The concentrations of LREE and Zr in a granitic melt formed by anatexis of a metapelitic protolith will be buffered by the stability of monazite and zircon respectively. The rate at which equilibrium is reached between dissolving monazite and zircon and a static melt is limited by the rate at which Zr and LREE can diffuse away from dissolution sites. If melt extraction rates exceed the rates at which the LREE and Zr in the melt become homogenized by diffusion, extracted melts will be undersaturated with respect to these elements. Evidence from accessory phase thermometry suggests that for many Himalayan leucogranites generated by crustal anatexis, the melts equilibrated with restitic monazite and zircon prior to extraction. In contrast, discordant temperatures determined from accessory phase thermometry suggest that tourmaline leucogranites from the Zanskar region of NW India did not equilibrate prior to extraction. Quantitative interpretation of this discordance assumes that the melt was static prior to extraction, and that accessory phase inheritance was minimal. Modelling of the time-dependant homogenization process suggests that tourmaline leucogranites generated at 700°C probably remained in contact with restitic monazite in the protolith for less than 7 ka and certainly less than 50 ka. Such rapid extraction rates suggest that deformation-driven mechanisms were important in removing these melts from their source.

Iowaite has been re-examined using new, well crystallized material from the Palabora open pit mine, Transvaal. Microprobe, carbon analyser and thermal analyses, powder and single-crystal X-ray diffraction, infrared, UV-visible and mass spectroscopic and optical studies were made. The ideal formula is (OH)16Cl2·4H2O. It is trigonal, R3̄m, a = 3.1183(9), c = 24.113(8) Å, V = 203.1(2) Å3, Z = 3/8; Dobs 2.09 g/cm3.; Dcalc 2.04 g/cm3; hardness (Mohs)=2 1/2. The interlayer Cl− ions are displaced from the threefold axis. It is uniaxial negative, with ω = 1.561 ± 0.002, ε = 1.543 ± 0.002; coloured crystals are intensely pleochroic, due to intervalence charge transfer between the Fe3+ and Fe2+ substituting for Mg2+, with O pale yellow, E deep blue-green.

This paper reviews recent applications of Monte Carlo methods for the study of cation ordering in minerals. We describe the program Ossia99, designed for the simulation of complex ordering processes and for use on parallel computers. A number of applications for the study of long-range and short-range order are described, including the use of the Monte Carlo methods to compute quantities measured in an NMR experiment. The method of thermodynamic integration for the determination of the free energy is described in some detail, and several applications of the method to determine the thermodynamics of disordered systems are outlined.

The weathering of the Mt. Prinzera serpentinites (Parma province, Northern Apennines, Italy) produced dominant smectite and minor Fe-hydroxides. The mobility of the elements during weathering has been estimated using the ratio Ki = MiS/MiR, where Mi indicates the mass of a generic component i before (R) and after (S) the weathering, and using TiO2 as a practically immobile component. For prevalently to tendentially mobile elements, the degree of mobility, which in our case increases as Ki decreases, is in the order Mn ≈ Cr = Fe < V ≈ Zn ≈ Co < Ni < Si < Mg < Ca. The elements Ti, Ga, Al and Zr are prevalently immobile. The mass chemically removed by the circulating waters during weathering may reach very high values (on average 52% of the original mass of serpentinite) and the main contribution to the mass loss is due to Si and Mg. The composition of the perennial and ephemeral springs in the area is in agreement with the degree of the element mobility at least for Cr, Mg and Ca.

The crystal structure of synthetic ‘plumbonacrite’, Pb5O(OH)2(CO3)3, hexagonal, P63cm, a = 9.0921(7), c = 24.923(3)Å, V = 1784.3(3)Å3, Z = 6, has been solved by direct methods and refined to R = 0.049. There are six symmetrically independent Pb2+ positions in the structure, the coordination polyhedra of which are strongly distorted due to the effect of s2 lone-electron pairs on the Pb2+ cations. The Pb(6) position is disordered with a Pb–Pb distance of 1.24 Å . The structure of ‘plumbonacrite’ is built from complex Pb–O layers parallel to the (001) plane similar to those observed in polymorphs of Pb4(OH)2(SO4)(CO3)2. The structure of these layers can be described in terms of Pb–O,OH motifs and CO3 groups. The smallest structural subunit is the oxocentred [OPb4] tetrahedron that shares three of its Pb-Pb edges with three [(OH)Pb3] distorted triangles to form [O(OH)3Pb7] clusters. These clusters are surrounded by CO3 groups, forming more complex clusters. Due to the disorder in the Pb(6) site, the clusters comprising this site are linked with each other via OH(10) groups to give continuous sheets of Pb–O,OH bonds which are parallel to the (001) plane. The [O(OH)3Pb7] clusters in ‘plumbonacrite’ may be important in more complex Pb carbonate oxo/hydroxo complexes that may exist in aqueous environments.

The exact nature of tripuhyite remains controversial more than 100 years after the first description of the mineral. Different stoichiometries and crystal structures (rutile or tri-rutile types) have been suggested for this Fe-Sb-oxide. To address these uncertainties, we studied tripuhyite from Tripuhy, Minas Gerais, Brazil (type material) and Falotta, Grisons, Switzerland using single-crystal and powder X-ray diffraction (XRD), optical microscopy and electron microprobe analysis.

Electron microprobe analyses showed the Fe/Sb ratios to be close to one in tripuhyite from both localities. Single crystal XRD studies revealed that tripuhyite from the type locality and from Falotta have the rutile structure (P42mnm, a = 4.625(4) c = 3.059(5) and a = 4.6433(10) c= 3.0815(9) Å, respectively). Despite careful examination, no evidence for a tripled c parameter, characteristic of the tri-rutile structure, was found and hence the structure was refined with the rutile model and complete Fe-Sb disorder over the cationic sites in both cases (type material: R1 = 3.61%; Falotta material: R1 = 3.96%). The specular reflectance values of type material tripuhyite and lewisite were measured and the following refractive indices calculated (after Koenigsberger): tripuhyite nmin = 2.14, nmax = 2.27; lewisite (cubic) n = 2.04.

These results, together with those of 57Fe and 121Sb Mössbauer spectroscopy on natural and synthetic tripuhyites reported in the literature, indicate that the chemical formula of tripuhyite is Fe3+Sb5+O4 (FeSbO4). Thus, tripuhyite can no longer be attributed to the tapiolite group of minerals of general type AB2O6. A comparison of the results presented with the mineralogical data of squawcreekite suggests that tripuhyite and squawcreekite are identical. In consequence, tripuhyite was redefined as Fe3+Sb5+O4 with a rutile-type structure. Both the proposed new formula and unit cell (rutile-type) of tripuhyite as well as the discreditation of squawcreekite have been approved by the Commission on New Mineral and Mineral Names (CNMMN) of the International Mineralogical Association (IMA).

The crystal structure of the clay mineral dickite (Al2Si2H4O9) has been refined to a greater accuracy than that reported in an earlier analysis. Improved lattiçe parameters are: a 5·15±0·001, b 8·940±0·001, c 14·424 ± 0·002Å., β 96° 44′± 1′. The dickite structure shows several significant distortions from the geometry of the idealized kaolin layer, including deformation and rotation of the silica tetra-hedra. The most striking features of the octahedral layer are the extremely short shared edges of 2·37 Å. Although the analysis was not sufficiently accurate to position the hydrogen atoms with certainty, a model consistent with the infrared absorption spectra is proposed. The stacking sequences of kaolin-layer minerals have been considered with reference to the structural features observed in dickite. There are thirty-six ways of superposing two kaolin layers commensurate with the OH-O bonds found in kaolinite, dickite, and nacrite. The twelve sequences showing the least amount of cation-cation superposition between consecutive kaolin layers can be used to construct two one-layer cells, kaolinite and its mirror image, and twelve two-layer cells, including dickite and nacrite. The distortions of the kaolin layer introduce secondary variations in the interlayer bonding that suggest that dickite and nacrite are the most stable of the kaolin layer structures, since they possess the shortest oxygen-hydroxyl contacts.

The distribution of Au and associated trace elements in pyrite and arsenopyrite from late Archean Hutti and Hira-Buddini orogenic gold deposits, eastern Dharwar Craton, southern India was investigated by laser ablation-inductively coupled plasma-mass spectrometry. X-ray element maps acquired by electron probe microanalyser reveal oscillatory zoning of Co and As indicating the crystallization of pyrite and arsenopyrite in an episodic fluid flow regime in which fluid salinity fluctuated due to fault-valve actions. The absence of any relationship between Au and As in pyrite obviate the role of As in the incorporation of Au into pyrite, particularly here and may be generally the case in orogenic gold deposits. On the other hand, positive correlations of Au with Cu, Ag and Te suggest possible influence of these chalcophile elements in the enhanced gold concentrationin sulfides. Pb-Bi-Te-Au-Ag bearing micro-particles (<2 μm) are observed exclusively in micro-fractures and pores in arsenopyrite. The absence of replacement features and element gradient suggests direct precipitation of Pb, Bi, Te, Au and Ag from a fluid that was unreactive towards arsenopyrite. An intermittent fall in fluid pressure caused by the fault-valve action would have resulted in the sporadic precipitation of Au, Pb, Ag, Bi and Te.

Oriented inclusions of monazite occur in the dark core of apatite porphyroblasts in a muscovite schist from the Archaean Hemlo gold deposit, Ontario, Canada. The monazite inclusions are elongated along the b-axis and parallel to the c-axis of the apatite host; the complete orientation relationship of the monazite/apatite intergrowth is bMnz//cAp, cMnz//aAp. From analysis by SIMS and EMP, the dark core of the apatite porphyroblasts is depleted in LREE (LaN/YbN = 0.56). The monazite inclusions are correspondingly enriched in LREE, but markedly depleted in HREE, compared with monazite grains in the rock matrix and cross-cutting veins. The monazite inclusions precipitated by oriented reaction through rock-fluid interactions during a late hydrothermal alteration. Their unusual REE composition is probably related to both a preferential leaching of LREE from the dark core and a selective transfer of HREE out of the apatite porphyroblasts.

The type locality for erionite has been identified and specimens compared with Eakle's original material. New determinations of the physical properties and a chemical analysis have been made. Correlation of X-ray powder and fibre rotation data with electron diffraction of single crystals has shown that the unit cell is hexagonal with a 13·26, c 15·12 Å., space-group P31c, P¯31c, P63mc, P¯62c, or P63/mmc, giving a calculated sp. Gr. of 2·07 and atomic cell contents (Ca, Mg, Na2, K2)4·5Al9Si27O72.27H2O. A structure is proposed for the aluminosilicate frame, with space-group P63/mmc, which gives satisfactory correlation between observed and calculated structure factors for the X-ray fibre rotation pattern.

Saddle dolomite is a common product of late-stage diagenesis and hydrothermal activity. It has been suggested that during growth Ca enrichment occurs towards crystal edges leading to a lattice expansion relative to face centres. However, backscatter scanning electron microscopy of eight samples has revealed that, instead of edge associated Ca enrichment, saddle dolomites have a series of edge associated Mg enriched wedges, between 5 and 20 µm thick and 300 µm long. Wedge geometry implies development of extra lattice layers at edges relative to face centres. It is suggested that the wedges develop during rapid, transport-controlled, crystal growth. The wedges possibly reflect a switching from continuous growth across the face to edge-nucleated growth as the boundary layer solution becomes progressively depleted. Continuous growth might be reinstigated through convective turnover of the boundary layer presenting fresh solution to the growing crystal.

Near infrared absorption (NIR) spectra of natural morphologically cubic polycrystalline diamonds (cuboid) were obtained at room temperature, and the stretching plus bending combination band of molecular water was observed. The spectrum consisted of the main band at 5180 cm-1 due to liquid water and a shoulder at 5000 cm-1. The 5000 cm-1 band suggests the presence of a phase with stronger hydrogen bonding in inclusions in the diamond. This shoulder absorption decreased on heating to 120°C. The combination band of H2O at high pressure and temperature was measured using a resistively heated diamond cell and the pressure dependence of the peak position was obtained. Comparison with the present experimental results indicates that the spectral changes induced by heating of the cuboid corresponded to melting of a high-pressure form of ice, and the shoulder absorption at 5000 cm-1 arises from ice VI at 1.9 GPa. On the other hand, the liquid water, a main component of the fluid inclusions in the cuboid, was not under high pressure judging from the frequency of the combination band. This contrast might relate to the texture of the cuboid diamond. The spectral observation enables us to estimate the residual pressure of mantle fluid encapsulated in these diamonds. The diamond-cell data also provide high-P-T NIR fingerprint spectra that could be useful for identifying H2O phases and confining pressures in other samples.

During the past 70 years, more than 2000 metric tonnes of Pu, and substantial quantities of the ‘minor’ actinides such as Np, Am and Cm, have been generated in nuclear reactors. Some of these transuranium elements can be a source of energy in fission reactions (e.g. 239Pu), a source of fissile material for nuclear weapons (e.g. 239Pu and 2Np), and of environmental concern because of their long half-lives and radiotoxicity (e.g. 239Pu and 237Np). There are two basic strategies for the disposition of these transuranium elements: (1) to ‘burn’ or fission the actinides using nuclear reactors or accelerators; (2) to dispose of the actinides directly as spent nuclear fuel or to ‘sequester’ the actinides in chemically durable, radiation-resistant materials that are also suitable for geological disposal. For the latter strategy, there has been substantial interest in the use of actinide-bearing minerals, especially isometric pyrochlore, A2B2Oi (A = rare earths; B = Ti, Zr, Sn, Hf), for the immobilization of actinides, particularly plutonium, both as inert matrix fuels and nuclear waste forms. Systematic studies of rare-earth pyrochlores have led to the discovery that certain compositions (B = Zr, Hf) are stable to very high doses of α-decay event damage. Recent developments in the understanding of the properties of actinide-bearing solids have opened up new possibilities for the design of advanced nuclear materials that can be used as fuels and waste forms. As an example, the amount of radiation damage that accumulates over time can be controlled by the selection of an appropriate composition for the pyrochlore and a consideration of the thermal environment of disposal. In the case of deep borehole disposal (3—5 km), the natural geothermal gradient may provide enough heat to reduce the amount of accumulated radiation damage by thermal annealing.

The Western Gneiss Region (WGR) of Norway consists largely of Proterozoic orthogneisses, but also contains paragneisses, peridotites, anorthosites, gabbros and coarse-grained intermediate-acid ‘rapakivi granites’. All of these lithologies enclose eclogites. Structural and isotopic data suggest that many of these rocks were juxtaposed by early Caledonian thrusting prior to eclogite formation at ca. 425 Ma.

Low-P protoliths can be demonstrated for many eclogites. Prograde metamorphism to eclogite facies is demonstrated by inclusion suites within garnet grains and zoning of eclogite minerals. The regional distribution of KD (gnt/cpx) and Xcpxjd shows a decrease in Tmax, and in the corresponding P, away from the present coastline. The lowest values (500 °C, 10 kbar) are found in the Sunnfjord area and the highest (∼ 800 °C) along the coast of Sunnmøre and Nordmøre.

Maximum pressures were reached at temperatures 100–200° < Tmax. This P-T-t path is consistent with the preservation of jadeite-rich cpx (and possible coesite) in the coastal regions. Earlier overestimates of Pmax, based on partitioning of Al between opx and gnt, resulted from combination of early low-T (low-Al) opx and T values derived from cpx/gnt equilibrated at Tmax. Despite pervasive later amphibolitization, high-P assemblages (phengite + kyanite, omphacite + quartz) are locally preserved within gneisses near the coast. The high-P metamorphism can be explained by westward subduction of the Baltic continental plate beneath the Greenland plate, during the Caledonian orogeny.

At least some of the Mg-Cr garnet peridotites of the WGR were derived from low-P protoliths (spinel ± chlorite peridotites, enclosing high-Al pyroxenites). While Sm-Nd mineral ages of most eclogites cluster around 425 Ma, garnet peridotites and their enclosed garnet pyroxenites give Proterozoic Sm-Nd mineral ages (1700–1000 Ma). The tectonic position of the Mg-Cr garnet peridotites, relative to the Caledonian high-pressure metamorphism, remains to be resolved.

Diagenetic palaeotemperatures determined from aqueous fluid inclusions can be affected by re-equilibration during burial heating. Calculations based on the observed behaviour of inclusions in fluorite under external confining pressure allows prediction of the temperatures and depths of burial necessary to initiate re-equilibration of aqueous inclusions in the common size range 40 to 4 µm. Heating of 20° to 60°C over the initial trapping temperature may cause errors of 10° to 20°C in the homogenization temperature. This suggests re-equilibration may cause aqueous inclusions in carbonates to yield a poor record of their low-temperature history, but a useful record of the maximum temperature experienced by the host rock. Previous work suggests inclusions containing petroleum fluids will be less susceptible to re-equilibration.

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.

The Transdanubian Volcanic Region (TVR) is composed mainly of Pliocene alkali basalts, basanites, olivine basalts and olivine tholeiites, as well as rare nephelinites. The partial melting and genesis of alkali basaltic liquids is a consequence of an upwelling of the upper mantle which also caused thinning of the lithosphere and recent sinking of the Pannonian Basin.

Four different types of lower crustal and upper-mantle xenoliths are found within the TVR: garnet-free and garnet-bearing granulites, clinopyroxenites and spinel lherzolites. We present mineralogical and geochemical data on granulite facies and clinopyroxenite xenoliths from three localities in the Hungarian part of the TVR (Bondoróhegy, Szentbékálla and Szigliget). It is concluded that, whilst the protoliths of the granulite facies xenoliths were tholeiitic igneous rocks and could be part of an ancient crust, the clinopyroxenite xenoliths represent recent underplating and may have formed from an alkali basaltic liquid similar to the host lava. Planar contact relations between clinopyroxenites and spinel lherzolites as observed in composite xenoliths, as well as high Al-contents in clinopyroxenes, point to a high-pressure genesis in the upper mantle for these rocks. In contrast, geobarometrical estimates yielded only a moderate pressure range characteristic of lower crustal levels for the garnet-free granulite xenoliths (7–9 kbar). Nevertheless, two-pyroxene geothermometry yielded high temperatures of equilibration (>900°C) for these xenoliths, probably caused by advective heat transfer connected with underplating and in agreement with the high present-day geothermal gradient of this region. In the Central Range localities only garnet-free granulite xenoliths occur, whereas at the border of the TVR both garnet-free and garnet-bearing granulite facies nodules are found. It is possible that the incoming of garnet is retarded by higher temperatures in the lower crust below the Central Range.

It is also suggested that the difference in seismically measured crustal thickness between the Central Range and adjacent basin areas may be connected with different thermal conditions below these regions and that the seismically defined Moho and the petrological Moho do not necessarily coincide.

Rare earth minerals in ankeritic ferrocar-bonatite and associated magnetite ore, as well as in hematite-calcite-(dolomite) carbonatite (rødberg) derived from the ferrocarbonatite by post-magmatic alteration, have been studied by electron microprobe. The minerals found are monazite, parisite, and bastnäsite (identifications confirmed by X-ray diffraction) as well as an aluminous silicate with allanite composition, and possibly, synchysite. The rare earth element (REE) distribution patterns of the minerals change from light rare earth (LREE)-enriched in magnetite ore and ferrocarbonatite to less LREE-enriched, or middle REE-enriched in the most strongly re-equilibrated carbonatites. Two distinct mineral varieties, monazite-(Ce,Nd) and a Nd-fluorocarbonate, have been found in rødberg. The LREE were leached from their host minerals during re-equilibration of the carbonatite, most likely because of the influence of fluoride-bearing hydrothermal solutions.

Iron minerals influence the environmental redox behaviour and mobility of metals including the long-lived radionuclide technetium. Technetium is highly mobile in its oxidized form pertechnetate (Tc(VII)O4–), however, when it is reduced to Tc(IV) it immobilizes readily via precipitation or sorption. In low concentration tracer experiments, and in higher concentration XAS experiments, pertechnetate was added to samples of biogenic and abiotically synthesized Fe(II)-bearing minerals (bio-magnetite, bio-vivianite, bio-siderite and an abiotically precipitated Fe(II) gel). Each mineral scavenged different quantities of Tc(VII) from solution with essentially complete removal in Fe(II)-gel and bio-magnetite systems and with 84±4% removal onto bio-siderite and 68±5% removal onto bio-vivianite over 45 days. In select, higher concentration, Tc XAS experiments, XANES spectra showed reductive precipitation to Tc(IV) in all samples. Furthermore, EXAFS spectra for bio-siderite, bio-vivianite and Fe(II)-gel showed that Tc(IV) was present as short range ordered hydrous Tc(IV)O2-like phases in the minerals and for some systems suggested possible incorporation in an octahedral coordination environment. Low concentration reoxidation experiments with air-, and in the case of the Fe(II) gel, nitrate-oxidation of the Tc(IV)-labelled samples resulted in only partial remobilization of Tc. Upon exposure to air, the Tc bound to the Fe-minerals was resistant to oxidative remobilization with a maximum of ∼15% Tc remobilized in the bio-vivianite system after 45 days of air exposure. Nitrate mediated oxidation of Fe(II)-gel inoculated with a stable consortium of nitrate-reducing, Fe(II)-oxidizing bacteria showed only 3.8±0.4% remobilization of reduced Tc(IV), again highlighting the recalcitrance of Tc(IV) to oxidative remobilization in Fe-bearing systems. The resultant XANES spectra of the reoxidized minerals showed Tc(IV)-like spectra in the reoxidized Fe-phases. Overall, this study highlights the role that Fe-bearing biogenic mineral phases have in controlling reductive scavenging of Tc(VII) to hydrous TcO2-like phases onto a range of Fe(II)-bearing minerals. In addition, it suggests that on reoxidation of these phases, Fe-bound Tc(IV) may be octahedrally coordinated and is largely recalcitrant to reoxidation over medium-term timescales. This has implications when considering remediation approaches and in predictions of the long-term fate of Tc in the nuclear legacy.

The crystal structure of botallackite, Cu2(OH)3Cl, monoclinic, a = 5.717(1), b = 6.126(1), c = 5.636(1)Å, β = 93.07(1)°, V = 197.06(5)Å3, space group P21/m, Z = 1, has been refined to an R index of 3.8% for 350 observed (4σ) reflections, measured with Mo-Kα X-radiation on an automatic four-circle diffractometer. The structure consists of sheets of edge-sharing Cuϕ6 (ϕ = unspecified anion) octahedra of composition Cu2(OH)3Cl; these sheets are // {100}, and are joined by hydrogen bonding between oxygen and chlorine anions, thus accounting for the perfect {100} cleavage and the platy habit of botallackite.