The effect of gypsum additions on the physical performance of lime-stabilized kaolinite has been determined. Kaolinite containing different amounts of lime (i.e. 6 and 14 wt%) and gypsum (i.e. 2,4,6 and 8 wt%) was compacted into cylinders and moist cured at 30°C and 100% r.h. for periods from 2 days up to 20 weeks. Unconfined compressive strength, expansion during curing and subsequent soaking, and water absorption and swelling pressure were determined. The addition of lime and subsequent moist curing was found to reduce substantially the water absorption, linear expansion and swelling pressure of the kaolinite. Although small amounts of gypsum further reduced these parameters, higher gypsum levels (up to 8 wt%) produced substantial water absorption, extreme expansion and high swelling pressures. This excessive volume instability when in contact with water was found, for a particular lime content, to be very sensitive to both the initial moist curing time and the gypsum content. The results indicate that the overriding expansion mechanism operating is imbibition of water or transfer of water by osmosis. The question of what drives this process is the subject of Part II of this paper.

Rock weathering has been investigated from atomic to global scales through the different but complementary approaches of mineralogy, petrography, geomorphology and geochemistry. The sequences of mineral reactions involved in the alteration process are now well known. They explain the global trend of weathering phenomena but do not account for the actual rock transformation dynamics. In particular, they ignore the intimate relation of the mineral reaction progress with the increase in connected porosity. At the hand specimen scale, heterogeneity is the rule: mineral reactions are controlled by local physicochemical conditions. Alteration processes depend largely on the rock microstructure properties. They proceed through nearly-closed, semi- and completely open microsystems which are interconnected by fractures or pores. Before being leached out by the solutions which flow in the large fractures (flux), the soluble elements migrate inside the connected porosity through chemical diffusion. The dissolution of the primary minerals is mediated through local gradients of chemical potential. With increasing alteration, the rock porosity increases, as does the length of the fluid passageways and their constrictivity and tortuosity. Consequently, the apparent diffusion coefficient for the most soluble elements decreases. The amplitude of the chemical potential gradients for the most soluble elements is reduced by the progressive coating of the reactive surfaces by clays and Fe oxyhydroxides. The residence time of these elements inside the weathered rock increases as alteration progresses; an effect enhanced by their temporary adsorption on the exchangeable sites of clays and Fe oxyhydroxides. Consequently, the weathering rate decreases with time. A possible new way to calculate weathering rates could be to measure the residence time of soluble elements inside the different microsystems during their migration towards the diluted solution which occurs in the large fractures.

The determination of kaolinite order-disorder by X-ray diffraction is problematic due to overlapping peaks from associated kaolin minerals and X-ray amorphous phases. This paper presents a new index (Aparicio-Gala´n-Ferrell index — AGFI), measured on 02l and 11l reflections after decomposing individual peaks in the complex diffraction band in an effort to reduce interferences. The new index was tested with three kaolins, of varying structural order, and their admixtures containing different percentages of quartz, feldspar, illite, smectite, chlorite, halloysite and Fe hydroxides and silica gels. The AGFI is highly correlated with the percentage of low-defect kaolinite and the Hinckley Index. It is not as prone to interference by associated minerals and X-ray amorphous phases as other indices. The AGFI can be used to determine kaolinite order-disorder in a wide variety of kaolins and kaolinitic rocks; the only prerequisite is that the kaolinite content should be >10 wt.% in order for the results to be reproducible.

Distribution coefficients and isotherms for the adsorption of radioiodide, caesium and strontium ions (125I−, 134Cs+ and 85Sr2+) were determined in untreated vermiculite and in vermiculite treated with the chloride salt of hexadecylpyridinium (HDPy+). Experimental data reveal that some of the alkylammonium ions were incorporated as HDPyCl ion pairs into the vermiculite. The fraction of ion pairs adsorbed is reflected by an increase in distribution coefficients with increasing saturation levels. Consequently, a considerable part of the iodide adsorption could be attributed to an anion exchange process. At smaller amounts of Cs+ and Sr2+ adsorbed, distribution coefficients of the modified clay mineral are significantly reduced in comparison with the original material. These differences are less pronounced when greater amounts of cations are adsorbed. Generally, larger distribution coefficients were found for the Cs+ compared with the Sr2+ ion in the untreated and modified samples.

The OH-OD exchange of kaolin minerals through contact with D2O introduced into interlayer space via intersalation resulted in a partial shift of the OH absorption bands. The total decrease in OH absorbance upon deuteralion was 52, 56, and 47% for the kaolinite, dickite-nacrite, and halloysite respectively, but the percentage decrease differed for the different absorption maxima of any one mineral. A secondary OH—OD exchange in the deuterated specimens was also observed upon heating to 350 and 400° C. These data together with the lack of deuteration in montmorillonite, and available orientation data on the kaolin OH groups by infrared spectroscopy, suggest that only two-thirds of the inner-surface OH groups form the interlayer OH—O bonds.

Imogolite structures in allophanic clays can be recognized and semi-quantitatively estimated by an absorption band at 348 cm−1. Allowance can be made for interference by aluminous dioctahedral layer silicates present in small amounts.

Strongly held carbonates anions in the interlayer region of pyroaurite-type compounds, [MlII1−xM2IIIx(OH)2]x+[(CO3)x/2yH2O]x− (x = 0·15−0·44), can be relatively easily exchanged by other anions such as NO3−, Cl− or SO42− dissolved in heated glycerol. Some Fe(III) of pyroaurite is reduced to Fe(II) by the glycerol treatment. If pyroaurite is treated with glycerol in the absence of dissolved anions or with glycerol vapour at 120°C, glycerol becomes intercalated in the interlayers. In all examples the interlayer CO32− is partially or completely lost as CO2. In aqueous salt solutions a glycerol intercalated form allows other anions to substitute in the interlayer. Expansion in the c-axis direction following glycerol treatment depends on (1) the method of glycerol treatment, (2) the trivalent metal in the octahedral sheet, and (3) the interlayer anions. Heated glycerol causes a different expansion to that produced by its vapour phase at 120°C. The variation in d(003) follows the series: hydrotalcitevap. > pyroauritevap. > hydrotalciteliquid > pyroauriteliquid > SO42−-pyroauritevap. > SO42−-hydrotalcitevap., where liquid refers to glycerol used at 160–180°C and vap. refers to glycerol vapour at 120°C Carbonate-free, glycerol-intercalated pyroaurite compounds may serve as re-usable anion absorbers. Glycerol intercalates of pyroaurite-type compounds may also be useful to study and identify stacking sequences and interlayer compositions in these minerals.

Close relationships are demonstrated between reservoir quality, lithofacies, provenance and burial history in the Jurassic Brent and Viking Groups in the Norwegian North Sea. Porosity and permeability are strongly and systematically related to the initial texture and composition of the sandstones. Porosity variations are related to the amount of compaction, which is more severe in matrix-rich than in clean facies, and quartz cementation, which is most important in clean facies. Permeability variations are related to porosity and facies-controlled variations in grain size, and abundance and texture of intergranular fines. Illitization of early diagenetic kaolins require K, which is derived mainly from dissolution of K-feldspar. Sediments were sourced from K-feldspar- poor provenances during the maximum progradation of the Brent Group, and sandstones deposited at this time are less exposed to illitization and have better permeability at deep burial than reservoir sandstones that initially contained more K-feldspar.

X-ray diffraction (XRD) patterns of a pore-lining diagenetic chlorite (14 Å) from a reservoir sandstone, offshore Norway, show broad odd-order and sharp even-order basal reflections indicating that it contains 7 Å layers. Using NEWMOD, simulated XRD patterns with 15% 7 Å serpentine layers and a maximum crystallite thickness of 30 layers match the natural mineral well. Microprobe analyses of the 7 Å-14 Å mineral indicate that it is Fe-rich and aluminous suggesting that it is interstratified berthierine-chamosite. Apparent octahedral vacancies, however, suggest a significant dioctahedral component, and an alternative interpretation is interstratified kaolinite-chlorite. Indeed, chemical analyses of the mineral suggest a mixture of chlorite with 15% kaolinite, precisely the proportion of 7 Å layers indicated by XRD. Two other examples from the literature, previously identified as diagenetic chlorite, are probably also 7 Å-14 Å interstratified minerals, and the proportion of 7 Å layers indicated by XRD is also correlated with their structural formulae, if the 7 Å layers are, in fact, kaolinitic. This type of interstratification could explain why Fe-rich diagenetic chlorites appear to be compositionally distinct from metamorphic chlorites. The structure and chemistry of the Norwegian chlorite tend to support the idea that pore-lining chlorites form early in the diagenetic history, inhibiting the precipitation of later diagenetic minerals, and hence preserving abnormally high porosity at greater depths.

Recent examination of clay-materials from several different sources has suggested to us the existence of a type of chlorite capable of the same kind of expansion along the c-axis by imbibition of glycerol, as is shown by montmorillonoids, vermiculites and halloysites. The expansion occurs within the range of 14 kX to 18 kX.

It is necessary to discuss the definition of chlorite in this connexion, since such expansion is not regarded as characteristic of any of the minerals to which the name has been given. The characteristics by which chlorites are generally identified from their X-ray diffraction patterns are twofold: (1) they give basal reflexions at approximately 14 kX and submultiples, the first four orders being usually strong and of comparable intensity, though differing in different species of chlorite; (2) these reflexions persist after heating at 500°C.

This article reviews that clay literature from the last ten years, which is devoted to the applications of clay minerals in the interpretation of geological processes in sedimentary basins. The results, selected by the author as being of particular interest, are presented, arranged according to the successive phases of the rock cycle.

Porous, high surface area solids have been prepared by intercalation of a trinuclear acetato hydroxy-iron(III) complex cation between the layers of montmorillonite and the resulting materials have been characterized in order to identify the nature of the iron intercalates formed during and after the cation exchange step. Spectroscopic studies demonstrated that at 623 K, the iron complex was partially decomposed and α-Fe2O3 was only detected in samples heated at high temperatures, > 923 K. Under these conditions, the dehydroxylation of the montmorillonite layers led to the collapse of the structure.

The distribution of Fe3+-kaolinite, Al-goethite and Al-hematite and their contents of Fe and Al in bauxites and ferricretes are controlled by water activity, dissolved silica activity, temperature and particle size. The proposed model, based on ideal solid-solution equilibria in the Fe2O3-Al2O3-SiO2-H2O system, takes into account water and silica activities. By using the same considerations as those previously developed for the Fe2O3-Al2O3-H2O system, the model calculates the amounts of coexisting phases, Al or Fe substitution ratios in goethite, hematite or kaolinite, and the stability field distributions of the minerals under various conditions. Thermodynamic equilibrium conditions and element distributions within the mineral constituents are shown to be dependent on the parameters cited above. The model yields results compatible with natural observations on lateritic profiles.

The adsorption of cerium(IV) by both natural and Na-exchanged kaolinite from aqueous solutions of ceric ammonium nitrate was studied in equilibrium systems. Cerium may be adsorbed either as a monomeric species or as a polymeric hydroxy cation. The species adsorbed depends on the concentration of cerium in the stock solution, the age of this solution prior to the preparation of the equilibrium system and on the equilibration period. Adsorbed cations undergo polymerization on the surface of the kaolinite; the resulting polymeric species forms strong bonds with the clay surface—it is not desorbed by sulphuric acid—and may be considered fixed. Adsorption of cerium reaches a maximum in solutions containing 0·15 M sulphuric acid.

This study focused on whether the presence of clay minerals (montmorillonite and kaolinite) in marine or coastal environments contaminated with high concentrations of heavy-oil spills were able to support the growth of hydrocarbon degraders to enable bioremediation. The bacterial growth experiment utilizing ~150 g/l of heavy oil (from the Nakhodka oil spill) was conducted with 1500 mg/l of montmorillonite or kaolinite. Bacterial strain Pseudomonas aeruginosa (isolated from Atake seashore, Ishikawa Prefecture, Japan), capable of degrading heavy oil, was employed in combination with other hydrocarbon degraders inhabiting the heavy oil and seawater (collected from the Sea of Japan). The interactions among microbial cells, clay minerals and heavy oil were studied. Both clays were capable of promoting microbial growth and allowed microorganisms to proliferate (to a greater degree than in a control sample which contained no clay) in an extremely high concentration of heavy oil. Observation by transmission electron microscopy of the clay-oil-cell complexes showed that microbial cells tended to be bound primarily on the edges of the clays. X-ray diffraction analysis showed that the clay-oil and clay-oil-cell complexes involved the adsorption of microbial cells and/or heavy oil on the external surfaces of the clays. How do the interactions among clay minerals, microbial cells and heavy oil contribute to environmental factors influencing the bioremediation process? To our knowledge, there are no previous reports on the use of clay minerals in the bioremediation of the Nakhodka oil spill in combination with biofilm formation.

The phase changes that took place upon heating an Fe-rich illite (OECD #5) to 1300°C in an oxidizing atmosphere were studied by a variety of mineralogical techniques. Infrared spectra, showing the stepwise dehydroxylation of the illite, showed good agreement with variations in sample colour and Mössbauer spectra. Dehydroxylation did not lead to noticeable variations in X-ray powder diffraction patterns until the structural breakdown of illite and formation of new phases at about 900°C Mössbauer spectroscopy proved to be very sensitive to all changes induced by heating, showing the disappearance of Fe2+ at 250°C, the gradual dehydroxylation between about 350 and 900°C, and characteristic features of the products formed at higher temperatures, e.g. the formation of hematite as the illite structure breaks down and the subsequent disappearance of hematite due to the incorporation of Fe in glass above 1200°C. The formation of hematite in clusters large enough to order magnetically at room temperature was first observed in the sample heated to 900°C, whereas at 4.2 K, significant proportions of a magnetically ordered phase could already be identified in the sample heated to 650°C.

Water-sorption isotherms and interlamellar spacings were measured for Ca montmorillonite (from Redhill. UK) over the relative pressure range 1 > P/P0 > 0. By taking account of the change in interlamellar volume with relative pressure, it is shown that internal and external surfaces can be calculated by a modified t-plot analysis. The results also show that sorption on the external surfaces of the montmorillonite is quantitatively similar to that on reference oxide surfaces. Desorption-sorption hysteresis occurred and was apparently caused by an ageing process in which the interlamellar volume increased at the expense of the external surfaces.

The kaolin minerals in lateritic weathering profiles on dolerite and granite in Western Australia have been characterized by intercalation tests for halloysites, and also by their particle morphologies. Towards the surface of the profiles there is a decrease in both total kaolin mineral content, and in the expandibility of those minerals to intercalation. Tubular kaolinite that is non-expandible by any of the intercalation tests for halloysite was identified in the upper few metres of both profiles. Hydrated halloysite is most common at the base of both profiles. Formamide expands some anhydrous kaolin minerals while the sequence of hydrazine/water/glycerol (HWG) expands more of these minerals. Non-tubular (subhedral to sub-hexagonal platy) kaolinite is also present. Hydrated tubular halloysite apparently alters to tubular kaolinite via dehydrated halloysite that is expandible by formamide and a tubular ‘kaolin’ that is expandible by HWG but not by formamide.

The influence of grinding on colour and particle-size properties of talc and smectite from a white bentonite were studied and compared with a fine-grained calcite from a chalk. Grinding decreased the grain size of all three minerals. The crystallite size and structure of smectite was not affected but the crystallite size of talc decreased. The Si–O–Mg and Mg–O bonds of talc were disrupted and cation exchange capacity increased with increasing grinding. Delamination of talc crystallites was observed in the initial stages of grinding, whereas with more intense treatment, amorphous material was formed. Comminution improved the colour properties of all three minerals, namely brightness, L* (lightness) and ΔE*ab (deviation from perfect white diffuser). Grinding time exerts greater influence on the reflectance from calcite surfaces than from clay minerals. This difference is attributed to continuous formation of progressively smaller diffuse reflection units forming a smoother calcite surface. Decrease of grain size does not form considerably smaller diffuse reflection units in clay minerals unless delamination takes place. With prolonged grinding, amorphization forms additional diffuse reflection units and a smoother surface due to comminution.

Deeply buried (> 3·5 km) Rotliegend aeolian sandstones in the Southern North Sea Basin display a number of interesting diagenetic features including (i) zoned iron-rich carbonate cements, (ii) anhydrite, halite and baryte cements, (iii) at least two generations of authigenic illite, and (iv) significant secondary porosity created by cement and framework-grain dissolution. The creation and destruction of secondary porosity is the result of changes in porewater chemistry during burial and subsequent uplift. Three pore-fluid regimes can be identified: (1) alkaline, oxidizing conditions during shallow to intermediate burial; (2) acid, reducing conditions during intermediate to deep burial; (3) alkaline, reducing conditions during deep burial and uplift. The transition from stage 1 to stage 2 was probably caused by expulsion of waters from the underlying Carboniferous shales. The transition to stage 3 probably began when faulting associated with uplift allowed invasion by alkaline fluids derived from Zechstein sediments.