The alteration process of a subvolcanic rock with calcic plagioclase, pyroxene, and olivine as major components was investigated by X-ray diffraction (XRD) and analytical and transmission electron microscopy (TEM/AEM). Experimental interaction with 1 M NaOH solution led to the formation of dioctahedral beidellite to Fe-rich montmorillonite after 1 and 3 d of reaction. This range of smectite composition is similar to that from natural subvolcanic-derived soil formed from the same parent material. After 14 d of reaction, a berthierine-smectite (B-S) interstratified clay had partially replaced the smectite. Although, the presence of smectite interlayers prevented analysis of pure berthierine, berthierine-rich BS interstratifications have a composition similar to pure berthierine. After 40 d, the alteration process led to a 7-Å S interstratification whose composition falls between greenalite and lizardite. A series of amorphous materials were also found in the 14 and 40-d experiments. The most abundant of these is a Si-CaFe-rich material, whose chemical composition approaches that of the starting rock. In contrast, two other amorphous materials had a smectitic composition.

Experimental illitization of smectite was studied by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Experiments were performed on the <2 µm fraction consisting entirely of smectite separated from a soil formed on subvolcanic rock located in the External Zone of the Betic Cordilleras (southern Spain). Amounts of 0.25 g were added to different solutions: seawater, and three K-enriched seawater solutions prepared by adding KOH to seawater whose final [K] values were 0.1, 0.5 and 1 M, respectively. The experiments were performed at 50°C over a period of 30 days. The XRD patterns showed no mineralogical changes in residues from seawater or from the 0.1 M [K] solution. With increasing pH and K molarity, the smectite peak, initially at 1.4 nm, became broader. This change in the smectite peak was more significant in the residue from the 1 M [K] solution. The appearance of a small shoulder at 1.0 nm in the residue from a 0.5 M [K] solution showed the beginning of illite formation. However, its appearance was clearer in XRD patterns of the residue corresponding to the 1 M [K] solution. The XRD data from air-dried, glycolated, and heated samples from the 1 M [K] solution indicated the presence of smectite, disordered interstratified illite-smectite (I-S) and illite.

The TEM/AEM studies were performed on the residue corresponding to the 1 M [K] experiment. The HRTEM images revealed that smectite and illite occurred as separated packets with a ferroan lizardite, as a by-product of the smectite-to-illite reaction, interstratified and intergrown with illite. Smectite occurs both as ‘rims’ on the illite packet and in its core. The presence of smectite in the core of illite packet indicates that the lateral transition from smectite to illite was incomplete, taking place by direct replacement of smectite layers as a whole through a dissolution-precipitation mechanism. The experimental study shows that smectite may transform in a wide range of geological and artificial environments involving high-pH K-rich solutions.

Mössbauer spectroscopy and electron microscopy were combined to study one Al-poor anthophyllite and one Al-rich gedrite. TEM show that Al-rich gedrite is not homogeneous and that the complexity of its Mössbauer spectrum is due to sub-microscopic intergrowth of chlorite and lizardite.

The crystal structure of lizardite-1T from Gew-graze, Cornwall, has been refined by single-crystal X-ray diffraction to R1 of 0.0263 and 0.0557, for two crystals having P31m space group and lattice parameters a = 5.2905(5) Å, c = 7.2815(8) Å, and a = 5.3111(10) Å, c = 7.2907(15) Å, respectively. The Gew-graze lizardite is very close to the end-member composition, so these refinements confirm the existence of well crystallized pure Mg-lizardite and show this to be the most weakly H-bonded lizardite ever refined. With regard to its lattice parameters, Si–O bond distances and geometrical parameters controlled by interlayer interactions (i.e. H-bonding), the Gew-graze Mg end-member lizardite yields slight but observable geometrical differences compared with previous refined structures for specifically, aluminous, lizardites.

Lizardite-1T crystals from Gew-graze at the Lizard, Cornwall, of an apparent composition (Mg2.94Fe0.03Al0.03)(Si1.97Al0.03)05(OH)4, have been observed to contain 2–5% of thin interstratifications of clinochlore when investigated by analytical transmission electron microscopy (TEM). The clinochlore is usually only a few unit layers thick but has an extensive lateral dimension parallel to the lizardite layers. Analytical TEM confirms the existence of very low-Al lizardite with a planar structure interstratified with occasional thin units of clinochlore containing substantial Al. Compositionally, such clinochlore (invisible by X-ray diffraction) interstratified throughout the lizardite crystals, could account for most of the Al present. We suggest that an occasional influx of Al causes the nucleation and growth of clinochlore at the expense of lizardite. The possibility of clinochlore contributing to the measured Al content in lizardite samples highlights the need for future investigations of Al-bearing serpentines to include careful examination and interpretation using imaging and analysis by TEM.

It has crept into serpentine discussions that lizardite cannot form without the coupled substitution of Al to relieve the misfit between the sheets of octahedra and tetrahedra. The lizardite at Gew-graze is almost Al-free, forms well-crystallized planar crystals and demonstrates that Al is not an essential element for lizardite crystallization.

A chrysotile disc is proposed as the fundamental seed structure for the formation of chrysotile asbestos fibres, polygonal serpentine fibres and polyhedral lizardite spheres. The curvature, fivefold symmetry and hydrogen-bonding alignment of the layers in the seed disc control the formation of the 15 or 30 sectors in polygonal serpentine and the orientations of the planar arrays of 15 or 30 radial crystals in polyhedral serpentine. A polygonized disc precursor to polygonal fibre formation has been observed at an arrested stage of growth in a synthesis experiment.