Odinite is a Fe3+-rich green clay that is widespread in the form of infillings or replacements of microtests, bioclasts, faecal pellets, or mineral debris on shallow marine shelfs and reef lagoonal areas in tropical latitudes. The structure is based on a 1 : 1 serpentine-type layer that is intermediate between dioctahedral and trioctahedral. Octahedral cation totals range from 2·30 to 2·54 cations per 3·0 sites for 10 samples. The structural formula for the purest sample is Both monoclinic and trigonal polytypes are present in most samples, with 1M more abundant than 1T. Unit-cell dimensions are 1M: a = 5·373(3), b = 9·326(7), c = 7·363(6) Å, β = 104·0(1)°; 1T: a = 5·366(5), b = 9·334(9), c = 7·161(8), β = 90° (on orthohexagonal axes). The name is for Dr. Gilles Serge Odin, Département de Géologie Dynamique, Université Pierre et Marie Curie, Paris, who has done most of the pioneering work on this new mineral.

The (02,11) X-ray diffraction band from a low-defect kaolinite from Cornwall (Hinckley index HI = 1·22) was examined to determine the defect structure. No combination of interlayer translations and admixing of dickite layers accurately modelled the observed diffraction pattern. Calculated diffraction patterns which gave a good agreement with the shape, position, and intensity of the observed peaks, uniformly had inter-peak intensities which were too weak. By treating the kaolinite as a mixture of low-defect (HI = 1·76) and moderate-defect (HI = 0·29) kaolinites, the agreement between the observed and calculated patterns was improved substantially. The existence of a mixture of two kaolinites was also found for a number of low-defect samples (HI > 0·4) from Georgia and Cornwall, and may be of even wider occurrence. The HI, which is very sensitive to the inner-peak intensities, does not estimate the types or abundances of various structural defects (the classical “crystallinity”), but is related directly, in a non-linear fashion, to the proportions of the two kinds of kaolinite which are present in the sample.

Vermiculite prepared from biotite by interlayer cation exchange was reacted with solutions exhibiting redox potentials between 625 and 765 mV. The redox potential was controlled by the Fe2+/Fe3+ activity ratio, measured with a Pt electrode, and kept constant by addition of hydrogen peroxide to balance electron transfer from structural Fe2+ to Fe3+ in solution. Oxidation of structural Fe2+ was followed by Eh-stat titration and the rate of oxidation was shown to depend on the amount of Fe3+ penetrating into interlayer positions. Consequently, it was affected not only by the redox potential, but also by the activity between Fe3+ and all other cations present in solution or in an exchangeable state. Oxidation and cation exchange are coupled reactions. In contrast to the redox potential in solution, the effective redox potential controlling the oxidation of structural Fe2+ was increased by preferential sorption of the Fe3+ ion.

The dominant source of oxalate-soluble Al in the B horizon of a brown podzolic soil developed on andesite appears to be hydroxyaluminium interlayers in a dioctahedral vermiculite in the clay and silt fractions, of which the latter contributes most to the total extractable Al and fluoride reactivity of the whole soil. Cold sodium carbonate solutions extract as much interlayer Al as does oxalate, indicating that this fraction of the interlayer material is highly reactive, and sharply distinguished from more resistant interlayers which are also present.

The clay fraction of soils from a toposequence developed on a sandy clay Tertiary sediment in the Brazilian Amazonia was studied. Clayey Acrorthox located at the upper part of the sequence have transformed progressively into sandy Tropohumods down the slope. Along the slope important chemical and mineralogical changes linked to modifications in the weathering conditions were observed. In the Acrorthox the hydrolysis process largely prevails and the clay fraction is composed mainly of Fe-rich kaolinite. Fe and Al amorphous compounds become increasingly abundant along the slope. In the Spodosols, hydrolysis and acidocomplexolysis processes have both been effective, and the clay fractions contain not only more gibbsite, but also amorphous materials which are particularly abundant in the Bh horizons.

Fe oxides deposited in ditches draining a bog in the Harz Mountains, Northern Germany, consist essentially of a two-XRD line ferrihydrite that has a magnetic hyperfine field of only 46·5 T at 4·2 K. Pyrophosphate extraction led to an incomplete separation of this from organically-bound Fe, which was depleted in the residue and particularly enriched in the dialysate of the extract. Decomposition of humics with H2O2 led to a further depletion of organic Fe, but also increased the number of XRD lines of the ferrihydrite to six, and raised the hyperfine field by ∼1 T. These modifications are probably the result of an improved interparticle coherence.

Seven diagenetic illitie clays have been investigated by Mössbauer spectroscopy to characterize the forms of iron. Four specimens had measurable amounts of iron oxide impurity phases, accounting for up to ∼95% of the total Fe. Goethite, microcrystalline and probably aluminous, was identified as the oxide phase in three of these samples, the other containing hematite. This latter sample was also the only one which had tetrahedral Fe(III). Five of the samples contained measurable amounts of Fe(II), but the aluminosilicate Fe was present largely as 6-coordinated Fe(III) which had two distinctly different sets of parameters. These results are discussed in terms of the structural properties of illites.

The characterization of clay mineral assemblages in the diatomite-dominated Tripoli Formation (Lower Messinian, central Sicily) has resulted in delineation of suites dominated by generally well-crystallized dioctahedral smectite and illite of low crystallinity, with lesser amounts of kaolinite and chlorite. These minerals are thought to have a mainly detrital origin related to the calcareous and marly formations exposed in the margins of the depositional area. Vertical fluctuations of the montmorillonite/illite ratio and changes of the crystallinity and chemical composition of these phyllosilicates support environmental interpretations from isotopic data of associated carbonates, and point to a wide variability of depositional conditions ranging from evaporating to brackish. Early diagenesis of the clay minerals was controlled by the primary composition of the sediment which, in turn, affected the porewater chemistry.

Temperature programmed desorption (TPD) and IR spectroscopy were used to examine the desorption of pyridine, 2-methyl-, 4-methyl- and 2,6-dimethylpyridine from Al3+- and Cr3+-montmorillonite. Pyridine desorbed from Lewis sites at 150°C and from Bronsted sites at 340°C. 4-methylpyridine desorbed from Lewis and Bronsted centres at 210°C and 410°C respectively, some 60°C higher than pyridine due to its higher basicity. Conversely, the 2-methyl- and 2,6-dimethylpyridine, which are sterically hampered with respect to their coordination to Lewis centres, desorbed from these sites near 100°C, but due to their greater basicity desorbed from Bronsted sites at higher temperatures. These interpretations were confirmed by IR spectroscopy.