Intruded into the Palaeogene lava field and underlying Moine (Neoproterozoic) crystalline basement rocks around Loch Scridain, Isle of Mull, Scotland, is a suite of high-level, inclined, xenolithic sheets, ranging in composition from basalt, through andesite and dacite, to rhyolite. These sheets, associated with the Mull central volcano, were emplaced post 55 Ma. As well as numerous crustal xenoliths, the more basic members of the complex contain a diverse suite of ultrabasic and basic xenoliths. Xenolith types include feldspathic peridotite with cumulus olivine, pyroxenite, gabbro with cumulus plagioclase and cumulus clinopyroxene, and pure anorthosite. Mineralogical data, coupled with whole-rock major- and trace-element data from a small number of the xenoliths suggest that the xenoliths represent early-formed cumulates cognate with their host basalts. Sr and Nd isotope data from the xenoliths confirms the cognate origin, and also shows that the basic magmas suffered crustal contamination at an early stage.

In 1962 Dawson described a calcite carbonatite (specimen BD83) from the Tanzanian volcano Oldoinyo Lengai as a sövite, thus implying that at an earlier stage in its evolution this volcano had crystallized magmatic calciocarbonatites as well as the highly alkalic natrocarbonatite lava that has been erupted in more recent times. This proposition is difficult to reconcile with the currently fashionable hypothesis whereby the natrocarbonatite lava separated immiscibly from a type of nephelinite magma, most recently thought to be a wollastonite nephelinite. In 1993 Dawson sought to discredit the magmatic origin of this sövite specimen by arguing that it was derived from natrocarbonatite lava through extreme alteration (calcitization) in which process the original nyerereite was replaced by calcite in near-perfect pseudomorphs. We suggest that the arguments advanced in support of this concept are unconvincing and that the specimen is exactly what it was originally described as, namely a magmatic sövite in which the calcite crystallized from a magma rather than having replaced nyerereite. We do not seek to discredit the liquid immiscibility hypothesis but do believe that whatever process is responsible for the Oldoinyo Lengai natrocarbonatites and silicate rocks must also allow for the crystallization of calciocarbonatite.

This paper is based on microprobe analysis (Ta, Nb, Fe, Mn, Ti, W, Sn) and Fe3+ EPR spectra of cassiterite samples from 14 tin deposits from the Iberian Hercynian Massif. The interpretation of microprobe data, atomic ratios (Fe+Mn)/(Nb+Ta), and Fe3+ EPR spectra reveal that the coupled substitution: 3Sn4+ = (Fe,Mn)2+ + 2(Nb,Ta)5+ is dominant in cassiterites from pegmatites, and high-temperature quartz veins and in the dark zones of cassiterites.

The mechanisms:

2Sn4+ = Fe3+ + (Nb,Ta)5+ and

Sn4+ + O2− = Fe3+ + OH−

are dominant in those from medium-low temperature quartz veins and in the light zones of cassiterites.

Platinum-group minerals (PGM) from placer deposits in Colombia, California, Oregon and Alaska were investigated with the electron microprobe, proton microprobe (μ-PIXE) and ion probe to analyse their major and trace element contents and 187Os/186Os isotopic ratios. Most of the grains in the samples investigated proved to be essentially homogeneous alloys of Pt-Fe and Os-Ir-Ru although a few of them contained inclusions of other PGM such as cooperite and laurite. Detailed analyses were undertaken on the Os-Ir-Ru alloy phases.

The 187Os/186Os isotope ratios fell into a range from 1.005 to 1.156 and are consistent with data published on PGM from other placer deposits from these regions. The ratios, together with the trace element data (and in particular the low rhenium content) determined by ion probe and μ-PIXE, indicate that crustal osmium was not incorporated in the grains and that no significant evolution of the 187Os/186Os ratios occurred during their history. These data, along with mineralogical and textural evidence, are consistent with a mantle origin for the grains through ultramafic intrusions, although the data do not entirely rule out alternative interpretations.

Remarkable single crystal galena formations in the unique form of cylindrical or steep conical ‘pillars’ with ‘capitals’ of small rhombododecahedral single crystals of sphalerite, are described. It is suggested that the pillars result from a highly specific process of anisotropic mineral dissolution controlled by a system of internal channels in the original skeletal crystals and represent a kind of dissolution whiskers.

Several complex Cu-Pb-Bi, Cu-Pb-Bi-Sb and Ag-Pb-Bi sulphosalt minerals have been identified in samples from hydrothermal vein mineralisation associated with the Toroiaga sub-volcanic body in the Baia Borşa area of Maramureş County, northwest Romania. This is the first chemically-documented report of Bi-sulphosalts in the Neogene metallogenic province around Baia Mare. The investigated samples contain abundant amounts of matildite solid solution within galena, the Cu-Pb/Bi sulphosalts aikinite, friedrichite, krupkaite, hammarite, lindströmite and gladite as well as nuffieldite and berryite. Within the Ag-Pb/Bi group, the majority of analysed grains can be regarded as members of the lillianite homologous series. Three distinct lillianite homologues were identified, which correspond to (i) phases along the lillianite-gustavite solid solution join (Pb3Bi2S6-AgPbBi3S6), (ii) phases within solid solution field of heyrovskyite, and (iii) compositions which best correspond to ‘schirmerite’, sensu Makovicky and Karup-Møller (1977b), but may represent disordered gustavite, vikingite or eskimoite. Some of the analysed lillianite homologues contain excess Cu, which may occupy interstitial sites. Furthermore, a large proportion of the lillianite homologues display significant substitution of Sb for Bi within the limits predicted by experimental investigations. Cosalite, also showing a range of compositions including Sb-rich varieties is recognised. Izoklakeite, Cu2Pb22(Sb,Bi)22S57, is an abundant phase throughout the analysed samples, its composition is in good agreement with previously published analyses, except for excess Cu and Fe beyond the limits previously reported. The description of several minerals from this new occurrence and compositional data on them, including the Sb-bearing varieties, provides valuable additional information on compositional limits in natural samples.

During research on the influence of temperature on cation partitioning in natural Mg-Al-Fe2+-Fe3+ spinels, some crystals were accidentally oxidized during heat treatment. The oxidation product, studied by means of single-crystal X-ray diffraction, turned out to be a phase retaining the Fd3m parent spinel structure, but with cell edge a and oxygen coordinate u considerably smaller than the parent ones (a ∼ 8.087 as compared with ∼ 8.111 Å; u ∼ 0.2609 vs. 0.2617–0.2636) and with vacant sites due to oxidation.

Assuming that the oxidation process must occur due to the addition of oxygen to the crystal boundary as cations are being preserved and rising in total valence, the site population was determined and compared with that of untreated and heated samples. It was found that, on oxidation, a charge enrichment in the tetrahedral site T had occurred, this phenomenon following that observed during heating at increasing temperatures also in other spinel series. This continuity was always in the direction of an increase in random charge distribution. Cation vacancies produced during oxidation were restricted to the octahedral site M.

Examination of bulk sections by reflected light microscopy showed a few hematite lamellae as inclusions in the oxidized samples, not detectable by microprobe analysis or single-crystal structural refinement. However, hematite played a marginal part in oxidation. Vacancy-oxygen distances in oxidized spinels were determined from experimental data in the literature.

Two C2/c pyroxene suites from sodic alkaline rocks (Basanite-Phonolite: B-Ph and Alkali basalt-Trachyphonolite: AB-T) belonging to the McMurdo Volcanic Group (Mt. Melbourne province and Mt. Erebus, Antarctica) were investigated by single-crystal X-ray diffraction combined with electron probe microanalysis which together provide accurate site occupancy and site configuration parameters. Variations in site volumes distinguish the clinopyroxenes belonging to the more alkaline B-Ph suite from those of the AB-T suite. The former have higher VM2 and, for similar cell volume, lower VM1 and higher VT. In these C2/c pyroxenes, the bond lengths of M1 depend on R3+ content, necessary to balance AlIV in the T site. M1 geometric variations are similar for both B-Ph and AB-T suites. However, the M2 site is crucial for variations in polyhedral configurations. The increase in AlIV affects the shortest M2-O bond lengths in different ways depending on (Ca+Na) contents in the M2 site. Thus, the clinopyroxenes were distinguished in two different groups not related to the two suites. The first group is characterized by (Ca+Na) higher than 0.90 atoms per formula unit but shows a good positive correlation between the shortest M2-O bond lengths and AlIV content, at quite constant (Ca+Na). The second group has (Ca+Na) less than 0.90 atoms per formula unit but shows a poor correlation between the shortest M2-O bond lengths and AlIV content. In general, shortening of the longest M2-O bond lengths is associated with increase in AlIV. The cell and M1 volumes suggest that the clinopyroxenes, including the larger and sometimes resorbed macrocrysts, crystallized at a pressure lower than 5 kbar, fitting the petrography and evolved character of the rocks in question.

The crystal structure of averievite, Cu5O2(VO4)2·nMX has been determined. Trigonal system, space group P3, a = 6.375(1), c = 8.399(1) Å, V = 295.6(1) Å3, Z = 1, Dx = 4.01(1) g/cm3. The atomic arrangement is characterized by infinite nets parallel to (001) composed of [OCu4]6+ tetrahedra linked via corners in hexagonal rings. The bases of neigbouring tetrahedra are in one plane and their non-shared corners are turned to the opposite sides. The [VO4]3− tetrahedra are attached to the bases of [OCu4] tetrahedra. There are large (R >3.2 Å) channels in the structure where large molecular particles can enter. The comparison of the averievite structure with related compounds (in particular, copper oxovanadates) is given from the point of view of [OT4] polyion crystal chemistry.

A Ba-rich celestine (Sr0.87Ba0.13SO4) filling cavities of volcanoclastic rocks from Montecchio Maggiore (Vicenza, Italy) was studied. The role of the Ba content in the mineral was determined using X-ray powder data, single crystal X-ray refinement, thermal and chemical analyses. The unit cell parameters (obtained by single crystal diffraction) are a = 8.408, b = 5.372, c = 6.897 Å, and the refinement in the space group Pnma (Z = 4) gives the final R value of 0.039. The average (Sr,Ba)-oxygen bond length is 2.842 Å and agrees with an occupancy of Sr 87% and Ba 13%. Individual bond lengths (Sr,Ba)-O and bond strength calculations confirm that all twelve interactions are significant and define an irregular array around the cation.

High-resolution intensity profiles can be generated from X-ray diffraction films using a desk-top scanner and computer image analysis. The resulting intensity profiles have spatial resolutions equal to, or exceeding that of modern powder diffractometers — at a fraction of the cost. This technique provides an economical way of preserving the information stored in libraries of old (and deteriorating) powder diffraction films. The same technique can also be extended to permit quantitative analysis of single-crystal diffraction films.