in relation to the phase diagrams for the systems PbO-CO2 and PbO-PbSO4.

The results obtained from this study of kaolinite dehydroxylation explain why different investigators have ascribed both first-order kinetics and a diffusion mechanism to this reaction. The fact that activation energies reported by these workers agree well, in spite of the different kinetics assumed when performing the calculations, is also explained. From a comparison of the results obtained by isothermal and non-isothermal methods it is concluded that, for reacted fractions, α, <0·6, kaolinite dehydroxylation is controlled by a diffusion process. A reaction mechanism explaining this behaviour is proposed.

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.

Much interest has been shown in IR cells capable of maintaining one or more samples at constant temperature, constant water vapour or gas pressure, or under vacuum conditions (Farmer, 1974). This note describes a cell capable of maintaining a vacuum between 10-3 torr and 10-4 tort from room temperature to 1000°C whilst the spectrum is being recorded; such cells have been constructed previously but for less severe conditions.

The cell and associated vacuum system are shown schematically in Fig. 1. The vacuum in the cell body is produced by an Edwards rotary pump and a normal mercury diffusion pump. To obtain a vacuum of 10-3 to 10-4 torr, a liquid nitrogen trap and foreline trap are used. The trap is filled with activated alumina. The O-ring seals in the cell are made of Viton. The constant vacuum control is obtained with Pirani and Penning gauges.

Petrological studies of the Sherwood Sandstone of the Marchwood Borehole show that the formation is made up of two units of differing primary lithological character: a lower unit with lithic sandstone and conglomerate, and an upper unit with arkosic sandstone. A combination of compaction and calcite cementation (early and late) has severely reduced porosity and permeability in the lower unit. In the upper unit compaction is again important, but several beds have largely escaped cementation, and their primary porosity has been enhanced by leaching of feldspars. The secondary porosity reaches 7% in some samples. Oxygen and carbon isotope data for the early (calcrete) cements indicate isotopic equilibrium with typical freshwater compositions. The later cements yield more variable values, indicating precipitation under a wider range of conditions.

The spectrum of Ni-substituted lizardite, (Mg,Ni)3Si2O5(OH)4, has been discussed by many authors, who have successively given contradictory interpretations concerning the symmetry of the Ni-sites. Lakshman & Reddy (1973) affirmed that in garnierites Ni is in a tetrahedral site. Faye (1974) rejected this conclusion and showed that Ni2+ occupies an octahedral site. However, the Ni … O distance of 2·01 Å which he deduced from the intensity of the crystal field is unacceptable. Recently, using a completely different approach to the interpretation of the spectrum, Cervelle & Maquet (1982) claimed that Ni2+ occupies a six-coordinated site of C3v symmetry, and concluded that the mean Ni … O distance is 2·06 Å.

The aim of this note is to show that it is possible to interpret the spectrum of Ni-lizardite as arising from a predominantly octahedral field with a weak C2v component which provokes a small increase in width of the absorption bands.

Two iron ore samples from Nigeria have been examined using TG, DTA, EGA, XRD, and optical and electron microscopy. Itakpe iron ore is hematite-rich, this mineral being intergrown with magnetite, and silica is the major impurity. Agbaja ore is an acidic oölite ore consisting of goethite and magnetite, with alumina, silica and phosphorus as major impurities. Itakpe is typical of a rich ore formed by magmatic segregation whilst Agbaja is a lean ore of sedimentary origin. Isothermal mass-change measurements in hydrogen and carbon monoxide in the range 800–1100°C show Agbaja to be less reducible than Itakpe; in particular, Agbaja is very irreducible at 1100°C because of sintering of the ore. Characterization and reducibility experiments were also carried out on Corby (Northamptonshire, UK) iron ore for comparison.