Electron-probe microanalysis (EPMA) is applicable to rare-earth elements (REE) in minerals with relatively high REE concentrations (e.g. hundreds of parts per million). However, given that each of the 14 REE has at least 12 X-ray lines in the L spectrum, finding peak-free regions for background measurement can be problematical. Also, measured peak intensities are liable to require correction for interferences. Hitherto, little attention has been paid to the optimisation of background offsets and the implications of the wide variation in REE distribution patterns in different minerals. The ‘Virtual WDS’ program, which enables complex multi-element spectra to be synthesised, has been used to refine the conditions used for different REE distributions. Choices include whether to use the Lβ1 rather than the Lα1 line, background offsets, and counting times for comparable relative precision. Correction factors for interferences affecting peak and background measurements have also been derived.

The 1800 m thick preserved remnant of the Tertiary lava succession of Mull and Morvern consists of three basic mantle-derived magma types, with compositions varying from tholeiitic to mildly alkalic, and from picritic basalts to trachytes. This results in a similarly wide range in mineral compositions. Contrary to the suggestions of previous workers the mineral chemistry of the lava succession (in conjunction with published major and trace element chemistry) is strongly supportive of a fractional crystallisation origin for the more evolved lavas.

Resorped and regrown (with more basic material) plagioclase phenocrysts found in the more-evolved are indicative of magma mixing processes involving replenishment of an evolving magma chamber with more-basic magma. Lavas containing 15–20 vol.% plagioclase phenocrysts probably represent eruptions from the top of a magma chamber where flotation cumulates of plagioclase had developed. Fragmental phenocrysts found in some highly plagioclase phyric lavas (from near the top of the preserved lava succession) suggest that the eruption of lavas may have been explosive.

For complex rocks in which the structure of minerals, rather than their chemical composition, changes with progressive evolution of the system, it makes sense to try and monitor such an evolving system through the progressive change in the crystal structures of the constituent phases. In effect, the paragenetic sequences of minerals in such complex environments should be related to the crystal structures of the constituent minerals. In order to consider variations in structure topology, we need to organize crystal structures into hierarchical schemes, using the hypothesis that structures may be hierarchically ordered according to the polymerization of the coordination polyhedra with higher bondstrengths. Structural units are organized according to the mode of polymerization: unconnected polyhedra, clusters, chains, sheets and frameworks.

The bond-valence structure of (OH) and (H2O) shows that on one side, (OH) and H2O are strong Lewis bases; on the other side, they are weak Lewis acids. As a result, a very important role of both (OH) and (H2O) is to prevent polymerization of the structural unit in specific directions. Thus, the dimensionality of the structural unit is controlled primarily by the amount and role of hydrogen in the structure. The way in which we have formulated these ideas also allows development of a predictive framework within which specific aspects of the chemistry and structure of phosphates can be considered.

This approach to mineral structure, applied via the idea of a structural unit, can play a major role in developing structural hierarchies in order to bring about some sort of order to the plethora of hydroxyhydrated-phosphate structures. Furthermore, by combining the idea of binary structural representation with bond-valence theory, we see the eventual possibility of predicting stoichiometry and structural characteristics of these minerals, particularly those in complex low-temperature hydrothermal environments

A Tertiary, dacitic volcanic land-form in Kelowna, British Columbia, shows layering that has not been recognized elsewhere. Layering is expressed as thin (0.5 m) layers separated by thick (4.5 m) layers exposed along a weathered fault scarp. The major elements show that both thick and thin layers are dacitic and geochemically very similar. Trace element modelling indicates that thin layers formed from thick layers via crystal fractionation involving removal of plagioclase, biotite and magnetite in the proportions 75:20:5, and with only 12% fractionation. The thin layers represent segregation veins generated during crystallization of the dacite. They formed when the crystal mush at the bottom of the upper crust successively, thermally contracted, fractured and foundered, siphoning evolved interstitial liquid from the mush into the horizontal crack. Cooling of the segregation veins led to further fracturing. Later, fluids following these fractures altered the thin layers and precipitated secondary carbonate minerals. The altered thin layers weather preferentially, thus visually accentuating the small primary chemical differences between thick and thin layers. The scale of layering, mode of formation and differentiation mechanisms appear different from those in felsic magma chambers and it is unclear how common this phenomenon is. However, similar layering is more easily identified and commonly developed in mafic lava flows.

How can the equilibrium and non-equilibrium thermodynamics of minerals be understood from their atomic-scale structural features? How can they be predicted, simply from models for the forces between atoms? Advances in analytical theory, statistical mechanics, experimental solid-state science, computational power, and the sophistication of a mineralogical approach that brings all of these together, means that these questions, once imponderable, are now realistically tractable. These questions have been exercising the minds of mineralogists over the last decade or so, and have motivated many developments in the science. Acting as way-markers along the path, there are a number of publications which have followed from meetings where these questions have been addressed. It is now twelve years since the publication of Microscopic to Macroscopic, an edition of Reviews in Mineralogy (Kieffer and Navrotsky, 1985) that sought to identify the fundamental controls on the bulk properties of minerals in terms of their atomic-scale characteristics.

Petrographic and compositional variations in the Lower Main Zone (LMZ) of the western Bushveld Complex indicate changing regimes of magma replenishment. The lowermost unit of the LMZ, designated N-I, is an enigmatic sequence of leuconoritic cumulates, characterized primarily by up-sequence increases in both orthopyroxene Mg# and whole-rock Sr isotope initial ratio. The Sr isotope profile of N-I is ascribed to injection and progressive integration of small influxes of fresh magma with high (Main Zone-type) Sr isotope initial ratios. The basal Fe-enrichment in N-I, on the other hand, is ascribed to a separate, later mechanism involving the downward migration of late-stage Fe-rich liquids. The overlying two units, N-II and G-I, delineated chiefly in terms of basal Mg-enrichment of orthopyroxene, are ascribed to injections of fresh magma into the chamber. Poikilitic orthopyroxene grains in the basal parts of both N-II and G-I suggest entrainment and partial resorption of plagioclase grains from the semi-crystalline resident material into which the fresh magma was intruded.

Reactions between olivine and plagioclase form kelyphytic corona textures in the Rymmen gabbro, southern Sweden. The coronas surround olivine and consist of enstatite ± amphibole and phlogopite, combined with an outer rim of symplectic intergrowth of green spinel and amphibole. Corona reactions took place in fractures within olivine prior to the formation of chlorite, serpentine, and magnetite in the fractures at cooler conditions. Disequilibrium between olivine and plagioclase has been put forward as an explanation for the corona formation. However, inclusions of plagioclase in olivine show that there is no reaction between these minerals, since no new minerals formed between them. The conclusion drawn is that the most important factor for development of kelyphytic structures in the Rymmen gabbro is contact with a late deuteric fluid in an environment where olivine and plagioclase are close to each other. Temperature estimates for the formation of the kelyphytic coronas in the Rymmen gabbro yield consistent temperatures of around 800 ± 30°C and pressures 6–8 kbar, which indicate emplacement at a depth of 20–30 km in the crust. Late deuteric fluids caused olivine replacement by intergrown orthopyroxene and magnetite, in Fe-Ti oxide-rich rocks only. In these, plagioclase is replaced by symplectite when in contact with ilmenite and magnetite. It is noted that the symplectite minerals have low Ti contents. This suggests that the Fe-Ti oxide was a catalyst for the reaction between plagioclase and late-stage aqueous fluids rather than being a reactant, alternatively that the magnetite/ilmenite was a reactant and Ti was retained in the oxide.

The equilibrium structures of cubic, tetragonal and orthorhombic phases of magnesium silicate perovskite are found from first principles electronic structure calculations. Zone centre and zone boundary phonons of each phase are also calculated from ab initio forces from finite displacments, and phase transitions between the phases are analysed in terms of phonon instabilities, and coupling between modes. Both the cubic and tetragonal phases have strongly unstable modes dominated by rotation of the SiO6 octahedra, which freeze in to ultimately form the orthorhombic phase. First priniciples molecular dynamics simulations at finite temperatures are used to further investigate the stability of the intermediate tetragonal phase and the coupling between participating phonon modes. The implications for a transition temperature between orthorhombic and tetragonal phases are discussed.

The crystal structure of macphersonite (Pb4SO4(CO3)2(OH)2, Pcab, a = 9.242(2), b = 23.050(5), c = 10.383(2) Å) from Leadhills, Scotland has been determined to an R = 0.053. The structure has many features in common with its polymorph leadhillite including three distinct types of layers. Layer A includes sulphate tetrahedra, Layer B is composed of Pb and OH, while Layer C is composed of Pb and CO3 with topology identical to that in cerussite. In both macphersonite and leadhillite these layers are stacked along [010] as …BABCCBABCC… The double CC layer is almost identical in the two structures and forms a structural backbone and occurs in other structures including hydrocerussite and plumbonacrite. The sulphate layer shows the greatest difference between the two structures and can be described by a pattern of up or down pointing tetrahedra. For macphersonite the sequence along [001] is …UDUDUD… while in leadhillite the sequence along [010] is …UDDUUDDU… This latter sequence effectively doubles b relative to the equivalent direction in macphersonite. Susannite, a third polymorph, may have yet another sequence of sulphates to give trigonal symmetry; by heating leadhillite, displacive movements of sulphate groups may occur with a conversion to susannite.

The rhythmic modal layering in the Nunarssuit syenite has a vertical extent of >150 m and a lateral extent of >15 km. Individual layers average 20 cm thick and grade from a relatively melanocratic base into more leucocratic syenite over a distance of up to 5 cm. The major cumulus phases are alkali feldspar, ferro-salite/hedenbergite and fayalite. Two basic stratigraphic cycles have been identified in which faint modal layering becomes more pronounced up section, each cycle terminating in a thick melanocratic zone. Slumps, slump breccias, troughs, micro-rhythmic layering and one occurrence of crossed layers were observed.

Qualitative grain size analysis indicates no size sorting in the layers. Preliminary application of crystal size distribution theory to ferro-salite/hedenbergite and fayalite from the bases of individual layers gives results which may be interpreted as indicating a relative lack of coarse grains. If the layers were deposited from density currents it would be expected that the coarsest grains would be deposited close to the source of the currents. There is no evidence in the majority of the syenite that the cumulus pile underwent compaction during crystallization.

There was little, or no, primary chemical variation across individual layers. Whole-rock compositions and the ferro-salite/hedenbergite, fayalite, biotite and amphibole present in the syenites show a slight, but statistically significant, increase in the ratio Mg/(Mg+Fetotal), from the base up to the top of the layered succession.

A model is suggested in which successive magma layers become more ferroan towards the top of the chamber. Cooling is concentrated at the top of the chamber and layers of magma crystallize sequentially, the uppermost, ferroan layers first. As layers of magma cool and crystallize they sink, as crystal-melt plumes, to the bottom of the chamber where they source density currents from which layers are deposited.

A suite of ultramafic-mafic alkaline igneous rocks in the Damodar Valley, eastern India, contains carbonate, phosphate and titanate minerals that are not characteristic or common in minettes or lamproites, but are typical of orangeites (Group II kimberlite) from southern Africa. Phlogopite grains from the Damodar alkaline rocks yield mean 40Ar/39Ar ages of 116.6±0.8 Ma, 113.5±0.5 Ma and 109.1±0.7 Ma (1σ errors) using laser dating techniques. These ages are similar to the Rb-Sr ages of African orangeites, which lie mostly in the range 121 to 114 Ma. Prior to this study, only one possible occurrence of orangeite (the ∼820 m.y.-old Aries pipe, Western Australia) was known outside the Kaapvaal craton and its environs. If the Damodar alkaline rocks are bona fide orangeites, it is likely that they were generated at depths of >150 km, within the stability field of diamond.

The structure of a synthetic end-member wairakite (CaAl2Si4O12·2H2O) has been determined using Rietveld analysis of high-resolution, synchrotron X-ray powder diffraction data, and 29Si and 27Al magic angle spinning nuclear magnetic resonance spectroscopy. The framework in the synthetic sample is more disordered than that in natural wairakite. Ca is distributed over the cavity cation sites M2, M12A, M12B in the approximate proportions 0.8:0.1:0.1, respectively, with M11 being vacant. 29Si MAS NMR data are consistent with about 80% of the Si occupying tetrahedral T11 and T12 sites linked to two Al atoms [Q4(2Al) silicons]. Tetrahedral and cavity cation site disorder are coupled so that Al mainly occupies T2 sites, with Ca in M12A and M12B being balanced by Al in T12A and T12B; T11A and T11B sites appear to only contain Si, in agreement with the M11 site being vacant. The crystal chemistries of the wide range of stoichiometries which crystallize with the leucite/pollucite structure-type are also reviewed, with particular attention being paid to the tetrahedral ordering configurations present in these phases, and the implications to crystallographic phase transitions.

A peralkaline nephelinite lava ([Na+K]/Al 2.15) from the active carbonatite volcano Oldoinyo Lengai, contains combeite, Ba lamprophyllite, a phase with affinities to delhayelite, CeSrNb perovskite, a CaNa phosphate high in Sr, Ba and K, and peralkaline glass; in addition to Fe-rich nepheline, aegirine-rich clinopyroxene and FeK-rich sodalite. The high alkali concentrations relative to alumina in the bulk rock could not have been achieved by fractionational crystallisation of the known Al-rich phenocryst phases (nepheline and sodalite) and some other process must be invoked.

Unusual corundum-bearing rocks occur in the Bond Range, northern Tasmania, in a hydrothermally altered Cambrian quartz porphyry. The assemblage exhibits quartz and corundum in mutual contact, a rare phenomenon, in association with andalusite, pyrophyllite, diaspore and other minerals. This metastable assemblage apparently resulted from advanced argillic alteration at moderate temperature and low pressure, followed by rapid depressurisation accompanying boiling of hydrothermal, granite-derived fluids. This corundum occurrence appears to be unrelated to the sapphires in placer deposits in Tasmania.

Computer simulation techniques have been used to investigate defect formation and the diffusion of Ca and Mg in diopside. It was found that isolated, non-interacting CaO and MgO Schottky defects had the lowest formation energies (3.66 and 3.97 eV respectively); oxygen Frenkel defects are the most favourable oxygen defects (formation energies 3.93 eV). Magnesium and calcium self-diffusion in the c-direction of diopside is easiest by a vacancy mechanism involving either direct jumps along the c-direction, or double jumps in the b-c plane. In the extrinsic regime, diffusion activation energies for Mg are predicted to be 9.82 eV (direct route) and 1.97 eV (double jump route); for Ca diffusion, activation energies are predicted to be 6.62 eV (direct route) and 5.63 eV (double jump route). If additional vacancies (oxygen or magnesium) are present in the vicinity of the diffusion path, Ca migration energies fall to 1.97–2.59 eV. At elevated temperatures in the intrinsic regime, diffusion activation energies of ⩾ 5.95 eV are predicted for Mg self-diffusion and 9.29–10.28 eV for Ca self-diffusion. The values for Ca diffusion are comparable with published experimental data. It is inferred that a divacancy mechanism may operate in diopside crystals.

High temperature microthermometry and Scanning Electron Microprobe (SEM) analyses were used to study natural magmatic remnants in quartz crystals in granitoids from the Timna Igneous Complex, southern Israel, and to constrain physicochemical parameters during their crystallization. For the porphyritic granite, alkali granite and quartz monzodiorite, liquidus temperatures are 710–770, 770–830 and 770–840°C, respectively; solidus temperatures are 690–770, 710–790 and 770°C, respectively. Pressures during crystallization and water content in the magmas were determined using the phase diagram of the modal granite system. The determined P-T-conditions are typical for water-saturated granitoid magmas (>4–8 wt.%) generated and crystallized at a shallow crustal level.

SEM data on melt inclusions support conclusions of previous investigations on two types of granitoid magmas exposed in the Timna Igneous Complex: the porphyritic and alkali granites. Different trends of crystallization are proposed for these granites. Crystallization of the porphyritic granite started with cotectic crystallization of plagioclase and terminated in residual K-feldspar-rich crystallization; crystallization of the alkali granite took place at higher temperatures, starting with K-rich alkali-feldspar crystallization and terminating in residual Na-rich eutectic crystallization.

Parameters not available from other sources — temperature and pressure of the liquidus and solidus stages, water content, trends of crystallization — were obtained for the porphyritic and alkali granites.

Natrocarbonatite magma, erupted as lava flows in the Tanzanian volcano Oldoinyo Lengai in June and November of 1988, has evolved chemically since its formation. The June and November flows of 1988 display increasing Cl, F, Ba, K, Mg and Mn, concomitantly with Na, Ca and P depletion. Furthermore, the June magma, at the time of eruption, had higher Cl, F, Ba and K contents and lower Ca than the November magma and evolved to higher levels of Cl, F, Ba and K content and lower Ca, Na and P. The mineralogy of the lavas reflects these trends. Crystallization of fluorite and halite–sylvite solid solution, usually as a symplectic intergrowth, occurs when Cl and F concentrations reach the critical value necessary to stabilize both minerals and explains why neither occurs as a phenocryst phase. Natrocarbonatite magma has undergone considerable and rapid magmatic evolution, probably in small and separate magma chambers. Two minerals, nyerereite and gregoryite, have dominated the crystallization history of natrocarbonatite magma, and many lavas are phenocryst-rich. However, because most of the lavas are composed principally of these two minerals, crystal accumulation has not greatly changed their composition and, consequently, we suggest that the bulk composition of the lavas closely approximates that of the parental magma.

The crystal structure of szenicsite, Cu3MoO4(OH)4, orthorhombic, a = 8.5201(8), b = 12.545(1), c = 6.0794(6) Å, V = 649.8(2) Å3, space group Pnnm, Z = 4, has been solved by direct methods and refined by least-squares techniques to an agreement index (R) of 3.34% and a goodness-of-fit (S) of 1.11 for 686 unique observed [|F| ⩾ 4σF] reflections collected using graphite-monochromated Mo-Kα X-radiation and a CCD area detector. The structure contains three unique Cu2+ positions that are each coordinated by six anions in distorted octahedral arrangements; the distortions of the octahedra are due to the Jahn-Teller effect associated with a d9 metal in an octahedral ligand-field. The single unique Mo6+ position is tetrahedrally coordinated by four O2− anions. The Cu2+ϕ6 (ϕ: unspecified ligand) octahedra share trans edges to form rutile-like chains, three of which join by the sharing of octahedral edges to form triple chains that are parallel to [001]. The MoO4 tetrahedra are linked to either side of the triple chain of Cu2+ϕ6 octahedra by the sharing of two vertices per tetrahedron, and the resulting chains are cross-linked through tetrahedral-octahedral vertex sharing to form a framework structure. The structure of szenicsite is closely related to that of antlerite, Cu3SO4(OH)4, which contains similar triple chains of edge-sharing Cu2+ϕ6 octahedra.

Apatite-dolomite carbonatite at Lesnaya Varaka, Kola Peninsula, Russia, hosts intricate mineral intergrowths composed of lueshite in the core and pyrochlore-group minerals in the rim. Lueshite is a primary Nb-bearing phase in the carbonatite and ranges in composition from cerian lueshite to almost pure NaNbO3. For comparison, the compositional variation of lueshite from the Kovdor and Sallanlatvi carbonatites is described. At Lesnaya Varaka, lueshite is replaced by nearly stoichiometric Na-Ca pyrochlore due to late-stage re-equilibration in the carbonatite system. X-ray powder diffraction data for both minerals are presented. Barian strontiopyrochlore, occurring as replacement mantles on Na-Ca pyrochlore, contains up to 43% Sr and 8–18% Ba at the A-site, and shows a high degree of hydration and strong ionic deficiency at the A- and Y-sites. This mineral is metamict and, upon heating, recrystallises to an aeschynite-type structure. Monazite-(Ce) found as minute crystals in fractures, represents the solid solution between monazite-(Ce) CePO4, brabantite CaTh(PO4)2 and SrTh(PO4)2. Our data indicate the high capacity of the monazite structure for Th and accompanying divalent cations at low temperatures and pressures that has a direct relevance to solving the problem of long-term conservation of radioactive wastes. Monazite-(Ce) and barian strontiopyrochlore are products of low-temperature hydrothermal or secondary (hypergene) alteration of the primary mineral assemblage of the carbonatite.

Time-of-flight neutron powder diffraction has been employed to determine precise occupancies of the M1 and M2 metal cation sites in synthetic olivines of compositions (Fe0.3Mn0.7)2SiO4, (Fe0.5Mn0.5)2−SiO4, and (Fe0.7Mn0.3)2SiO4. The distribution coefficient for Fe-Mn exchange in these samples has values of 4.864, 3.976, and 4.078, reflecting the preference of Mn2+ for the M2 site, over Fe2+. These results, and the behaviour of the difference in mean bond lengths of the two sites, indicate that, while showing a tendency towards ordering, the composition-dependence of the solid solution is near ideal.