The equilibrium H- and O-isotope fractionations can be approximated by the following equations which are based on experimental, empirical and/or theoretical data:

The equilibrium H-isotope fractionation factors vs. 106 × T−2 for kaolinite and probably smectite and illite are monotonic curves between 350-0°C. More complex curves, with a minimum fractionation near 200°C, are probably influenced by surface effects and/or disequilibrium fractionations among the different hydrogen sites. The H-isotope fractionations between smectite-water increase by ~70‰ from Fe-poor montmorillonite to nontronite at low temperatures. The pore-interlayer water in smectite H-isotope fractionation at low temperatures is ~20±10‰. The presence of organic matter can modify both the δD value of the clay analysis and its ‘water’ content. Clays — kaolinite, illite, smectite and probably halloysite — tend to retain their D/H and 18O/16O ratios unless subjected to more extreme diagenetic or metamorphic conditions or special local processes. Kinetic information is still only qualitative: for comparable grain sizes, hydrogen exchanges more rapidly than oxygen in the absence of recrystallization. Low-temperature diffusion coefficients cannot be calculated with sufficient precision from the higher temperature exchange data. The H- and O-isotope studies of clays can provide useful information about their conditions of formation.

Interpretation of K-Ar determinations of the apparent age of crystallization of diagenetic potassic layer silicates should take into account the current ideas concerning the smectite to illite conversion of clay minerals. These minerals are the major K-bearing neogenic phases in sedimentary rocks and, therefore, it is important to keep in mind their origin and the pathway of their evolution. Another important contributor to K and Ar content are detrital minerals which are not considered in detail in this paper. The radiogenic Ar retained by diagenetic illitic clay minerals (illite and illite-smectite interstratified minerals with a low smectite content) will be a function of: (1) the amount Ar lost through the destruction of mixed-layer and small grained illitic material dissolved to produce new, larger, illite-rich crystals; and (2) the amount of Ar produced and retained in the growing, stable illite mineral grains. Hence the K/Ar ratios in diagenetic illites depend on several variables. In samples where the detrital contribution is small, when the illite growth reaction is rapid, i. e. occurring over a short period of time, the accumulated radiogenic Ar can be used to date the geologic event which caused this crystal growth. However, if the process occurs over a significant period of time, as is usually the case in shales, the age deduced by radiogenic Ar content will indicate the changes in mineralogy and grain-sizes of the different participating phases. These changes will be the result of time and temperature variables of the sedimentation and burial of the samples studied. The radiogenic Ar accumulated will reflect a sequence of mineral changes over a period of time.

A mineralogical and geochemical study of the Gabasa outcrop (Huesca, NE Spain) was undertaken. It consists of Early Oligocene marly and clayey fluvial and lacustrine (playa-lake) sediments. The phases detected were quartz, amorphous silica, calcite, dolomite, palygorskite, illite, interstratified illite-smectite, Al-smectite and Mg-smectite. The palygorskite expands with ethyleneglycol. Statistical analysis of the geochemical data shows that the rare earth elements and transition trace elements are basically associated with the detrital phyllosilicates, although a considerable amount of the latter is contained in the palygorskite (ΣREE = 60–70 ppm, Cr+Co+Ni+V+Zn+Cu = 120–150 ppm), in contrast to the normally low values for neoformed minerals. This fact, together with the significant presence of Al and Fe in the palygorskite, suggest genesis involving alteration by dissolution of the 2:1 structure of the illite and/or Al-smectite, followed by re-ordering in a fibrous structure.

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.

Stichtite is the layered Mg-Cr(III) hydroxide carbonate of the pyroaurite group. The possibility of describing Cr(III) short range order (SRO) in stichtite by use of ion chromatography of the Cr(III)-hydroxo species following acid dissolution of the compound is described. Two synthetic stichtites of similar composition (average Mg5.73Cr(III)2.27(OH)15.93(O)0.07(CO3)1.10·xH2O) prepared in the absence or presence of hydroxy-bridged Cr(III) dimers and a sample from Dundas, Tasmania, Mg6.29Ni(II)0.02Cr(III)0.90Al0.65Fe(III)0.15(OH)15.26(OH2)0.74(CO3)1.23·xH2O have been examined. Ion chromatography showed the highest degree of SRO for the Dundas stichtite. For the synthetic stichtites the sample synthesized from Cr(III) dimers had the highest SRO. No information on cation ordering could be extracted from powder X-ray diffraction data. Visible spectroscopy indicates that for constant Mg:Cr(III) ratio the crystal field splitting increases with increasing SRO. Two different OH-stretching IR absorption bands (3585 and 3472 cm−1) are assigned to OH coordinated to 3Mg and OH coordinated to 2MgCr or Mg2Cr, respectively.

Goethite is an important component of many soils and its transformation to hematite by fire may affect phosphate retention. This study deals with the kinetics of phosphate sorption and desorption by synthetic aluminous goethites and their dehydroxylated products. Phosphate sorption and subsequent desorption were measured for periods up to 128 h. Phosphate sorption increased with equilibrium solution concentration, Al substitution and surface area, and decreased with increasing crystal size. The trend in amount of phosphate sorbed was: partially dehydroxylated goethite > hematite > goethite. Sorption and desorption kinetics are well described by the modified Elovich equation. Desorption of a minor proportion of the sorbed P was rapid and this was sometimes followed by minor resorption. The amount of P desorbed directly reflected the amount that was initially sorbed. Acid dissolution of the Fe oxides with sorbed phosphate suggested that most phosphate was present at the crystal surface and not in relatively poorly accessible micropores.

Nitrogen adsorption and desorption isotherms were obtained for microcrystalline, platy crystals of synthetic Al-substituted goethites synthesized from the ferrous system and heated to 260°C. Specific surface area, cumulative pore area and frequency of mesopore wall-separations of 2–15 nm in size increased as Al substitution increased. Nanometre-size micropores developed at heating temperatures between 200 and 240°C and decreased during the growth of hematite crystals between 240 and 260°C. Aluminium substitution had little effect on micropore development and a moderate effect on mesopore development. The increases in micropore volume and specific surface area due to heating are much smaller than is reported in the literature for large, lath-like crystals of goethite that develop abundant slit-shaped micropores.

Aqueous suspensions of sepiolite, tagged with fluorescent dyes, have been studied using electro-fluorescence polarization spectroscopy. The binding modes of some 37 fluorescent dyes and optical brightening agents to the rod-like sepiolite particles have been determined. Many of the dyes are found to bind with a degree of order to the clay particle's major axis. The binding geometries of the cationic dye molecules tested were found to be dependent upon molecular size. This supports the view that these cationic dye molecules are constrained within the channels which are characteristic of the mineral sepiolite. Results for uncharged and anionic dye molecules are also presented; no dependence of binding geometry upon molecular size was found. The anionic molecules are most likely to associate with the exterior cationic magnesium surface. The results indicate that some of the anionic dyes are too large to fit in the channels. Some of the uncharged molecules adopt a number of orientations upon binding which gives rise to an average geometry being observed for these dyes.

Les substrats argile-alkylammonium sont utilisés dans ce travail comme des modèles de sol, dans le but d'étudier les interactions entre un pesticide neutre peu soluble dans l'eau, le dinoseb, et des substrats dont les surfaces ont été rendues hydrophobes. Les spectrométries infrarouge (IR), Raman et de réflexion diffuse dans l'UV-visible sont utilisées de façon complémentaire aux isothermes d'adsorption pour préciser la localisation et l'état des molécules pesticide retenues sur les substrats. Dans le cas de la vermiculite-décylammonium, la fixation du dinoseb est observée à la fois sur les surfaces externes et dans les espaces interfoliaires, les molécules de pesticide sont directement en interaction avec les atomes d'oxygène de la surface des feuillets et avec les cations ammonium, par liaisons hydrogène. Le taux de molécules de dinoseb retenues sur l'hectorite-décylammonium est beaucoup plus faible. Les molécules fixées ont alors une structure voisine de celle des molécules libres. Ces analyses montrent que le caractère hydrophobe de la surface des complexes organominéraux est une condition nécessaire, mais non suffisante, pour la fixation de molécules peu solubles dans l'eau. Notre étude souligne l'importance des interactions spécifiques par liaison hydrogène entre le pesticide et le feuillet de vermiculite dans le processus de rétention.

Clay mineral assemblages in both shales and sandstones of Miocene age have been studied in a well from the Ulleung Basin, a back-arc basin in the East Sea. Samples were examined from burial depths of ~800 to 3000 m. At the shallowest depths the shales contain assemblages dominated by R0 mixed-layer illite-smectite (I-S) together with illite, kaolinite and minor chlorite. The sandstones also contain I-S, but are dominated by large amounts of authigenic kaolinite. In both shales and sandstones I-S becomes R1 ordered at ~ 1000 m depth and at 2000 m depth, and deeper, I-S expandabilities are <20%. At ~ 2400 m depth, kaolinite in the sandstones is replaced by abundant Li-tosudite, indicating that clay mineral diagenesis has been affected by a hydrothermal episode. Furthermore, organic maturity data indicate that much of the succession has experienced considerably higher temperatures in the past. Vitrinite reflectance data are best modelled by a short lived (0.1–0.01 Ma) heating event in the Pliocene. This suggests that the shallow depths over which the smectite to illite reaction is completed and the extensive kaolinitization of the Miocene sandstones may also be related to the hydrothermal event.

La nacrite constitue le plus rare polytype des kaolinites. Traditionnellement, on attribue á ce minéral une genèse hydrothermale (Ross & Kerr, 1931; Hanson et al., 1981 ), cependant Btihmann (1988) décrit sa formation en condition normale de température et de pression dans des milieux de solution et de force ionique élevées. Dans ce travail, la nacrite est mise en évidence dans deux anciens gisements de Pb-Zn situés dans les massifs de Jbel Slata et Garn Halfaya au nord de la Tunisie (Fig.l).