Structural modifications with temperature of adamite, Zn2(AsO4)(OH), were determined by single-crystal X-ray diffraction up to dehydration and collapse of the crystal structure. In the temperature range 25–400°C, adamite shows positive and linear expansion. Axial thermal expansion coefficients, determined over this temperature range, are αa = 1.06(2) × 10–5 K–1, αb = 1.99(2) × 10–5 K–1, αc = 3.7(1) × 10–6 K–1 and αV = 3.43(3) × 10–5 K–1. Axial expansion is then strongly anisotropic with αa:αb:αc = 2.86: 5.38 : 1. Structure refinements of X-ray diffraction data collected at different temperatures allowed us to characterize the mechanisms by which the adamite structure accommodates variations in temperature. Expansion is limited mainly by edge sharing Zn(2) dimers along a and by edge sharing Zn(1) octahedra chains along c; on the other hand, connections of polyhedra along b, the direction of maximum expansion, is governed by corner sharing. Increasing temperature induces mainly an axial expansion of Zn(1) octahedron, which becomes more elongated, and no significant variations of the Zn(2) trigonal bipyramids and As tetrahedra. Starting from 400°C, deviation from a linear evolution of unit-cell parameters is observed, associated with some deterioration of the crystal, a sign of incipient dehydration. The process leads to the formation of Zn4(AsO4)2O.

A series of long-term laboratory experiments was started in 1995 to investigate longer-term dissolution/ precipitation reactions that may occur in the alkaline disturbed zone surrounding a cementitious repository for radioactive waste. They consist of samples of UK basement rock reacting with either Na-K-Ca-OH water ('young' cement porewater) or Ca-OH water ('evolved' cement porewater) at 70°C. This paper summarizes results of reactions occurring over the first 15 months. Experiments of both fluid types showed many similar features, though primary mineral dissolution and secondary mineral precipitation were more extensive in the experiments involving Na-K-Ca (younger) cement porefluids compared to more evolved (Ca-rich) cement porefluids. Dissolution of dolomite, and to a lesser extent silicates (probably K-feldspar, but also possibly mica) occurred relatively rapidly at 70°C. Dolomite dissolution may have been a key factor in reducing pH values, and may be a key mineral in controlling the extent of alkaline disturbed zones. Dissolution was followed by precipitation of brucite close to dolomite grains, at least two generations of C-S-H phases (which may have contained variable amounts of K, Al and Mg); overgrowths of calcite; small crystals of hydroxyapophyllite; and elongate crystals of celestite. Though hydroxyapophyllite was observed (a phase commonly associated with zeolites), there was no evidence for the formation of zeolites in the experiments. Fluid chemical changes track the mineralogical changes, with C-S-H phases being a major control on fluid chemistry. In the 'young' porewater experiments there were decreases in pH, and K, Ca and Mg concentrations, together with transitory increases in SiO2 concentrations. In the 'evolved' porewater experiments there were decreases in pH, Mg, Ca and Sr concentrations, together with small increases in K and SiO2 concentrations. A number of experiments are still running, and will be sampled in coming years.

Phases present in slags from Araxá (Brazil), Oka (Quebec) and Fen (Norway) resulting from the production of ferroniobium by the aluminothermic reduction of pyrochlore-group minerals are a function of composition of the pyrochlore feed and the diverse fluxes (CaO, CaF2) added to the alumina and iron oxide used in the reduction process. Absent from all slags investigated are Fe-bearing compounds. All of the slags are modally-dominated by prismatic crystals of β-alumina or hibonite, with a wide variety of Th-Ba-Ti-Nb-Al-oxide compounds and silico-aluminate glasses occurring in the interstices between these crystals. Slag from Fen consists of a framework of β-alumina (Ba and/or CaTi varieties) with a barian titanian niobate, considered to be an highly reduced Nb3+- and Ti3+-bearing anion deficient perovskite, as the first oxide phase to crystallize. This was followed by a Zr-Ti-Th-niobate (21.7–24.1 wt.% ThO2), a Nb-rich, Thbearing zirconolite-like phase (17.7–21.2 wt.%; Nb2O5; 6.8–9.5 wt.% ThO2) and diverse Th-Nb-rich, Alpoor (< 1 wt.% Al2O3) perovskites (29.4–40.5 wt.% Nb2O5; 3.3–11.4 wt.% ThO2). The latter represents a NaNbO3–CaTiO3–Na2/3Th1/3TiO3–ThTi2O6 solid solution. Late Na-rich silicate glass contains celsian. Slag from Araxá also consists of a framework of β-alumina (Ti-poor). Interstitial compounds differ from Fen in being predominantly rare-earth element (REE)-Nb-Al-Th-perovskites belonging to a REEAlO3–Ca2AlNbO6–CaTiO3–ThTi2O6 solid solution with minor NaNbO3 and CaZrO3, and compositionally diverse barium calcium aluminates [(Ba, Ca)Al2O4] set in a F-bearing (6–7 wt.%) Na-Ba-Si-aluminate glass with minor Ba4Nb2O9, CaF2, BaF2 and NaF. Slag from Oka consists of a framework of hibonite [(Ca, REE) (Al, Ti, Mg)12O19] zoned with respect to the REE content. Interstitial compounds are CaZr4O9, Nb-Th-poor perovskites belonging to the REEAlO3–CaTiO3 series with minor CaZrO3 set in a F-bearing (5–6 wt.%) calcium aluminate glass. These data demonstrate that during ferroniobium production REE, Zr, Th, U and significant amounts of Nb are sequestered in the oxide phases in accord with their lithophile geochemical character. None of these elements are present as compounds in the siderophillic ferroniobium alloys. These data demonstrate that the aluminothermic reduction process results in the loss of significant amounts of Nb to the slag. Perovskite-group compounds are present in all of the slags but differ widely in their composition as a result of compositional differences in the feed pyrochlores and fluxes added to the smelting process. Slags originating from ferroniobium production are enriched in Th and U and could be considered as an environmental hazard if these elements are mobilized during chemical weathering of slag.

“Envelope crystals” collected during The Great Barrier Reef Expedition in May 1929 have been studied using low-temperature synchrotron single-crystal X-ray diffraction. The crystals are shown to be weddellite, with the largest content of zeolitic water reported to date. A new H2O site has been located within the crystal structure. Study of the crystals show that the end-member formula for weddellite should be reported as CaC2O4·(2.5 – x)H2O, where 0≤x≤ 0.25, instead of CaC2O4·(2H2O or CaC2O4·(2 + x )H2O. This is also the first report of weddellite occurring in a coral reef.

Hakite, ideally Cu10Hg2Sb4Se13, is a Se-dominant member of the tetrahedrite group occurring at only a few localities in the World. A new occurrence of this mineral in the Příbram uranium and base-metal ore district, Central Bohemia, Czech Republic, is reported in this paper. Hakite was found to be locally abundant and was identified in several samples with Se mineralization. Three chemically distinct types of hakite were distinguished based on electron microprobe study, Hg-rich hakite (hakite sensu stricto), Zn-rich hakite and Cd-rich hakite. Hg-hakite dominates among the samples studied. Its average empirical formula based on 29 apfu (n = 54) is (Cu5.61Ag0.39)∑6.00Cu4.00(Hg1.61Zn0.20Cu0.19Cd0.15Fe0.04)∑2.19(Sb3.85As0.28)∑4.13(Se11.55S1.14)∑12.69 . Less common is the Zn-hakite, (Cu5.80Ag0.20)∑6.00Cu4.00(Zn1.33Hg0.42Cd0.22Cu0.18Fe0.01)∑2.16(Sb3.85As0.26)∑4.11(Se10.92S1.81)∑12.73 (n = 22), and rare Cd-hakite has an empirical formula (n = 7) of (Cu5.84Ag0.16)∑6.00Cu4.00(Cd1.27Zn0.60Cu0.10Hg0.07Fe0.02)∑2.06(Sb4.00As0.19)∑4.19(Se12.14S0.61)∑12.75. The refined unit cell of Hg-hakite from Příbram, obtained from powder X-ray diffraction data, is a = 10.8783(3) Å with V = 1287.3(1) Å3 (Z = 4, for the cubic space group I4̄3m). Structure refinement from the precession electron diffraction data collected on the transmission electron microscope (R = 24.4% for 424 observed reflections), confirmed that hakite is isostructural with tetrahedrite. The evolution of hydrothermal fluids, from which Se mineralization formed, suggests a distinct enrichment in sulfur and depletion in selenium over the time span of crystallization.

Lithium cannot be determined by electron microprobe, but it may be an essential component in tourmalinesupergroup minerals. Therefore, its estimation is important for structural formula calculation and nomenclature. In this paper, we present a method to estimate Li content in tourmaline from microprobe data based on a multiple linear-regression model, which is not reliant on a particular normalization scheme. The results derived from this model are reasonably accurate, particularly for low-Mg tourmalines (<2 wt.% MgO) with Li2O contents higher than ∼0.3 wt.%. Furthermore, it provides a better fitness compared with estimations of Li assuming that Li fills any cation deficiency at the Y site.

Proposal 16-C was accepted by the Commission on New Minerals and Mineral Names of the International Mineralogical Association, and parabariomicrolite is discredited as identical to hydrokenomicrolite-3R. There are now two type localities: Alto do Giz pegmatite, Equador Co., Rio Grande do Norte, Brazil and Volta Grande pegmatite, Nazareno, Minas Gerais, Brazil.