Basalt glass from Kilauea, Hawaii (SBG) starts to crystallize upon heat treatment in air at ∽840°C. In addition, oxidation takes place. The kinetics of both processes may be readily quantified though the mechanism is difficult to access. This work investigates the relationship between these processes, crystallization and oxidation, and the escape of volatiles from the glass/liquid upon reheating. Evolved gas analyses and differential scanning calorimetry are the techniques used. In addition, isothermal heat treatment in argon is carried out in order to eliminate the external reason for oxidation, the oxygen gradient, and to focus on intrinsic oxidation. Products are examined with 57Fe Mössbauer spectroscopy. As expected, degassing temperatures of SBG, and of two MORB samples, considered for comparison, are above the glass transition temperature. We find no convincing evidence of intrinsic oxidation. Degassing is likely to induce interface-controlled crystallization.

In the large serpentinite body at Zöblitz, which is part of the Gneiss-Eclogite Unit of the Saxonian Erzgebirge, ilmenite rods have been detected in olivine. Although these rods are ≤1 μm wide, they can be unequivocally identified as ilmenite using electron backscatter diffraction. We also applied this method to prove that ilmenite is topotactically intergrown with the olivine host ([100]ol ‖ [001]ilm). This relation was found previously, e.g. for ilmenite exsolved from olivine of garnet peridotite from Alpe Arami, Swiss Alps. The degree of this exsolution phenomenon in the Alpe Arami rocks was taken as an indication of the original formation of a Ti-bearing mineral at depths of ∽300 km. As in the olivines of the serpentinite from Zöblitz, the density of the ilmenite rods is significantly less than in the rock from Alpe Arami. We think that our observation is compatible with previous P-T estimates of close to 4 GPa and 1000–1100°C for the ultramafic bodies in the central Saxonian Erzgebirge.

Naujakasite (Na6(Fe,Mn)Al4Si8O26) is a characteristic, rock-forming mineral of hyperagpaitic naujakasite lujavrite (arfvedsonite + naujakasite + steenstrupine + albite ± relict nepheline ± microcline ± ussingite) from the Ilímaussaq complex, South Greenland, and is only known from this complex. The qualitative stability relationships of naujakasite-bearing, low-variance liquidus mineral assemblages at near-solidus conditions in lujavritic magma can be modelled within the six-component system Si-Al-Fe-Na-O-H. The modelling suggests that an uncommon combination of elevated water activity and low oxygen fugacity is needed to stabilize arfvedsonite + naujakasite mineral assemblages in highly sodic liquids. These conditions are incompatible with the stable coexistence of aegirine and arfvedsonite. They are met in the arfvedsonite-bearing lujavrites of Ilímaussaq, but apparently not in rocks of similar composition in the Khibina and Lovozero complexes, Kola Peninsula, where aegirine- or aegirine-arfvedsonite-bearing mineral assemblages are characteristic. Liquid lines of descent leading to crystallization of naujakasite have to pass through the albite+nepheline+arfvedsonite liquidus field in the Si-Al-Fe-Na-O-H system, reaching this field at the high-Na side of the albite-nepheline-arfvedsonite plane.

A gonnardite-thomsonite-chabazite-calcite assemblage forms a cement in the Foveaux Formation, a fossiliferous gabbroic boulder bed that accumulated at the base of a sea cliff cut in a Permian igneous complex during late Oligocene±early Miocene time. Gonnardite was the earliest zeolite to form, locally following minor calcite. It was followed epitaxially by thomsonite, co-precipitating with chabazite. Crystal habits indicate a low-temperature origin. The maximum temperature to which the deposit may have been subjected is estimated as not more than ∽30°C. The chabazites are Ca-poor chabazite-K and chabazite-Na. Representative electron microprobe analyses are as follows, all + nH2O:

• thomsonite: Na3.77Ca7.73(Al19.39Si20.65)O80 and Na3.78K0.04Ca7.25Mg0.05(Al19.13Si21.05)O80;

• gonnardite: Na6.95K0.03Ca4.73(Al16.99Si23.15)O80 and Na8.56K0.03Ca4.05(Al17.32Si22.84)O80;

• chabazite-K: Na1.18K1.72Ca0.08Mg0.23(Al3.51Si8.49)O24 and Na1.67K1.92Ca0.18Mg0.17(Al4.11Si7.85)O24;

• chabazite-Na: Na2.51K1.13Ca0.17Mg0.02(Al4.08Si7.93)O24.

Such a Si-poor zeolite assemblage is unusual for marine sediments and is attributed to precipitation from marine water impoverished in silica in the gabbroic boulder bed and interacting with shell material and calcic plagioclase. In contrast, a dioritic clast in the boulder bed provides an example of less silica-poor zeolites originally formed in the parent igneous complex. Veinlets in the clast contain scolecite averaging Na1.19Ca7.36(Al15.84Si24.14)O80.nH2O, and mesolite averaging Na5.13K0.03Ca5.24 (Al15.93Si24.13)O80.nH2O, in part as sub-microscopic intergrowths. The composition of scolecite closely corresponds to the most Na-rich scolecite reported hitherto.

Tiny green crystals from Kabwe, Zambia, associated with hopeite and tarbuttite (and probably first recorded in 1908 but never adequately characterized because of their scarcity) have been studied by X-ray diffraction, microchemical and electron probe microanalysis, infrared spectroscopy, and synthesis experiments. They are shown to be orthorhombic, stoichiometric CuZnPO4OH, of species rank, forming the end-member of a solid-solution series to libethenite, Cu2PO4OH, and are named zincolibethenite. The libethenite structure is unwilling to accommodate any more Zn substituting for Cu at atmospheric pressure, syntheses using Zn-rich solutions precipitating a mixture of zincolibethenite with hopeite, Zn3(PO4)2.4H2O. Single-crystal X-ray data confirm that the Cu(II) occupies the Jahn-Teller distorted 6-coordinate cation site in the libethenite lattice, and the Zn(II) occupies the 5-coordinate site. The space group of zincolibethenite is Pnnm, the same as that of libethenite, with unit-cell parameters a = 8.326, b = 8.260, c = 5.877 Å , V = 404.5 Å 3, Z = 4, calculated density = 3.972 g/cm3 (libethenite has a = 8.076, b = 8.407, c = 5.898 Å , V = 400.44 Å 3, Z = 4, calculated density = 3.965 g/cm3). Zincolibethenite is biaxial negative, with 2Vα(calc.) of 49°, r<v, and α = 1.660, β = 1.705, and γ = 1.715 The mineral is named for its relationship to libethenite.

The mineral conichalcite from the western part of Bagdad mine, Bagdad, Eureka District, Yavapai County, Arizona, USA has been characterized by electronic, near-infrared (NIR), Raman and infrared (IR) spectroscopy. Scanning electron microscopy (SEM) images show that the mineral consists of bundles of fibres. Calculations based on the results of the energy dispersive X-ray analyses on a stoichiometric basis show the substitution of arsenate by 12 wt.% of phosphate in the mineral. Raman and IR bands are assigned in terms of the fundamental modes of AsO43− and PO43− molecules and are related to the mineral structure. Near-IR reflectance spectroscopy shows the presence of adsorbed water and hydroxyl units in the mineral. The Cu(II) coordination polyhedron in conichalcite can have at best pseudo-tetragonal geometry. The crystal field and tetragonal field parameters of the Cu(II) complex were calculated and found to agree well with the values reported for known tetragonal distortion octahedral complexes.

Two mixites from Boss Tweed Mine, Tintic District, Juab County, Utah and Tin Stope, Majuba Hill, Pershing County, Nevada, USA, were analysed by scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis and by Raman spectroscopy. The SEM images show the mixite crystals to be elongated fibres up to 200 μm long and 2 μm wide. Detailed images of the mixite crystals show the mineral to be composed of bundles of fibres. The EDX analyses depend on the crystal studied, though the Majuba mixite gave analyses which matched the formula BiCu6(AsO4)3(OH)6.3H2O. Raman bands observed in the 880–910 cm−1 and 867–870 cm−1 regions are assigned to the AsO-stretching vibrations of (HAsO4)2− and (H2AsO4)− units, whilst bands at 803 and 833 cm−1 are assigned to the stretching vibrations of uncomplexed (AsO4)3- units. Intense bands observed at 473.7 and 475.4 cm−1 are assigned to the v4 bending mode of AsO4 units. Bands observed at 386.5, 395.3 and 423.1 cm−1 are assigned to the v2 bending modes of the HAsO4 (434 and 400 cm−1) and the AsO4 groups (324 cm−1). Raman spectroscopy lends itself to the identification of minerals on host matrices and is especially useful for the identification of mixites.

Europium LIII-edge X-ray absorption near-edge structure (XANES) was employed to determine the Eu(II)/Eu(III) ratios in minerals. This ratio can be determined based on the peak-area ratio of white lines, the resonance peak, in normalized XANES spectra for Eu(II) and Eu(III) species. For precise determination of the Eu(II)/Eu(III) ratios, however, it was revealed that the transition probabilities for each individual Eu(II) and Eu(III) species in the system must be quantified, because we found that the peak area in normalized XANES spectra is different in each Eu(II) and Eu(III) species. Despite this ambiguity, the method was applied to Eu in natural hydrothermal apatites (Eu = 39 and 64 ppm) and fluocerite (Eu = 282 ppm). The relationship between the Eu(II)/Eu(III) ratio in these hydrothermal minerals, and the distribution coefficients of Eu(II) and Eu(III) were discussed, taking into account Eu anomalies in their REE patterns. It is considered that by combining the Eu(II)/Eu(III) ratios determined by XANES and the degree of Eu anomaly in REE patterns, we can provide new information on the distribution of Eu(II) and Eu(III) in various geochemical studies.

Detrital chrome-spinels are contaminant grains within heavy-mineral concentrates found in the Murray Basin of southeastern Australia. The presence of even minor levels of chromia in the predominantly ilmenite-rich concentrates downgrades their market value as potential feedstocks for the production of titania pigment.

Compositions from a database of close to 5000 chrome-spinel analyses show a broad range in chemistry. The major element components and their ranges (wt.%) are Cr: 3.10–52.06, Al: 0.46–32.50, Fe: 3.50–44.48 and Mg: 0.03–15.79. Minor components include; Ti: 0.01–6.41, Zn: 0.00–23.00 and Mn: 0.00–5.82. The broad variation in composition suggests multiple source areas for the chrome-spinels although detailed textural examination indicates that variation has also been introduced through pre- and post-deposition alteration processes.

The Murray Basin chrome-spinel database has the potential to be used in interpreting and predicting the effects of various processing conditions used to separate the chrome-spinels from the ilmenite.

The thermal expansion coefficients for natural troilite, FeS, Ni-rich pyrrhotite, Fe0.84Ni0.11S, and Ni-poor pyrrhotite, Fe0.87Ni0.02S, were measured during cooling by in situ neutron powder diffraction over the temperature range 873–373 K. Between 873 and 573 K, the mean thermal expansion coefficients for the three compositions are 7.4(3)×10−5 {FeS}, 8.0(4)×10−5 {Fe0.84Ni0.11S} and 8.5(4)×10−5 K−1 {Fe0.87Ni0.02S}. Below 573 down to 373 K, the first two increase considerably to 14.1(7)×10−5 {FeS} and 9.3(5)×10−5 {Fe0.84Ni0.11S} while the latter sample shows no significant variation, 8.4(5)×10−5 K−1. Below 573 K, the thermal expansion is highly anisotropic, with Δa/100 K−1 ranging from 0.89(9)% {FeS} to 0.48(12)% {Fe0.87Ni0.02S} while Δc/100 K−1 ranges from −0.39(11)% {FeS} to −0.13(2)% {Fe0.87Ni0.02S}.

Upon cooling through 573 K, troilite and pyrrhotite undergo a transition where the FeS6 octahedra distort and in the case of pyrrhotite, cation-vacancy clustering occurs. The thermal expansion coefficients are bigger for low cation-vacancy concentrations and decrease as the pyrrhotites become less stoichiometric. This indicates that the thermal expansion in these minerals is damped by vacancy ordering or clustering. The thermal expansion coefficients for troilite and pyrrhotite are amongst the largest reported for sulphide minerals and their role in the formation of ore textures is discussed briefly.