Moganite, monoclinic SiO2, is a component of microcrystalline, quartz-bearing, sinters of New Zealand derived from crystallization of non-crystalline and paracrystalline opaline silicas. It occurs at levels of <13 vol.% of the SiO2 phases present in sinters between 20,000 and 200,000 y old but is generally either absent or below the level of detection in Tertiary sinters. Unambiguous identification of moganite is most readily accomplished by laser Raman spectroscopy; the technique allows individual microtextural elements of a sinter's fabric to be analysed. Conventional scanning X-ray powder diffraction procedures are limited in their ability to discern the characteristic moganite diffraction lines from the very similar quartz pattern, especially in those samples where moganite is at low concentration and/or unanticipated. However, powder diffraction, using a position-sensitive detector system, allows not only the identification of the moganite pattern in the presence of a large proportion of quartz, but also semiquantitative estimates of the different silica phases present in bulk sinter samples of ~450 mg. Moganite is part of the sinter maturation sequence. It occurs as a metastable phase that will ultimately transform to quartz, given sufficient time or a change in ambient conditions.

New data on the Gongo Soco palladium-oxygenated compounds are presented for the first time since the work of Johnson and Lampadius (1837). A variety of PdO species is documented, always in association with Cu, Fe and Mn, and includes Pd(OH)2 or PdO.H2O, and phases with metal excess in relation to oxygen, interpreted as metastable. Their remarkable occurrence in ‘ouro preto’ (black gold) and jacutinga (auriferous itabirite/iron ore) is the result of mertieite-II alteration. It involves leaching of Sb and As, limited removal of Pd, and incorporation of Cu, Mn and Hg into PdO species. The locus of Hg-bearing PdO species in microfractures parallel to the enclosing gold-mineralized shear band suggests at least one low-temperature hydrothermal generation. The presence of a halite crystal attached to gold testifies to the involvement of Cl-saturated hydrothermal fluids in the oxidizing environment of jacutinga formation.

An investigation into the relative stabilities and equations of state of stoichiometric FeS was conducted using first-principles pseudopotential calculations. These calculations were based on density functional theory and performed using ultrasoft Vanderbilt pseudopotentials within the generalized gradient approximation. We have identified four stable polymorphs of FeS along the 0 K isotherm as a function of pressure: troilite, an orthorhombic MnP-type structure, a monoclinic structure, and a CsCl-type structure. The calculated internal energy as a function of volume for each polymorph was fitted to 4th order logarithmic and 3rd order Birch-Murnaghan equations of state, yielding values for the bulk modulus, K, and its first and second derivatives with respect to pressure, K′ and K″. These equations of state may be used to characterize models of planetary cores.

The structural and thermodynamic properties of minerals are strongly affected by cation site-ordering processes. We describe methods to determine the main interatomic interactions that drive the ordering process, which are based on parameterizing model Hamiltonians using empirical interatomic potentials and/or ab initio quantum mechanics methods. The methods are illustrated by a number of case study examples, including Al/Si ordering in aluminosilicates, Mg/Ca ordering in garnets, simultaneous Al/Si and Mg/Al ordering in pyroxenes, micas and amphiboles, and Mg/Al non-convergent ordering in spinel using only quantum mechanical methods.

This paper reviews recent applications of Monte Carlo methods for the study of cation ordering in minerals. We describe the program Ossia99, designed for the simulation of complex ordering processes and for use on parallel computers. A number of applications for the study of long-range and short-range order are described, including the use of the Monte Carlo methods to compute quantities measured in an NMR experiment. The method of thermodynamic integration for the determination of the free energy is described in some detail, and several applications of the method to determine the thermodynamics of disordered systems are outlined.

More than 19,000 analytical data mainly from the literature were used to study statistically the distribution patterns of F and the oxides of minor and trace elements (Ti, Sn, Sc, V, Cr, Ga, Mn, Co, Ni, Zn, Sr, Ba, Rb, Cs) in trioctahedral micas of the system phlogopite-annite/siderophyllite-polylithionite (PASP), which is divided here into seven varieties, whose compositional ranges are defined by the parameter mgli (= octahedral Mg minus Li). Plots of trace-element contents vs. mgli reveal that the elements form distinct groups according to the configuration of their distribution patterns. Substitution of most of these elements was established as a function of mgli. Micas incorporate the elements in different abundances of up to four orders of magnitude between the concentration highs and lows in micas of ‘normal’ composition. Only Zn, Sr and Sc are poorly correlated to mgli. In compositional extremes, some elements (Zn, Mn, Ba, Sr, Cs, Rb) may be enriched by up to 2–3 orders of magnitude relative to their mean abundance in the respective mica variety. Mica/melt partition coefficients calculated for Variscan granites of the German Erzgebirge demonstrate that trace-element partitioning is strongly dependent on the position of the mica in the PASP system, which has to be considered in petrogenetic modelling.

This review indicates that for a number of trace elements, the concentration ranges are poorly known for some of the mica varieties, as they are for particular host rocks (i.e. igneous rocks of A-type affiliation). The study should help to develop optimal analytical strategies and to provide a tool to distinguish between micas of ‘normal’ and ‘abnormal’ trace-element composition.

An inclusion of corundum (ruby) was found in a clinopyroxene xenocryst in alkali basalt from the late-Cenozoic Chanthaburi-Trat volcanics of eastern Thailand. The clinopyroxene is fairly sodic, highly aluminous and magnesian (0.12–0.14 Na, 0.31–0.33 AlIV and 0.36–0.40 AlVI per 6(O), and Mg/(Mg+Fe2+) > 0.9)) and is chemically similar to clinopyroxene inclusions in rubies from nearby alluvial gem deposits, suggesting a common origin for the two types of occurrence. Sapphirine (Mg/(Mg+Fe2+) = 0.91–0.94) and garnet (py56–67alm11–18grs18–23) also occur as inclusions in alluvial rubies. Thermodynamic calculation of the equilibrium 2 di + 2 crn = 2 cats + en constrains the temperatures of clinopyroxene + corundum crystallization to between 800 and 1150 ± 100°C. Use of other equilibria as stability limits places the pressures of crystallization between 10 and 25 kbar, implying depths of between 35 and 88 km. The most Fe-rich clinopyroxene crystallized at a pressure in the lower part of the range. The pyropic garnet inclusions in corundum crystallized at pressures of >18 kbar (i.e. at depths > ~63 km).

The xenocrystic clinopyroxene could have coexisted in equilibrium with garnet of similar composition to the observed inclusions at the deduced temperatures of crystallization. The rubies probably crystallized in rocks of mafic composition, i.e. garnet-clinopyroxenites or garnet-pyriclasites, within the upper mantle.

Crystals of the compound Na4(UO2)(CO3)3 have been synthesized and the structure has been solved. It is trigonal with a= 9.3417(6), c = 12.824(1) Å, V = 969.2(1) Å3, space group Pc1 and Z = 4. The structure was refined on the basis of F2 (wR2 = 4.2%) for all unique data collected using Mo-Kα X-radiation and a CCD-based detector. The final R1 was 2.0%, calculated for 534 unique observed (Fo ≥ 4σF) reflections, and the goodness-of-fit (S) was 0.91. The structure contains a uranyl tricarbonate cluster composed of a uranyl hexagonal bipyramid that shares three equatorial edges with CO3 triangles. The uranyl tricarbonate clusters are connected through NaO6 and NaO5 polyhedra, forming a heteropolyhedral framework structure. This compound may be related to a uranyl carbonate phase with the same composition which has been reported as an alteration phase on the surface of Chernobyl ‘lava’, and as a mineral in the Jachymov ore district, Czech Republic.