The Li and B isotopic compositions of gem-quality Cu-bearing tourmalines were used (1) to distinguish among Paraiba tourmalines from Brazil and Cu-bearing tourmalines from Nigeria and Mozambique; and (2) to identify the likely source of Li and B for these gem-quality tourmalines. The δ11B values of tourmaline from Paraiba, Brazil, range from –42.4‰ to –32.9‰, whereas the δ11B values of Cu-bearing tourmaline from Nigeria and Mozambique range from –30.5‰ to –22.7‰ and –20.8‰ to –19.1‰ respectively. Tourmalines from each locality have relatively homogeneous δ11B values and display no overlap. There is slight overlap between δ7Li values of Paraiba tourmaline (+24.5‰ to +32.9‰) and Cu-bearing tourmaline from Nigeria (+32.4‰ to +35.4‰), and δ7Li values of Cu-bearing tourmaline from Nigeria and Mozambique (+31.5‰ to +46.8‰). Nevertheless, Cu-bearing tourmalines from each locality can be fingerprinted using a combination of their δ11B and δ7Li values. The very small δ11B values are consistent with a non-marine evaporite source, and are among the smallest reported for magmatic systems, expanding the global range of B isotopicc omposition for tourmaline by 12‰. The corresponding large δ7Li values are among the largest reported, although they are less diagnostic of the source of the Li. The large δ7Li values in conjunction with the small δ11B values suggest a non-marine evaporite or brine as a source for Li and B, either as constituent(s) of the magma source region or, by assimilation during magma ascent. The large range in δ11B and δ7Li values suggests that B and Li isotope fractionation occurred during magmatic degassing and late-stage magmatic-hydrothermal evolution of the granite-pegmatite system.

Holtite, a new mineral allied to dumortierite, occurred as pebbles with stibiotantalite and tantalite on an alluvial tin lease near Greenbushes, Western Australia, and is named after the late H. E. Holt, Prime Minister of Australia.

The mineral is orthorhombic with a 11·905 Å, b 20·355 Å, c 4·690 Å, space group Pmcn, weak supercell 2a, 2b, c developed. Crystals are elongated along c, D 3·90 ± 0·02, hardness 8½, fluorescent. Optical properties α 1·743−1·746, mainly yellow, ‖ [001], β 1·756−1·759, colourless, γ 1·758−1·761, colourless, 2Vα 49−55°, r < v. X-ray powder data are given.

Chemical analysis gave SiO2 20·30, Sb2O5 4·61, Al2O3 46·43, Ta2O5 11·24, Nb2O5 0·76, Fe2O3 0·27, MnO 0·05, TiO2 0·09, BeO 0·05, B2O3 1·82, Sb2O3 13·89, H2O+ 0·38, H2O− 0·08, sum 99·97%. On a water-free basis the unit cell contains Al24·5Sb2·56‴Ta1·36Sb0·76vNb0·16Fe0·10‴Be0·05Ti0·03Mn0·02B1·40‴Si9·09O66·85. Compared with dumortierite, 4[(A1,Fe)7BSi3O18] or 4 (X11O18), the holtite unit cell contains approximately 4(X10O17).

Type material is preserved at the Government Chemical Laboratories, Perth, Western Australia.

Three of the members of the plagionite group, fülöppite Pb3S8S15, plagionite Pb5Sb8S17, and semseyite Pb9Sb8S21, show linear correlations of cell volume and density versus PbS:Sb2S3 mol ratios. This relationship can be used better to define the nature of the fourth member of the group, heteromorphite, Pb7Sb8S19. The cell dimensions derived for heteromorphite are a 13·60, b 11·93, c 21·22 Å, β 90° 50′.

The crystal structure of synthetic Ni-rich tourmaline with a nickel content of 18.96 wt.% NiO (a = 15.890(2), c = 7.1815(8) Å) has been refined to R = 3.1% using single-crystal X-ray diffraction data. It has been shown that Ni is distributed not only over the Y, but also over the Z sites according to the ideal formula Na(Ni22+Al)(Al5Ni2+)(Si6O18)(BO3)3(OH)4. Based on bond valences and charge balance analysis it has been shown that this composition corresponds to the stable disordered member of the solid solution series NaAl3Al6(Si6O18)(BO3)3(O)3(OH) NaNi32+Al6(Si6O18)(BO3)3(OH)4.

Taking into consideration available structural data on Me2+ (Ni, Cu, Co, Fe, Mn)-rich tourmalines, cation-size mismatch and bond-valence calculations we assume that there are no structural constraints precluding occurrence of these cations in both octahedral sites. Divalent transitional metal-rich tourmalines have not been found in Nature probably due to the insufficient concentration of these elements in B-rich geological systems.

Loveringite-davidite members of the crichtonite group were synthesized at high pressure and temperature (7.5 kbar, 1000–1050 °C) from a melt of TiO2 and rare earth element (REE) enriched basaltic andesite composition. Four sets of partition coefficients for La, Srn, Ho, Lu and Sr (analogue for Eu2+) were obtained. These show that light and heavy REE are readily accommodated, but the intermediate REE are discriminated against in the loveringite—davidite structure. This confirms the previously proposed two sites (A and M) for REE substitution in the crichtonite group. Additional experiments verified the stability of REE-rich crichtonite group minerals to 20 kbar, 1300 °C and 30 kbar, 1000 °C, and indicate that this phase may be an important accessory repository for the light and heavy REE in the upper mantle.

We demonstrate the potential of X-ray photo-emission electron microscopy (XPEEM) to reveal valence-state images of the spatial distribution and relative concentration of metals in specific oxidation states. Additionally, XPEEM allows X-ray absorption spectra to be extracted from chosen pixel areas of the images. Using an in-house-built XPEEM instrument we show an application of the method in providing valence-state images of complex mineral intergrowths. The image resolution achieved with this instrument of simple design was ∼5 μm and reasonable quality X-ray absorption spectra were extracted from areas of ∼5×5 μm. These initial results suggest that by using commercial XPEEM instruments on 3rd generation, high-brightness synchrotron sources a spatial resolution of 100 nm or better could be achieved, with the ability to extract high-quality X-ray absorption spectra from areas of 0.1 μm2. Given that standard thin sections or polished blocks can be studied by XPEEM, and that each XPEEM image records ∼1000 μm2, XPEEM can be used in conjunction with other analytical methods such as EMPA and TEM-EELS/PEELS.

This study describes geochemical barriers that have developed at three different localities in sulfiderich tailings in the Kemerovo region of Western Siberia, Russia. Iron oxyhydroxides, gypsum, malachite, chalcanthite, goslarite, bianchite, gunningite and copper and zinc chloridescrystallized in the sequence specified at an evaporative barrier around glassy slag produced by the Belovo zinc processing plant. A complex cemented barrier that has developed within the old Salair sulfide tailings contains two well defined layers: an upper layer containing Fe(III) mineralsand gypsum as cements in which Pb, As, Mo, Ni and Co have been deposited; and (2) a lower calcite- and gypsum-bearing layer, in which phases containing Zn, Cd and Cu have been deposited. A complex organic-mineral barrier below the Ursk sulfide tailings consists of peaty organic matter, clayminerals and iron oxyhydroxides cemented by gypsum. Elements that have leached from the tailings are present in this barrier in a variety of different forms: Ca and Mn are present as water-soluble species; Cu, Fe and Zn are present as species produced by interaction with organic matter viaion-exchange, metal humate formation and cation bridging in organic-mineral complexes; Pb and As are co-precipitated with and/or adsorbed onto iron oxyhydroxides; gold has been deposited as minute particles of native metal. The mechanisms for the formation of the different geochemical barriersare discussed.

In the Apuane Alps (AA) metamorphic core complex, syn-metamorphic mineral deposits are mainly restricted to extensional shear zones in the Lower Plate Palaeozoic basement. By contrast, the extension structures at upper levels, such as the detachment fault, that are typically the seat of fluid circulation and mineralization in other core complexes, are barren in the AA. Extension veins hosted by the Jurassic Carrara marbles are among the few examples of (minor) mineralization located in the upper levels of the AA core complex. Calcite–dolomite geothermometry and fluid inclusion data suggest that the mineralizing process in these veins began under pressure (P)-temperature (T) conditions close to the metamorphic peak (about 400°C, 3 kbar). Progressive cooling and mixing between metamorphic and late stage meteoric fluids were probably responsible for most of the mineral deposition. Batches of relatively saline fluids presumably resulted from interaction with evaporitic levels located along the detachment fault. In agreement with previous estimates, fluid inclusion constraints on the P—T synmetamorphic path of the AA suggest a relatively rapid cooling of the core complex as a result of uplift. However, the maximum estimated geothermal gradient (about 35°C/km) is considerably lower than in other core complexes, where large-scale hydrothermal circulation was associated with extension and uplift. Hence, in the AA, fluid circulation at shallow levels and mixing among fluids of different origin were not favoured, thus precluding the formation of mineral deposits along major extensional structures.

Calcification within breast cancer is a diagnostically significant radiological feature that generally consists of hydroxylapatite. Samples from 30 cases of breast carcinoma with calcification were investigated using optical microscopy, energy-dispersive X-ray analysis, transmission-electron microscopy, Fourier-transform infrared spectroscopy, Raman spectroscopy, synchrotron radiation X-ray diffraction and X-ray fluorescence. Under optical microscopy, the calcifications were found to consist of either irregular aggregates with widths > 200 μm or spherical aggregates similar to psammoma bodies with an average diameter of 30 μm. Transmission-electron microscopy showed that short columnar or dumbbell-shaped crystals with widths of 10–15 nm and lengths of 20–50 nm were the most common morphology; spherical aggregates (~1 μm in diameter) with amorphous coatings of fibrous nanocrystals were also observed. Results indicated that hydroxylapatite was the dominant mineral phase in the calcifications, and both CO32– and cation substitutions (Na, Mg, Zn, Fe, Sr, Cu and Mn) were present in the hydroxylapatite structure. Fourier-transform infrared spectra show peaks at 872 and 880 cm–1 indicating that CO32– substituted both the OH– (A type) and PO43– (B type) sites of hydroxylapatite, making it an A and B mixed type. The ratio of B- to A-type substitution was estimated in the range of 1.1–18.7 from the ratio of peak intensities (I872/I880), accompanied with CO32– contents from 1.1% to 14.5%. Trace arsenic, detected in situ by synchrotron radiation X-ray fluorescence was found to be distributed uniformly in the calcifications in the form of AsO43– substituting for PO43–. It is therefore proposed that identifying these trace elements in breast cancer calcifications may be promising for future clinical diagnostics.

Previous work on the regular growth of crystals of salts on those of Minerals belonging to the same isostructural series led the author to the discovery that parallel deposition is conditioned by closeness, not of angle nor of axial ratios, but of molecular volume. Now although the substances previously examined resemble each other crystallographically, yet they exhibit such great differences in chemical properties, that reasonable doubt might be entertained whether conclusions drawn from them can be directly applied to isomorphous substances ; and it therefore became advisable to extend the observations to a group of the latter.

The hornfels discussed here was collected from Sparcraigs, near Whitecairns, eight miles to the north of Aberdeen, very close to the eastern contact of the basic igneous intrusion of Belhelvie. The Highland Schists of the district are very poorly exposed, but at this locality there are a few small isolated outcrops of high-grade hornfels, nearly all silica-poor types, with garnet, spinel, hypersthene, cordierite, plagioclase, and biotite as their chief mineral constituents. The actual contact is obscured, but the igneous rock, an olivine-gabbro, is exposed at about twenty yards from the hornfels.

The conversion of Ca(OH)2 to CaO has been studied by X-ray diffraction techniques. When Ca(OH)2 crystals are heated in vacuo the conversion is oriented, but not when they are heated at atmospheric pressure. This difference is attributed to the lowering of the decomposition temperature in vacuo and consequent lower thermal vibration.

Bismuthinite-bearing quartz veins from the Alston Block of the North Pennine Orefield are all close to, or above, the Rookhope and Tynehead cupolas of the buried Weardale Granite. They are uniform in composition and paragenesis and are earlier than the main fluorite-baryte-galena-sphalerite mineralization of the orefield. Rhythmical crystallization of quartz, chalcopyrite and minor pyrite is followed by fluorite-quartz-chalcopyrite-minor sphalerite-altered pyrrhotite mineralization. Early tin-bearing (up to 0.29 wt.% Sn) chalcopyrite encloses trace amounts of bismuthinite (Bi2S3), synchysite (CaREE(CO3)F2), argentopentlandite (Ag(FeNi)8S8) (close to being stoichiometric), pyrrhotite, cubanite and cosalite (Pb2Bi2S5), while early pyrite carries monoclinic pyrrhotite (close to Fe7S8) and tungsten-bearing cassiterite (up to 1.03 wt.% WO3). Bismuthinite is macroscopically visible and is associated with native bismuth and small, fine-grained, spherical aggregates that qualitative analysis suggests may be cosalite crystals. Synchysite and more rarely monazite, xenotime and adularia are intergrown with bismuthinite. These mineralogical data form part of the basis for an increasing awareness of the contribution of the Weardale Granite to the early phases of mineralization in the Alston Block.

Blackhead Quarry exploits a small Miocene (~10 Ma) basanitic volcanic centre in the Dunedin Volcanic Group, New Zealand. Vesicles near the quarry top contain Ca– and Na-rich zeolites, abundant calcite and rare pyrite resulting from localized low-T hydrothermal alteration (<100°C). Mineral assemblages were characterized by EDS and laser Raman spectroscopy with the latter the most useful in determining the identity of fibrous zeolite species. Secondary mineral assemblages crystallized during final stages of lava cooling from aqueous solutions enriched in Ca, Na, K, Ba and (CO3)2–leached from surrounding calcareous rocks and basanite. Phillipsite-K (generation I) crystallized first (in some places directly on fresh basanite) followed by the Ca-rich zeolites, chabazite-Ca, calcian phillipsite–K (generation II), gismondine and thomsonite. Later Na-rich fluids crystallized gonnardite and natrolite, and finally calcite from late Ca-rich fluids. Zeolite composition is not reflected by morphology. For example, both phacolitic and pseudocubic chabazite are chabazite-Ca, and although all phillipsite crystals have a similar habit, their composition varies widely. Various lithologies comprising the Blackhead volcanic centre have unique secondary mineral paragenetic sequences controlled largely by the rock structure and solution chemistry.

Compositional convection in magma chambers is thought to be an important process in the fractionation of liquid from crystals during the differentiation of magmas. It has been tested for in this study by undertaking isothermal crystal growth experiments in a silicate melt at atmospheric pressure in air. The melt used is a synthetic basalt in which iron is replaced by cobalt to minimise redox problems. Co-Mg olivine rims were overgrown on forsteritic olivine seeds cemented to the floor of a 2.4 cm deep alumina crucible. Following quenching and sectioning, glasses were examined optically for colour variations and by EPMA for compositional variations. It had been expected that the colour intensity of the blue glass would diminish in the Co-depleted zone that develops around crystal overgrowths, whereas in fact little difference is normally found, except for a slight fading of colour in glass above the apex of a seed in a few experiments. By contrast EPMA revealed zones up to 50 μm wide around seeds that are depleted in Co and Mg by up to 25 % at the crystal-glass interface and in patches above some crystals. Contour maps of X-ray count-rate data obtained in grids of analytical points show Co- and Mg-depleted glass around the overgrowths and in patches above the highest point of each seed, demonstrating that convection in the melt does occur during growth of individual crystals. As the experiments were carried out in a stable temperature gradient and the crystal seeds had no contact with the melt meniscus, thermal and surface-tensional convection are both eliminated, and the convection is inferred to be caused by a density difference resulting from compositional variation across the chemical boundary layer around a growing crystal. The density difference between the inside and outside of a boundary layer is calculated to be approximately −1%.

A multi-methodological investigation of a synthetic Cu/Fe-bearing blue beryl [IV(Be2.86Cu0.14)∑=3.00VI(Al1.83Fe3+0.14Mn2+0.03Mg0.03)∑=2.03IV(Si5.97Al0.03∑=6.00O18.(Li0.12Na0.04.0.40H2O)] has been performed by means of gemmological standard testing, electron microprobe chemical analyses, laser ablation inductively coupled plasma mass spectroscopy, thermo-gravimetric analyses, infrared spectroscopy and single-crystal X-ray diffraction in order to determine the gemmological properties, crystal structure and crystal-chemistry of this material. The increasing production of marketable hydrothermal synthetic beryls with 'exotic' colours and the small number of studies on the accurate location of chromophores in the crystal structure inspired this multi-methodological investigation. The X-ray structural refinements confirm that the space group of the Cu/Fe-bearing blue beryl is P6/mcc, with unit-cell parameters: 9.2483 ≤ a ≤ 9.2502 Å and 9.2184 ≤ c ≤ 9.2211 Å. The analysis of the difference Fourier maps of the electron density suggests that Cu is located at the tetrahedral site (Wyckoff 6fposition) along with Be, whereas Fe shares the octahedral site with Al (4c position). No evidence of extra-framework Cu/Fe-sites (i.e. channel sites) has been found. The Li is probably located at the extra-framework 2b site. Infrared spectra show that the H2O molecules are present with two configurations: one with the H···H vector oriented ‖[0001] and the other with H···H vector oriented ⊥[0001].