Clay minerals are the principal reactive, non-combustible, phases present in the pulverized coal burned in power station furnace units. Despite the short heating time involved, the clay mineral impurity is wholly transformed in the ignition.

Illitic clays are partially melted, fluxed by water and potash, to produce an alumino-silicate melt phase. The melt is frothed by the synchronous production of carbon dioxide in an iron oxide catalysed oxidation of associated carbonaceous matter. This produces the hollow, gasfilled, glass-walled spheres (cenospheres) characteristic of pulverized fuel ash (PFA). Partial, primary devitrification crystallization of mullite and quartz from the high-alumina glass is general and the extent of devitrification may influence the pozzolanic efficiency of the PFA cenospheres.

Without the advantage of potash fluxing, the kaolinite lattices are dehydrated and transformed, without melting, to amorphous aluminosilicate and crystalline mullite.

Oxidation of pyrite leads to coating of cenospheres by condensed magnetite and the emission of sulphur dioxide in the flue gases.

An extensive belt of A-type granite exists along the southeast coast of China. The granites are divided into peralkaline and more aluminous subgroups which differ in mineral assemblages, mineral compositions and textures. In the peralkaline subgroup, primary magmatic Th-rich zircon is typically overgrown by Th-poor zircon containing thorite micro-inclusions. REE minerals in this subgroup are dominated by allanite-(Ce), chevkinite-(Ce), titanite and pyrochlore. Fe-Ti oxides are titanian magnetite and Mn-rich ilmenite. In contrast, in the more aluminous subgroup rocks, zircon is weakly zoned and exhibits very low Th but relatively high U contents. The REE minerals are dominated by Th-rich monazite-(Ce). Titanium-poor magnetite, pyrophanite and rutile are the major Fe-Ti oxides. These occurrences indicate that peralkaline magmas favour the formation of REE silicates, whereas magmas with higher alumina saturation stabilize REE phosphates. Peralkaline granites crystallized at temperatures 50–100°C greater than the more aluminous granites, but under lower oxidation conditions. These differences in formation conditions of the two A-type granite subgroups, deduced by accessory mineralcharacteristics, are inferred to be related to magma derivation at different crustal levels, with peralkaline magma deriving from a deeper crustal level with more mantle input.

Recent experimental and theoretical studies provide new insight into the variety of high-pressure transformations in minerals that comprise the Earth’s deep mantle and core. Representative examples of reconstructive, displacive, electronic and magnetic transformations studied by new diamond-anvil cell techniques are examined. Despite reports for various transitions in (Mg,Fe)SiO3-perovskite, the stability field of the orthorhombic phase expands relative to magnesiowüstite + SiO2 with increasing pressure and temperature. The partitioning of Fe and Mg between Mg-rich silicate perovskite magnesiowüstite depends strongly on pressure, temperature, bulk Fe/Mg ratio, and ferric iron content. The soft-mode transition in SiO2 from the rutile- to CaCl2-type structure, originally documented by X-ray powder diffraction, Raman scattering, and first-principles theory has been explored in detail by single crystal diffraction, and transitions to higher-pressure forms have been examined. The effect of H on the transformations of various nominally anhydrous phases and transitions in dense hydrous Mg-silicates are also examined. New studies of the phase diagram of FeO include the transition to rhombohedral and higher-pressure NiAs polymorphs, and provide prototypical examples of coupled structural, electronic, and magnetic transitions. High-spin/low-spin transitions in FeO have been examined by high-resolution X-ray emission spectroscopy to 150 GPa, and the results are compared with similar studies of Fe2O3 and FeS. Finally, laser-heating studies to above 150 GPa and 2500K show that (hcp) ε-Fe has a large P-T stability field. Radial XRD measurements carried out at room temperature to 220 GPa have constrained the elasticity, rheology and sound velocities of ε-Fe at core pressures.

The course of all crystalline structural changes undergone by the mineral beryl, its melt and glass, has been followed as a function of widely differing but accurately known thermal history. Non-equilibrium ordering processes have been characterized by new techniques in high-temperature microscopy.

The relative influence that beryllium and aluminium ions exert on the phase changes has been established by studies on synthetic melts and glasses representing hypothetical beryls of differing ratios of Be2+:Al3+ ions.

The dynamic changes between the oxide and orthosilicate structures into which the systems reconstitute include the formation of a metastable hybrid beryllium aluminium silicate, which is viewed as a beryllium-containing mullite. The crystallochemical changes have been interpreted in terms of a structural model of the melts and glasses that is shown to be consistent with the ordering effects predicted from the field strengths of the cations.

Hydrothermal studies in the silica-rich region of the CaO-SiO2-H2O system have given information on the stability field of tobermorite. At saturated steam pressures tobermorite is unstable relative to xonotlite (C6S6H) above 140 °C but between 10 000 and 40 000 lb/in.2 (69 and 276 N/mm2), the decomposition temperature is raised to 285±5 °C. Tobermorite is stable at all compositions between C/S = 0·67 and 1·0 up to this temperature and has a formula close to C5S6H5. Variable compositions reported earlier are thought to be mixtures rather than lime-rich or silica-rich tobermorites.

Data have also been collected on the equilibrium assemblages below C/S = 0·67 and between C/S = 1·0 and 1·5 involving truscottite, gyrolite, xonotlite, foshagite, and hillebrandite.

In this paper the formation of a gelatinous hydrate phase from the natural dicalcium silicate minerals larnite and bredigite is described. Detailed study of the gel so formed indicates that the process of hydration is a solid reaction which is effeeted by diffusion. The preferred orientation of the hydrate phase suggests that the hydration is facilitated by a relationship between the structure of the anhydrous silicate and that of the hydrate phase produced.

In this investigation the variations in density, mean refractive index, and chemical composition of the natural gels have been determined and the characteristics of the adsorbed water studied by isothermal dehydration and rehydration. In discussing the mechanism of hydration it has been assumed that this obtains at constant volume. This assumption is based on the study of gel pseudomorphs after single crystals of larnite and bredigite in thin section.

A study of inclusions within garnet porphyroblasts demonstrates that planar inclusion bands and trails lie sub-parallel to one of the {110} planes of the host. The inclusions provide a relic of a rock fabric that existed before the growth of garnet. It is suggested that this fabric has determined the crystallographic orientation of garnet and may have arisen by the nucleation and epitaxial growth of garnet within or upon the mica lattice.

The intracrystalline cation distributions in fourteen natural Zn-aluminate spinels were determined by means of X-ray single-crystal structural refinement, supported for some samples by Mössbauer spectroscopy.

Zinc substitutes for Mg and subordinately Fe2+ and its relevant changes in content, from 0.10 to 0.96 atoms per formula unit (apfu), are not related to variations of cell parameter. The latter is determined mainly by the substitution Fe3+ ⇌ Al. In agreement with data from synthetic samples, a small but definite amount of Zn (up to 0.06 apfu) is located in the octahedral M site. Fe2+, when present, shows a preference for tetrahedral coordination.

An improved value of the tetrahedral Zn(T)-O distance (1.960 Å) was obtained, integrating the set of interatomic distances used for the determination of cation distribution in spinels.

Hydrobasaluminite and basaluminite, two hydrated basic aluminium sulphate minerals have been found in the weathering zone of the Oxford Clay at Crook Hill Brickyard, Chickerell, near Weymouth, Dorset. Hydrobasaluminite occurs as a reaction rim surrounding carbonate concretions, and is believed to have resulted from the neutralization of aluminium-bearing acid sulphate solutions formed by oxidation of pyrite and subsequent leaching of clay. Basaluminite is found only on concretions that have fallen to the floor of the pit, suggesting that it is formed as a dehydration product of hydrobasaluminite.

Chemical analysis of hydrobasaluminite yields the composition 2Al2O3 · SO3 · 20H2O, although this almost certainly includes substantial amounts of adsorbed water. Chemical analysis of basaluminite gives the composition 2Al2O3 · SO3 · 9H2O, which is equivalent to a formula of Al4SO4(OH)10 · 4H2O if it assumed that water is present only as water molecules or hydroxyl ions. The sulphate ions are readily exchangeable. Electron-optical and X-ray powder diffraction data show the minerals to be monoclinic rather than hexagonal as previously reported. Indexed X-ray powder patterns give unit-cell parameters of a = 14.911(5) Å, b = 9.993(2) Å, c = 13.640(5) Å, β = 112.40(4)° for hydrobasaluminite and a = 14.857(3) Å, b = 10.011(3) Å, c = 11.086(7) Å, β = 122.28(3)° for basaluminite. The specific gravity of basaluminite is found to be 2.10 and Z = 4.

Hydrobasaluminite dehydrates irreversibly to basaluminite under normal laboratory conditions, but can be preserved indefinitely at high relative humidity. A study of the dehydration of basaluminite using a diffractometer heating-stage shows the presence of three further distinct hydration states as well as interstratified intermediates. The dehydrations occur topotactically and involve major changes in the c* direction only. DTA and TGA curves can be interpreted in terms of progressive dehydration.

It is suggested that the minerals possess a layer structure, probably containing gibbsite-like double-hydroxide layers with interlayer sulphate ions and water molecules. The data also seem to show a close structural relationship between basaluminite and the hydrated basic aluminium carbonate mineral, scarbroite.

The unusual assemblage ferroglaucophane-chloritoid-paragonite-garnet-muscovite-chlorite-quartz has been found in metapelites of the phyllite series, north-east of Neapolis, southern Peloponnese, Greece. The chemical compositions of the coexisting phases are given, and the physical and chemical constraints which may control the appearance of this assemblage are briefly discussed.

A new analysis of the type material of cheralite specifies the individual rare earth elements. Unit cell contents are: (REE1.58Th1.15Ca1.03Pb0.05U0.15)3.96 (P3.67Si0.33)4.01O16. Refinement of the cell parameters based on new XRD data shows that a = 6.7515 ± 0,0005 Å, b = 6.9625 ± 0.0005, c = 6.468 ± 0.0005, β = 103° 53′, giving a cell volume of 295.2 Å3. Space group P21/n.

Markhininite, ideally TlBi(SO4)2, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Markhininite occurs as white pseudohexagonal plates associated with shcherbinaite, pauflerite, bobjonesite, karpovite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Markhininite is triclinic, P, a = 7.378(3), b = 10.657(3), c = 10.657(3) Å , α = 61.31(3), β = 70.964(7), γ = 70.964(7)º, V = 680.2(4) Å3, Z = 4 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 68/4.264/111, 100/3.441/113, 35/3.350/222, 24/3.125/122, 23/3.054/202, 45/2.717/022, 20/2.217/331, 34/2.114/204. Chemical composition determined by electron microprobe analysis is (wt.%): Tl2O 35.41, Bi2O3 38.91, SO3 25.19, total 99.51. The empirical formula based on 8 O a.p.f.u. is Tl1.04Bi1.05S1.97O8. The simplified formula is TlBi(SO4)2, which requires Tl2O 35.08, Bi2O3 38.48, SO3 26.44, total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.055 on the basis of 1425 independent observed reflections. The structure contains four Tl+ and two Bi3+ sites in holodirected symmetrical coordination. BiO8 tetragonal antiprisms and SO4 tetrahedra in markhininite share common O atoms to produce [Bi(SO4)2]– layers of the yavapaiite type. The layers are parallel to (111) and linked together through interlayer Tl+ cations. The mineral is named in honour of Professor Yevgeniy Konstantinovich Markhinin (b. 1926), Institute of Volcanology, Russian Academy of Sciences, Kamchatka peninsula, Russia, in recognition of his contributions to volcanology. Markhininite is the first oxysalt compound that contains both Tl and Bi in an ordered crystal structure.

The Afon Goch (Anglesey, UK) is a short (12 km source to estuary) stream highly contaminated by acid mine drainage (AMD) throughout its length, due to past-mining at the head of the stream. Metal distribution is strongly controlled by the pH, which increases downstream particularly at confluences with two unpolluted tributaries. A pH increase causes precipitation of metals, primarily Fe as hydroxide, thus altering the transport of the metal load, potentially allowing storage of metal within the river as deposited material. However, further work suggests that the controls on whether metal can behave non-conservatively, and therefore the controls on metal distribution, are more complicated than being purely pH dependent. This is because much of the Fe load, even at the low pH at the head of the stream, is not soluble Fe3+ but colloidal Fe hydroxide. Consequently, coagulation is a requisite intermediate step between precipitation and potential for settling. It is possible that in reaches of the stream away from tributary confluences, the process of coagulation is the predominant influence on metal distribution. Furthermore, because much of the metal load in the water column is very fine, its deposition results in a sediment in which the metals can be intimately associated with a biofilm at the sediment/water interface. Such associations change both deposition and erosion characteristics of the sediment and have implications for subsequent diagenesis and mineral morphology.

A detailed field study to determine quantitatively the distribution of K-feldspar megacrysts, mafic microgranular enclaves (MME) and metasedimentary xenoliths has been carried out in the Monte Capanne pluton (Elba, Italy) with a view to evaluating the utility of this approach to petrogenetic investigations. Mafic microgranular enclaves are inferred to result from interactions between mafic and felsic magmas, while xenoliths attest to crustal assimilation occurring in the Monte Capanne magma chamber. In particular, we emphasize, based on our field data, that both processes are intimately linked, such that xenolith dissolution during assimilation was triggered by replenishment with hot mafic magma. It is suggested that the previously defined ‘San Piero’ and ‘San Francesco’ facies do not differ substantially, and are thus amalgamated and renamed as the ‘Pomonte’ facies. Results also indicate that the abundance of K-feldspar megacrysts is positively correlated with the volumetric abundance of MME in the Sant’ Andrea facies, which we link to a recharging, mingling and textural coarsening event that occurred at a rather late stage of magma-chamber evolution prior to emplacement. This study demonstrates how petrogenetic processes can be deciphered by detailed field quantitative analyses of granite-forming components, thus complementing geochemical investigations.

This second recorded occurrence of yimengite, K(Cr, Ti, Fe, Mg, Al)12O19, is in a Precambrian kimberlitic sill in the Guaniamo District of Bolivar Province, Venezuela. The paragenesis is similar to that of the type area in Shandong Province, China, where the mineral is in kimberlite dykes. At both localities the yimengite is a K, Ti-bearing metasomatic product of chromium-rich spinel. In the Venezuela rocks the spinels are of the type occurring both as diamond inclusions and as a component of diamond-related Cr-rich garnet harzburgite mantle xenoliths. Yimengite contains significant amounts of barium (up to 3.4wt.% BaO) and is thus transitional to the recently described mineral hawthorneite, Ba(Cr, Ti, Fe, Mg)12O19. Both members are part of a suite of titanate minerals found in kimberlites and their inclusions which has been described by Haggerty and coworkers; they formed as a result of mantle metasomatism generated by K- and Ba-rich fluids. In Venezuela, metasomatism of this type would appear to be deeper than that usually recorded, namely in the basal lithosphere. The metasomatizing fluids are derived from the underlying, more oxygenated asthenosphere. The host kimberlitic rocks are not significantly enriched in K and Ba, but these elements are concentrated in later micaceous dykes which are conjectured to have been generated within similar metasomatized mantle.

The S. Domingos abandoned mine is a major source of pollutant-metals contamination. Slags from the 19th-20th century contain the most hazardous material. However, the release of pollutant metals depends on the metal-retention capability of weathering products. This work shows that Zn is not effectively retained by these weathering products while As and Pb are partially stored in sulphates. Copper, on the other hand, has a different behaviour and is the most leachable of the elements studied.

Preliminary geological work on samples from Davdar in China indicate that emerald occurs in quartz veins hosted within upper greenschist grade Permian metasedimentary rocks including quartzite, marble, phyllite and schist. Fluid inclusion studies indicate highly saline fluids ranging from approximately 34 to 41 wt.% NaCl equivalent, with minimal amounts of CO2 estimated at a mole fraction of 0.003. Fluid inclusion, stable isotope and petrographic studies indicate the Davdar emeralds crystallized from highly saline brines in greenschist facies conditions at a temperature of ∼350°C and a pressure of up to 160 MPa. The highly saline fluid inclusions in the emeralds, the trace-element chemistry and stable isotope signatures indicate that the Davdar emeralds have some similarities to the Khaltaro and Swat Valley emerald deposits in Pakistan, but they show the greatest similarity to neighbouring deposits at Panjshir in Afghanistan.

The thermal decomposition of portlandite, Ca(OH)2, has been studied in air and in vacuum using X-ray single-crystal techniques. In air, the crystals were decomposed in situ on the goniometer arcs whilst X-ray reflections were simultaneously recorded. The transformation to CaO was not accompanied by topotaxy; this is attributed to the high nucleation rate of CaO crystallites in air. When Ca(OH)2 single crystals were decomposed under vacuum (and subsequently exposed to X-rays), some orientation of the CaO crystallites occurred. These results are compared with those of previous workers using electron-diffraction techniques. Decomposition of Ca(OH)2 single crystals commences at ∼ 450 °C in air and at ∼ 230 °C in a vacuum of 10−6 mmHg; reaction commences at crystal edges and surface defects, the reaction boundary moving inwards to the centre of the crystal. This observation is consistent with a homogeneous mechanism of decomposition.

The composition, structure, X-ray powder diffraction pattern, optical properties, density, infrared, Raman and Mössbauer spectra, and thermal properties of a homogeneous sample of metavivianite from the Boa Vista pegmatite, near Galiléia, Minas Gerais, Brazil are reported for the first time. Metavivianite is biaxial (+) with α = 1.600(3), β = 1.640(3), γ = 1.685(3) and 2Vmeas = 85(5)°. The measured and calculated densities are Dmeas = 2.56(2) and Dcalc = 2.579 g cm–3. The chemical composition, based on electronmicroprobe analyses, Mössbauer spectroscopy (to determine the Fe2+:Fe3+ ratio) and gas chromatography (to determine H2O) is MgO 0.70, MnO 0.92, FeO 17.98, Fe2O3 26.60, P2O5 28.62, H2O 26.5; total 101.32 wt.%. The empirical formula is (Fe3+1.64Fe2+1.23Mg0.085Mn0.06)Σ3.015(PO4)1.98(OH)1.72·6.36H2O. Metavivianite is triclinic, P, a = 7.989(1), b = 9.321(2), c = 4.629(1) Å, α = 97.34(1), β = 95.96(1), γ = 108.59(2)°, V = 320.18(11) Å3 and Z = 1. The crystal structure was solved using a single-crystal techniques to an agreement index R = 6.0%. The dominant cations in the independent sites are Fe2+ and Fe3+, with multiplicities of 1 and 2, respectively. The simplified crystal-chemical formula for metavivianite is Fe2+ (Fe3+, Fe2+)2(PO4)2(OH,H2O)2·6H2O; the endmember formula is Fe2+Fe3+2(PO4)2(OH)2·6H2O, which is dimorphous with ferrostrunzite.