A system based on variation of the octahedrally coordinated cations is proposed for graphical presentation and subdivision of tri- and dioctahedral K micas, which makes use of elemental differences (in a.p.f.u.): (Mg – Li) [= mgli] and (Fetot + Mn + Ti – VIAl) [= feal]. All common true tri- and dioctahedral K micas are shown in a single polygon outlined by seven main compositional points forming its vertices. Sequentially clockwise, starting from Mg3 (phlogopite), these points are: Mg2.5Al0.5, Al2.167□0.833, Al1.75Li1.25, Li2Al (polylithionite), Fe22+Li, and Fe32+ (annite). Trilithionite (Li1.5Al1.5), Li1.5Fe2+Al0.5, Fe22+ Mg, and Mg2Fe2+ are also located on the perimeter of the polygon. IMA-siderophyllite (Fe2+2Al) and muscovite (Al2□) plot inside.

The classification conforms with the IMA-approved mica nomenclature and differentiates among the following mica species according to their position in a diagram consisting of mgli and feal axes plotted orthogonally; trioctahedral: phlogopite, biotite, siderophyllite, annite, zinnwaldite, lepidolite and tainiolite; dioctahedral: muscovite, phengite and celadonite. Potassium micas with [Si] <2.5 a.p.f.u. including IMA-siderophyllite, KFe22+ AlAl2Si2O10(OH)2, and IMA-eastonite, KMg2AlAl2Si2O10(OH)2 seem not to form in nature.

The proposed subdivision has several advantages. All common true, trioctahedral and dioctahedral K micas, whether Li-bearing or Li-free, are shown within one diagram, which is easy to use and gives every mica composition an unambiguously defined name. Mica analyses with Fe2+, Fe3+, Fe2+ + Fe3+, or Fetot can be considered, which is particularly valuable for microprobe analyses. It facilitates easy reconstruction of evolutionary pathways of mica compositions during crystallization, a feature having key importance in petrologically oriented research. Equally important, the subdivision has great potential for understanding many of the crystal-chemistry features of the K micas. In turn this may allow one to recognize and discriminate the extent to which crystal chemistry or bulk composition controls the occurrence of some seemingly possible or hypothetical K mica.

Intermediate levels of the Larga-Fatţa Báii field, Metaliferi Mts., Romania, are host to epithermal vein mineralization, small skarn-like bodies and ‘geode’-like replacement ores, that together form a complex hydrothermal system rooted in the subjacent andesite stock. Silver-Pb-Bi sulphosalts, some with Sb and/or Se, are intimately associated with hessite and a range of Bi-tellurides with Bi/(Te+S+Se) ≤1 (tetradymite, tellurobismuthite, tsumoite, Pb-free rucklidgeite) within all these ore types. Lillianite homologues, both ordered 4L and 7L derivatives (lillianite, gustavite), and disordered varieties are the most abundant sulphosalts, with subordinate bismuthinite derivatives (aikinite, krupkaite, bismuthinite). An exceptionally Ag-rich lillianite homologue, intimately intergrown with tetradymite and hessite, is identified as treasureite on the basis of chemical composition. Porphyry-style mineralization from 600 m beneath the studied level contains rucklidgeite as the single stable Bi-telluride. The trace mineralogy of the system is suggestive of a hydrothermal system strongly zoned with respect to fTe2 and, to a lesser extent, also fS2. Mineralogical and textural evidence suggests that initial crystallization took place at temperatures in excess of 400°C. The association of gold with Bi-minerals is linked to the role of Bimelt as a scavenger for gold, and deposition within ‘droplets’ simultaneous with the formation of arsenopyrite from löllingite + pyrrhotite. Both Bi-tellurosulphides and sulphosalts are commonly non-stoichiometric, a fact that can be correlated with order-disorder in both series. When widely distributed, as in the Larga system, trace amounts of Bi-minerals (sulphosalts, tellurides/tellurosulphides) have considerable, untapped potential as tracers of the physical-chemical character of an evolving hydrothermal system.

Wang et al. (2000) presented interesting new data on the occurrence of Hf-rich zircon in peralkaline granitic rocks. It is shown that the knowledge of the Hf distribution in zircon is important for the understanding of Zr/Hf ratios defined by whole-rock analysis. However, the processes leading to the unusual Zr/Hf fractionation are still poorly constrained. Some aspects are discussed further here. Analysis of available data demonstrates that extremely low Zr/Hf ratios found in topaz- and rare-metal bearing granites may be either a primary signature of some evolved granitic melts or, alternatively, they are produced during albitization of the rocks. Topaz- and rare-metal bearing granites may be P-rich and contain zircon moderately enriched in Hf (2—9 wt.% HfO2). Another group is P-poor and the Hf content in accessory zircon is high (up to 35 wt.% HfO2). Both types of intrusions may occur within a single orogen as demonstrated by the example of the Hercynian magmatism in the Erzgebirge/Krušné hory region (Germany/Czech Republic).

The low-temperature heat capacity of zinc chromite (ZnCr2O4) was measured between 6.5 K and 400 K using adiabatic calorimetry, and some thermochemical functions (CP(T), S(T), S°298, H(T)-H(0)) were derived from the results. The standard entropy (S°298 = 128.6±0.3 J mol-1 K-1) for zinc chromite was calculated from the results. Our calorimetric measurements indicate one extremely large anomaly in the heat capacity curve at ∼12.3 K which is related to the cubic-tetragonal transition in ZnCr2O4.

We have studied the structures of Al/Si disordered leucite and bicchulite with a quantum mechanical version of the virtual crystal approximation, VCA. In leucite, the average tetrahedron has a composition of (AlSi2)O4, while bicchulite represents an extreme case with (Al2Si)O4 tetrahedra. Both structures are well described with the VCA. In conjunction with an earlier study, where we have shown that the (AlSi)O4 tetrahedra in gehlenite and Al,Si-disordered octahedra are also well reproduced, we have now established that the VCA gives a reliable description of the averaged structure of disordered aluminosilicates over the whole compositional range. The current calculations confirm that Al/Si ordering is not driving the cubic to tetragonal phase transformation in leucite. In bicchulite, the model calculations are consistent with hydrogen on Wyckoff position 8c, in agreement with the result of a single crystal X-ray diffraction study, but in variance with results based on a neutron powder diffraction study.

Non-metamict betafite, a pyrochlore-group mineral with general formula A2−mB2XO6Y(O,OH,F)1−n·pH2O and 2 Ti > Nb+Ta and U > 20% at the A site, has been found at Le Carcarelle, (Latium, Italy). It occurs within miarolitic cavities of a foid-bearing syenitic ejectum enclosed within the pyroclastic formation known as “ignimbrite C”, which belongs to the main effusive phase of the Vico volcanic complex. The host rock is composed of K-feldspar, biotite, augitic clinopyroxene, magnetite and minor sodalite. Electron microprobe analyses gave the following crystal-chemical formula: (Ca1.24Na0.17U0.49REE0.03)Σ=1.93 (Ti1.05Nb0.76Zr0.14Fe0.04Ta0.01)Σ=2.00O6(O,OH). Compared with other occurrences reported in the mineralogical literature, betafite from Le Carcarelle is extremely enriched in U and depleted in Th. Due to its young age of formation (∼150 k.y.), this betafite sample is highly crystalline, thus allowing structure refinement of unheated material. Betafite from Le Carcarelle is cubic Fdm, with a = 10.2637(13) Å, and V = 1081.21(35) Å3, and has a smaller A site (consistent with the higher U content), and a larger and more distorted B site (consistent with the higher Ti content) than calciobetafite from Campi Flegrei, Italy (Mazzi and Munno, 1983). Analysis of the atomic displacement parameters provides evidence for static disorder at the X site.

Multispectral imaging of ore minerals under the microscope is a logical extension of quantitative colour analysis and microspectrophotometric analysis of minerals. This paper describes, step by step, how the proper calibration of a scientific video camera can be performed in order to obtain precise reflectance measurements at each pixel within the field of view. After having reviewed the different sources of noise and aberration, practical formulae are presented that allow for the acquisition of a set of images at different wavelengths in the visible spectrum.

The advantage of using a multispectral image acquisition system based on narrow bandwidth (10 nm) interference filters is discussed and quantitatively compared to colour imaging using tristimulus (red, green, blue) filters.

Images taken from major sulphide parageneses are shown as examples of well contrasted multispectral images. Finally, the potential for automatic identification of ore minerals is discussed with reference to supervised multivariate image classification algorithms similar to those used in remote sensing. Additional comments on extending the principles for handling optical anisotropy and developing a multiradial imaging system are made.

Static lattice energy calculations have been combined with cluster expansion formalism to predict pairwise ordering interactions in the pyrope–grossular solid solution. The ordering interactions, the Js, have been then used to calculate the activity-composition relations over a wide temperature range with the help of the Cluster Variation Method. It is shown that short-range ordering in the system is driven by size mismatch. The prediction of the right signs and magnitudes of the ordering interaction energies requires separation of the mixing enthalpy into the configuration-dependent (chemical) and the configuration-independent (elastic) components. The study predicts the existence of a miscibility gap below 500°C.

Four relatively intense and broad absorption bands centred at ∼12500, ∼19500, ∼21500 and ∼23000 cm–1 were recorded in polarized electronic single-crystal spectra of natural, optically uniaxial and pleochroic hydrogarnets with henritermierite contents ranging from 35 to 97 mol.%. These absorption bands arise from spin-allowed electronic d-d transitions in trivalent Mn located at the axially distorted six-coordinated site of the tetragonal hydrogarnet structure.

The crystal field stabilization energy (CFSE) for trivalent Mn at the Mn site, as derived from band energies, is ∼185 kJ/mol. This considerably higher CFSE for Mn3+ in tetragonal hydrogarnets as compared to cubic garnets (130 –145 kJ/mol) explains the natural occurrence of close to end-member tetragonal Mn3+-hydrogarnets while only limited Mn3+-substitution is observed in natural cubic garnets.

The fact that incorporation of Mn3+ at intermediate concentrations stabilizes the tetragonal hydrogarnets indicates the potential natural existence of a number of new, partially Mn3+-substituted, hydrogarnets, e.g. tetragonal Mn3+-bearing ‘hydroandradite’.

Holotype material and other specimens of ‘elfstorpite’ from the Sjögruvan deposit, Örebro, Sweden have been characterized by powder X-ray diffraction and chemical analysis. The mineral is indistinguishable from allactite, which has priority, and consequently ‘elfstorpite’ should be discredited. The IMA Commission on New Minerals and Mineral Names has approved the proposition.

In 2004, the International Mineralogical Association (IMA) amended the IMA 97 amphibole classification and nomenclature scheme byadding a fifth group to include the recently discovered B(LiNa) amphiboles ferriwhittakeriite and ferri-ottoliniite, which cannot be fitted into the four major amphibole groups. New root-names such as sodic-pedrizite in the Mg-Fe-Mn-Li group and obertiite and dellaventuraite in the sodic group along with two new prefixes, parvo and magno have also been added. As result it has become necessary to modify the AMPH-IMA97 amphibole-naming program. The new program (AMPH-IMA04) allows single input or automatic input of as many amphibole analyses as are available following a set input format. Any of three different calculation schemes for dealing with an amphibole analysis can be chosen: (1) complete chemical analyses can be calculated to 24(O,OH,F,Cl); (2) analyses with determined FeO and Fe2O3, MnO and Mn2O3 but without H2O can be calculated to 23(O); and (3) electron microprobe analyses with only total Fe determined and without H2O can be calculated to 23(O) with IMA97-recommended normalization for Fe3+ and Fe2+ values. In addition a stoichiometric calculation of Mn2+ and Mn3+ is considered and implemented for the Mn-bearing sodic amphiboles in order to take care of electron microprobe analyses of such amphiboles where the total Mn is given as Mn2+.

During investigations of the system Sc2O3-Al2O3-TiO2-SiO2, a new, unusual microporous compound, Cs3ScSi8O19, was synthesized as colourless plates from a CsF-MoO3 flux. The crystal structure was determined from single-crystal X-ray diffraction data (Mo-Kα radiation, CCD area detector). The compound is orthorhombic, space group Pnma, with a = 11.286(2), b = 7.033(1), c = 26.714(5) Å, and Z = 4 (R1(F) = 2.6% and wR2all(F2) = 7.3%, using 3066 ‘observed’ reflections with Fo > 4σ(Fo)). The crystal structure of Cs3ScSi8O19 represents a new microporous framework structure type (‘MCV-1’), and the compound is exceptional in being the first representative of a mixed octahedral-tetrahedral framework structure, in which the [TO4]:[MO6] ratio is >6:1. The structure is based on isolated, nearly regular ScO6 octahedra [dav(Sc—O) = 2.112 Å] sharing corners with SiO4 tetrahedra to form an open framework with four-, six- and eight-membered rings; the latter are formed by SiO4 tetrahedra only. Two fully occupied Cs positions are located in large framework voids close to the six-membered rings, whereas four partly occupied and disordered Cs positions are close to very large framework voids bordered by the puckered eight-membered rings. The cavities are linked into channels parallel to [100] and [010]. The structure is compared with that of Cs2TiSi6O15 and related microporous scandium-, REE-, titano- and zirconosilicate minerals and compounds. Cs3ScSi8O19 or derivatives may be important in the context of immobilization of radioactive 137Cs waste, cationic conductivity or catalysis.

The heat capacity of synthetic lazulite, MgAl2(PO4)2(OH)2, has been measured between 35 and 298 K by means of low-temperature adiabatic calorimetry. A lazulite third-law entropy (S2980) value of 204(3) J K–1 mol–1 was retrieved after extrapolation of the lazulite heat capacity by a cubic temperature function, down to absolute temperature. Identical measurements on α-Al2O3 yielded S2980 = 51.2 J mol–1 K–1 instead of the recommended 50.94 J mol–1 K–1 value. This new lazulite third-law entropy along with other phosphate entropy data either derived from low-temperature adiabatic calorimetry or experimental phase equilibria under pressure and temperature, were computed to retrieve a (S–V)P2O5 value of 57.4(2.9) to predict phosphate entropies from oxide summation. The predicted third-law entropy for trolleite, Al4(PO4)3(OH)3, amounts to 285.4(8.5) J mol–1 K–1 ~13% higher than the previously published value. We propose a new formation enthalpy from the elements of –6504.2 kJ mol–1 and a new third-law entropy of 281.7 J mol–1 K–1 for trolleite, compatible with the predicted entropy from oxide summation as well as with the published brackets on the trolleite = berlinite + corundum + water reaction.

Amphibole in the Larvik alkaline plutonic complex in the Oslo rift, Norway, has Ti-rich compositions from edenite through pargasite to kaersutite, and has a large H+ deficiency (0.7–1.1 atoms per formula unit: a.p.f.u.) with a large oxy component in the amphibole OH– site (O2– = 2 – (OH + F + Cl) = 0.2–0.9 a.p.f.u.), similar to the mantle-derived kaersutites. Their compositions reveal a characteristically low Fe3+/(Fe3++Fe2+) ratio (<0.23) and a high F concentration (0.3–0.9 a.p.f.u.). Correlation with the Fe3+ ratio caused by Fe2+ + OH– = Fe3+ + O2– + 1/2H2 substitution is negligible, which is supported by H and O isotope compositions. A possible substitution, [6]Al3+ + OH– = [6]Ti4+ + O2– may be operative for Larvik kaersutites when the O2–/Ti is 1.0. A relatively larger O2–/Ti ratio (1.2—2.0) suggests an another kaersutite substitution mechanism, [6]R2+ + 2OH– = [6]Ti4+ + 2O2–, where [6]R2+ = Fe2+ + Mg + Mn. These effects might result in the limited O2–/Ti ratio value from 1.0 to 2.0.

A negative correlation between Ti and F, suggesting F incorporation into kaersutite may diminish the O2–/Ti ratio, not only due to the occupation of this non-oxy species in the O3 site, but also due to F—Ti avoidance. Composition-dependent H and O isotope variations (δD = –106 to –71% and δ18O = 4.6–5.2%) suggest equilibrium in the closed-system magma with differentiation. The mineral chemistry of Larvik oxy-kaersutitic amphibole could reflect the crystallization in a closed-system magma during rifting with passive crustal thinning at the Oslo palaeorift.

One in four of the Cu-filled cation sites in clinoatacamite, the monoclinic polymorph of atacamite and botallackite, is angle- rather than Jahn-Teller-distorted. Experiments show that this site alone is susceptible to substitution by a non-Jahn-Teller distorting cation of suitable radius and charge, such as Zn2+, and also Ni2+, Co2+, Fe2+, Cd2+ and Mg2+. The crystal symmetry changes to rhombohedral when ∼⅓ of the Cu in this site is substituted by e.g. Zn, thus giving paratacamite; the Zn is essential for stability and forms, with larger proportions of Zn, a series to the end-member in which the site is fully occupied by Zn. This end-member, rhombohedral stoichiometric Cu3Zn(OH)6Cl2, has been characterized using natural specimens from Chile and Iran and is named herbertsmithite. The other cations mentioned behave similarly, producing stabilized rhombohedral paratacamites and end-members analogous to herbertsmithite, which if found in nature, as the Ni analogue has been, should be named species. Clinoatacamite, paratacamite and herbertsmithite have rather similar X-ray powder diffraction patterns, but are readily distinguished by infrared spectroscopy.

Zn-stabilized paratacamite forms blue-green crystals of rhombohedral habit, with vitreous lustre, e = 1.828-1.830, o = 1.835, uniaxial negative, weakly pleochroic O > E, density: 3.75 g cm-3, Mohs hardness: 3-3½; space group R, a = 13.654(5), c = 14.041(6) Å, Z = 24, with pronounced Rm substructure; six strongest XRD lines 5.452 (100), 2.895 (20), 2.760 (74), 2.262 (52), 1.817 (18), 1.708 (21).

Herbertsmithite forms dark green crystals of rhombohedral habit, with vitreous lustre, e = 1.817, o = 1.825, uniaxial negative, weakly pleochroic O > E, density: 3.95 g cm-3, Mohs hardness: 3-3½;; space group Rm with no superstructure observed, a = 6.834(1), c = 14.075(2) Å, Z = 3; six strongest XRD lines 5.466 (55), 4.702 (14), 2.764 (100), 2.266 (36), 1.820 (13), 1.709 (18).

The kinetics and mechanisms of dissolution of the major base metal sulphide minerals, pyrite, chalcopyrite, galena and sphalerite in acidic (chloride) media have been investigated. Minerals were ground in air, then dissolved in air-equilibrated solutions at pH 2.5, while monitoring the redox potential. Solution samples were analysed by ICP-AES and HPLC, and surfaces of residual sulphides analysed using XPS. Dissolution of aerial oxidation products on pyrite particles in the first 15 min apparently led to a sulphur-rich surface, and was followed by slower dissolution of pyrite itself, driven by oxygen reduction, and resulting in net production of protons. Chalcopyrite dissolution resulted in a Cu, S-rich (near) surface layer, accompanied by net consumption of protons. Apparently incongruent dissolution of galena and sphalerite may reflect the formation of elemental S at the surface. The rates of dissolution of chalcopyrite, galena and sphalerite in the presence of pyrite were determined, respectively, as 18, 31 and 1.5 times more rapid than in single-mineral experiments. These data were consistent with galvanically-promoted mineral oxidation of the other sulphides in the presence of pyrite. In the case of galena, the experimental data suggested extensive release of Pb ions and development of a sulphur-rich surface during galvanically-promoted dissolution.

The hydrous calcium carbonate mineral ikaite (CaCO3.6H2O) forms in nature at low temperature in carbonate- and Ca-rich waters. Ikaite crystallizes in the spacegroup C2/c, and consists of CaCO3.6H2O units with Ca ions coordinated by eight oxygens, six from H2O and two from the carbonate group. Hydrogen bonding links CaCO3.6H2O moieties to form the crystal structure.

We have used synchrotron X-ray powder diffraction at T = 243 K to refine the monoclinic structure of ikaite, and have measured unit-cell parameters of ikaite between T = 114 K and T = 293 K. Anisotropic thermal expansion in ikaite is evident, with the smallest relative increase occurring along the b direction parallel to 2-fold axes. The contribution of hydrogen bonding to thermal expansion is assessed by comparison of our data with previously published data for deuterated ikaite, ice and gypsum. Ikaite exhibits a coefficient of volume expansion intermediate between that of ice (Ih) and of deuterated gypsum (CaSO4.2D2O) between T = 114 K and T = 293 K.