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 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.

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.

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.

Structures of calcium-rare-earth (Ca-RE) fluorocarbonate minerals from southwest China have been investigated using selected area electron diffraction (SAED) and high-resolution transmission electron microscopy (HRTEM). They are described as combinations of layers of bastnäsite-(Ce), CeFCO3 (B layers), and synchysite-(Ce), CeFCO3·CaCO3 (S layers) (Donnay and Donnay, 1953). We report here the discovery of six new, regular, mixed-layer structures in parisite-(Ce) observed using SAED and HRTEM. The symmetry, cell parameters, chemical formulae and stacking of the structural unit layers, etc., were determined for each. The regular, mixed-layer structures are formed by stacking unit layers of bastnäsite-(Ce) and synchysite-(Ce) in varying proportions along the c axis. HRTEM shows that there are different distribution modes for the Ce-F ion layers, the CO3 ion groups between the Ce-F ion layers and the CO3 ion groups between the Ce-F and Ca ion layers. The minerals may be regarded as polymorphs with the same chemical composition and the same spacing of the unit layers, but different arrangements of ion layers in the structural unit layers and different stacking sequences of the structural unit layers.

The Fe 2p X-ray absorption spectra of single crystal gillespite, BaFeSi4O10, show a strong linear dichroism, i.e. a large difference in the absorption when measured with the polarization of the X-rays either parallel or perpendicular to the plane of the FeO4 group. The isotropic spectrum, obtained from measurement at the ‘magic angle’, and the polarization dependent spectra have been compared to atomic multiplet calculations and show an excellent agreement with theory. Analysis of the branching ratio, the linear dichroism, and the detailed peak structure confirms that the 5A1 level is the ground state at room temperature and pressure. The 5B2 level is sufficiently low in energy that a distortion of the electronic charge density, induced by increased pressure, may result in a 5B2 ground state.

Hyalotekite, a framework silicate of composition (Ba,Pb,K)4(Ca,Y)2Si8(B,Be)2 (Si,B)28F, is found in relatively high-temperature (⩾ 500°C) Mn skarns at Långban, Sweden, and peralkaline pegmatites at Dara-i-Pioz, Tajikistan. A new paragenesis at Dara-i-Pioz is pegmatite consisting of the Ba borosilicates leucosphenite and tienshanite, as well as caesium kupletskite, aegirine, pyrochlore, microcline and quartz. Hyalotekite has been partially replaced by barylite and danburite. This hyalotekite contains 1.29–1.78 wt.% Y2O3, equivalent to 0.172–0.238 Y pfu or 8–11% Y on the Ca site; its Pb/(Pb+Ba) ratio ranges 0.36–0.44. Electron microprobe F contents of Långban and Dara-i-Pioz hyalotekite range 1.04–1.45 wt.%, consistent with full occupancy of the F site. A new refinement of the structure factor data used in the original structural determination of a Långban hyalotekite resulted in a structural formula, (Pbl.96Bal.86K0.18)Ca2(B1.76Be0.24)(Sil.56B0.44)Si8O28F, consistent with chemical data and all cations with positive-definite thermal parameters, although with a slight excess of positive charge (+57.14 as opposed to the ideal +57.00). An unusual feature of the hyalotekite framework is that 4 of 28 oxygens are non-bridging; by merging these 4 oxygens into two, the framework topology of scapolite is obtained. The triclinic symmetry of hyalotekite observed at room temperature is obtained from a hypothetical tetragonal parent structure via a sequence of displacive phase transitions. Some of these transitions are associated with cation ordering, either Pb–Ba ordering in the large cation sites, or B–Be and Si–B ordering on tetrahedral sites. Others are largely displacive but affect the coordination of the large cations (Pb, Ba, K, Ca). High-resolution electron microscopy suggests that the undulatory extinction characteristic of hyalotekite is due to a fine mosaic microstructure. This suggests that at least one of these transitions occurs in nature during cooling, and that it is first order with a large volume change. A diffuse superstructure observed by electron diffraction implies the existence of a further stage of short-range cation ordering which probably involves both (Pb,K)–Ba and (BeSi,BB)–BSi.

The turquoise group has the general formula: A0–1B6(PO4)4−x(PO3OH)x(OH)8.4H2O, where x = 0–2, and consists of six members: planerite, turquoise, faustite, aheylite, chalcosiderite and an unnamed Fe2+-Fe3+ analogue. The existence of ‘coeruleolactite’ is doubtful. Planerite is revalidated as a species and is characterized by a dominant A-site vacancy. Aheylite is established as a new member of the group, and is characterized by having Fe2+ dominant in the A-site.

Chemical analyses of 15 pure samples of microcrystalline planerite, turquoise, and aheylite show that a maximum of two of the (PO4) groups are protonated (PO3OH) in planerite. Complete solid solution exists between planerite and turquoise. Other members of the group show variable A-site vacancy as well. Most samples of ‘turquoise’ are cation-deficient or are planerite. Direct determination of water indicates that there are 4 molecules of water.

Planerite, ideally ☐Al6(PO4)2(PO3OH)2(OH)8.4H2O, is white, pale blue or pale green, and occurs as mamillary, botryoidal crusts as much as several mm thick; may also be massive; microcrystalline, crystals typically 2–4 micrometres, luster chalky to earthy, H. 5, somewhat brittle, no cleavage observed, splintery fracture, Dm 2.68(2), Dc 2.71, not magnetic, not fluorescent, mean RI about 1.60. a 7.505(2), b 9.723(3), c 7.814(2) Å, α 111.43°, β 115.56°, γ 68.69°, V 464.2(1) Å3, Z = 1.

Aheylite, ideally Fe2+Al6(PO4)4(OH)8.4H2O, is pale blue or green, and occurs as isolated and aggregate clumps of hemispherical or spherical, radiating to interlocked masses of crystals that average 3 micrometres in maximum dimension; porcelaneous-subvitreous luster, moderate to brittle tenacity, no cleavage observed, hackly to splintery fracture, not magnetic, not fluorescent, biax. (+), mean RI is about 1.63, Dm 2.84(2), Dc 2.90. a 7.400(1), b 9.896(1), c 7.627(1) Å, α 110.87°, β 115.00°, γ 69.96°, V 460.62(9) Å3, Z = 1.

Polarized optical absorption spectra of single crystals of the two dimorphic Mn2AsO4(OH)-minerals eveite and sarkinite show that minor concentrations of Mn3+ at the octahedral site determine the colour and cause the distinct pleochroism in green and yellow of eveite. In the sarkinite spectra only absorption bands due to spin-forbidden d-d transitions in Mn2+ at six- and five-coordinated sites are observed, which produce a weak flesh-red mineral colour and a very faint pleochroism.

Duftite, PbCu(AsO4)(OH) is orthorhombic, space group P212121 with a = 7.768(1), b = 9. 211(1), c = 5.999(1) Å, Z = 4; the structure has been refined to R = 4.6% and Rw = 6.5% using 640 observed reflections [F> 2σ(F)]. The structure consists of chains of edge-sharing CuO6 ‘octahedra’, parallel to c; which are linked via AsO4 tetrahedra and Pb atoms in distorted square antiprismatic co-ordination to form a three dimensional network. The CuO6 ‘octahedra’ show Jahn-Teller distortion with the elongation running approximately along <627>. The hydrogen bonding network in the structure was characterized using bond valence calculations. ‘β-duftite’ is an intermediate in the duftite-conichalcite series, which has a modulated structure based on the intergrowth of the two structures in domains of approximately 50 Å. The origin of the modulation is thought to be associated with displacements in the oxygen lattice and is related to the orientation of the Jahn-Teller distortion of CuO6 ‘octahedra’. Approximately half of the strips show an elongation parallel to <627> while the other strips are elongated parallel to [010]. This ordering results in an increase in the b cell repeat compared to duftite and conichalcite.