The Denchai gem sapphire deposits in Phrae Province, northern Thailand are closely associated with late Cenozoic alkaline basaltic rocks. The sapphires occur in alluvial placer deposits in palaeo-channels at shallow depths. Electron microprobe analysis of minor and trace element contents (Fe, Ti, Cr, Ga and V) of the sapphires indicate the following oxide abundances: Fe2O3 (0.32–1.98 wt.%), TiO2 (0.01–0.23 wt.%), Cr2O3 (<0.01 wt.%), Ga2O3 (0.01–0.03 wt.%) and V2O5 (<0.03 wt.%). Optical studies of sapphires revealed three types of primary fluid/melt inclusions. CO2-rich inclusions (Type I) contain three phases (LH2O + LCO2 + V) with the vapour phase comprising <10–15 vol.%. The presence of CO2 was confirmed by microthermometry and laser Raman analysis. Polyphase inclusions (Type II) (vapour + liquid + solid) contain a fluid bubble (20–30 vol.%), an aqueous phase (10–15 vol.%) and several solid phases. Silicate-melt inclusions (Type III) comprise vapour bubbles, silicate glass and solid phases. Proton-induced X-ray emission (PIXE) analysis revealed high concentrations of K (~;4 wt.%) as well as Ca (~;0.5 wt.%), Ti (~;1 wt.%), Fe (~;2 wt.%), Mn (~;0.1 wt.%), V (<0.03 wt.%), Rb (~;70 ppm) and Zr (~;200 ppm) in the silicate glass. The Ga2O3 abundances and Cr2O3/Ga2O3 values (<1) of the sapphires favour their formation by magmatic processes. The presence of CO2-rich fluids and high K concentrations in the silicate melt inclusions link the origin of the Denchai gem sapphires to CO2-rich alkaline magmatism.

Stromatolitic carbonate in moat-fill of a 1.48 Ga caldera was converted to mineralized calc-silicate skarn by interaction with magma-derived brine at Ketcherside Gap in southeastern Missouri. The skarnrecords early low fO2 conditions similar to those of reduced W and Au skarns. Initial skarn-forming conditions were: PL ≤ 221 bar (22.1 MPa), XCO2 ≤ 0.10, T = 450–;400°C, log fO2 ≈ –30, and log fS2 ≤ –13. Late skarn records combined effects of T↓, fO2↑,fS2↑, XCO2↓, and appearance of an immiscible CO2-rich vapour. The absence of a contact aureole indicates that skarn reactions were driven by advective heat transfer from an infiltrating fluid. Elsewhere in the region, hypersaline, synvolcanic fluids produced oxidized endoskarn in rhyolite. Development of carbonate-hosted, reduced skarn in caldera moat sediments is attributed to: (1) the nature of the host rock and reaction along a lengthy flow path; (2) early, but temporary, dilution of brine influx by CO2-producing reactions; and (3) cooling, possibly accompanied by increased brine influx with time.

Chemical composition and cell parameters were ascertained on new data from Ti-Nb-Ta complex oxides from the miarolitic pegmatites of the Baveno pink granite (Southern Alps, NW Italy). The crystals are tiny, single or aggregated in small sprays, prismatic or tabular, from yellow-orange to brownish in colour. Typical associated minerals include fluorite, zinnwaldite, gadolinite-group minerals and Sc-minerals. Cavity paragenesis is typical of NYF pegmatites, and shows two stages of crystallization developing in magmatic-pneumatolitic and hydrothermal conditions. X-ray data show that some oxides belong to the aeschynite mineral group; others are polycrase and fersmite. Aeschynite and polycrase are chemically heterogeneous and structurally disordered because of their metamict state. This disorder does not always seem to be related to radionuclide contents. Two main trends are indicated, considering the behaviour of Y. The high Y contents fit with very low Ca and LREE contents in the A site; the HREE contents follow the Y trend. In the B site, Ti is the dominant cation, followed by some Nb and very little Ta. Small quantities of Y fit with increasing Ca, U, Th and REE contents. In the B site, Nb cations often exceed those of Ti. The Th contents are often greater than those of U. Besides the already known aeschynite-(Y) and vigezzite, new varieties, ‘titano-vigezzite’ and ‘niobo-aeschynite-(Y)’, are identified here in the Baveno miarolitic cavities. Samples 14 (analysis a) and 2502 (analysis b) have Ca as the main occupant of the A site, followed by Y, Th and REE; in the B site, Ti prevails over Nb. These compositions cannot be considered as pure vigezzite, but as a new variety called ‘titano-vigezzite’. In the same way, analysis a of sample 3 may be considered a new variety of aeschynite-(Y), with Nb prevailing over Ti in the B site, and here called ‘niobo-aeschynite-(Y)’. Neither variety has ever been mentioned in the literature. Epitaxial growth of aeschynite on polycrase (sample 3194) allows some inferences on the crystallization sequence.

Laumontite is a common zeolite mineral indicative of low-grade metamorphism of lavas and volcaniclastic sediments. Stoichiometric laumontite (CaAl2Si4O12·4.5H2O) dehydrates in air at 298.15 K, 1 bar to leonhardite (CaAl2Si4O12·3.5H2O) via loss of water from the W1 crystallographic site. Consideration of reported X-ray diffraction and calorimetric data indicates that the standard molal volume and entropy for dehydration of laumontite to leonhardite + liquid water are ∼13 cc/mol and ∼8 cal/molK, respectively, at 298.15 K, 1 bar. Equilibrium between laumontite and leonhardite occurs at 70 to 80% relative humidity at 298.15 K, 1 bar, corresponding to a standard molal Gibbs energy and enthalpy of reaction of ∼170±40 and ∼2630±100 cal/mol, respectively. Calculated univariant equilibrium for this reaction is nearly linear from 46±3°C at 1 bar to 235±3°C at 5000 bar. Comparison of geological observations with these results suggests that laumontite forms as ‘leonhardite’ during metamorphism and diagenesis. Consideration of ‘leonhardite’, instead of laumontite, in low-grade metamorphic phase relations facilitates prediction of the relative stabilities of zeolites in natural and geologic systems, where calculated entropies of reaction incorrectly predict that assemblages bearing fully hydrated laumontite are stable at lower temperatures than the zeolites heulandite and stilbite.

Routine monitoring of landfill leachates has been extended to include characterization of suspended solids recovered by filtration. Calcite is consistently identified as a suspended solid, with less frequent reports of quartz and clays (kaolinite, illite, chlorite). Morphologically, calcite occurs as discrete grains, coatings on quartz sand and as microconcretions. Preliminary stable isotope data for seven samples generally show positive δ13C values (relative to PDB) up to +3.5‰ and δ18O values between −5 and −8‰, consistent with an origin through precipitation from leachate. Geochemical modelling of leachate compositions for the same samples indicates that the leachates are saturated with respect to calcite, and that the degree of supersaturation decreases for older samples. Mass balance considerations show that the proportions of methane and carbon dioxide observed for landfill gas do not reflect the amount of bicarbonate that is potentially available from the anaerobic decomposition of putrescible waste. Overall, putrescible waste has the potential to form a maximum of 1.9 g of calcite for every gram of waste, although values less than this are likely to be achieved in practice. From these differing lines of evidence, there can be no doubt that calcite precipitation should be expected to take place within landfill systems as an essential part of the waste degradation and stabilization process, and should be considered in modelling both gas evolution and carbon emissions.

The commissioning and operation of apparatus for neutron diffraction at simultaneous high temperatures and pressures is reported. The basic design is based on the Paris-Edinburgh cell using opposed anvils, with internal heating. Temperature is measured using neutron radiography. The apparatus has been shown in both on-line and off-line tests to operate to a pressure of 7 GPa and temperature of 1700°C. The apparatus has been used in a neutron diffraction study of the crystal structure of deuterated brucite, and results for 520°C and 5.15 GPa are presented. The diffraction data that can be obtained from the apparatus are of comparable quality to previous high-pressure studies at ambient temperatures, and are clearly good enough for Rietveld refinement analysis to give structural data of reasonable quality.

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 crystal structure of hydrothermally synthesized Rb-feldspar (monoclinic, space group C2/m, a= 8.839(2)Å, b= 13.035(2)Å, c= 7.175(2)Å, β = 116.11(1)8, V= 742.3(3)Å3, Z= 4) has been refined to a final R of 0.0574 for 692 independent X-ray reflections. Microprobe analyses of the Rb-feldspar suggest deviation from stoichiometry, with excess Si and Al, resulting in a unit formula of Rb0.811□0.127Al1.059Si3.003O8. Infrared (IR) spectra indicate the structural occupancy of large H2O content, which implies that the □Si4O8 substitution favours the structural incorporation of the H2O molecule at the M-site. The mean T–O distances are 1.632 Å for T1 and 1.645 Å for T2, revealing highly disordered (Al,Si) distribution with Al/Si = 0.245/0.755 (T1 site) and 0.255/0.745 (T2 site).

There are two geochemical implications from this refinement: (1) identification of both rubicline triclinic with (Al,Si) ordered distribution and synthetic monoclinic RbAlSi3O8 with (Al,Si) disordered distribution implies that Rb cannot be one of factors disrupting the (Al,Si) ordered and disordered distributions in feldspars; and (2) natural and synthetic feldspars capable of accommodating the large cations tend to incorporate □Si4O8, excess Al and H2O components in their crystal structures.

Some zircons from the Hercynian Soultz granite, NE France, exhibit complex structures, with double cores and oscillatory-banded overgrowths. These glomeroporphyritic crystals are uncommon for zircons, in which synneusis has not previously been described. The cores of the zircons are considered to correspond to very quickly formed {100} or {110} prisms. These could slowly sediment in the magma chamber and cluster together while sinking. The overgrowth rims correspond to a slower growth rate.

U/Pb ion-probe dating of the cores and the overgrowth rims provided the same age of 327±6 Ma. Chemical electron microprobe analyses indicated that cores and rims have the same composition for major and trace elements.

The sinking of zircons accounts for the abnormally high percentages of zircon in the lower parts of the granite. The formation of clusters in the early stages of crystallization needs stable P/T conditions, a hot, liquid silicate melt with a high fluid content, and no other minerals crystallizing (liquidus phase).

Electron microprobe analyses of prehnites from the Way Linggo low-sulphidation epithermal Au-Ag deposit of southern Sumatra, show that the mole fraction of octahedral Fe3+, expressed as Fe3+/(Fe3++AlVI), ranges from 0.0 to ~0.6, the higher values being among the most iron-rich reported for prehnite in a hydrothermal environment. Prehnites from a diabase sill in the Heber geothermal field of California have mole fractions of octahedral Fe3+ ranging from 0.03 to 0.3. The Way Linggo prehnites formed below 220°C, some 20–30°C lower than those at the Heber field; the lower crystallization temperatures perhaps enhanced the opportunity for Fe3+ to substitute in octahedral sites. In both occurrences, prehnite predates late-stage calcite, consistent with the need for waters depositing prehnite to have aCO2 <0.01 moles. At higher CO2 activities the stability field of calcite would swamp the range of aCa2+/aH+ values appropriate for crystallizing prehnite. Consequently, the presence of prehnite in a hydrothermal environment primarily indicates that degassing of the hydrothermal fluid in CO2 occurred prior to deposition.

The removal of phosphorus from wastewaters is becoming very common, to meet water quality targets, and avoid environmental problems related to eutrophication. At the same time, agricultural application of P-rich sewage biosolids is diminishing for reasons of logistics and of public pressure. As a result P from wastewaters is ultimately disposed of in landfills. Over the long term, phosphate ore reserves will become depleted. Recycling of P from wastewaters may thus be a realistic prospect if scientific and technical issues can be resolved. At the centre of the scientific problems lie considerations about optimizing phosphate precipitation as Ca phosphates. A number of Ca phosphate minerals exist, although by far the most common of these is hydroxylapatite. Precipitation kinetic considerations, however, suggest that other Ca phosphates (such as brushite, octacalcium phosphate, whitlockite, monetite or amorphous Ca phosphate) may initially precipitate, and later recrystallize into the most stable hydroxylapatite. This article reviews the complex precipitation mineralogy, chemistry and kinetics of Ca phosphates.

Processes of mineral alteration involving the mobilization and deposition of more than 30 chemical elements during bauxite formation and epigenesis have been studied on specimens from the Devonian Schugorsk bauxite deposit, Timan, Russia. Chemical analyses of the minerals were obtained by electron microprobe and element distribution in the minerals was studied by element mapping. Interpretation of these data also utilized high-resolution BSE and SE images.

The main rock-forming minerals of the Vendian parent rock are calcite, dolomite, feldspar, aegirine, riebeckite, mica, chlorite and quartz; accessory minerals are pyrite, galena, apatite, ilmenite, monazite, xenotime, zircon, columbite, pyrochlore, chromite, bastnaesite and some others. Typically, the grainsize of the accessory minerals in both parent rock and bauxite is from 1 to 40 µm. However, even within these rather small grains, the processes of crystal growth and alteration during weathering can be determined from the zonal distribution of the elements. The most widespread processes observed are: (1) Decomposition of Ti-bearing minerals such as ilmenite, aegirine and riebeckite with the formation of ‘leucoxene’, which is the main concentrator of Nb, Cr, V and W. Crystal growth can be traced from the zonal distribution of Nb (up to 16 wt.%). Vein-like ‘leucoxene’ is also observed in association with organics. (2) Weathering of columbite and pyrochlore: the source of Nb in ‘leucoxene’ is now strongly weathered columbite, while the alteration of pyrochlore is expressed in the growth of plumbopyrochlore rims around Ca-rich cores. (3) Dissolution of sulphide minerals and apatite and the formation of crandallite group minerals: ‘crandallite’ crystals of up to 40 µm size show a very clear zonation. From the core to the rim of a crystal, the following sequence of elements is observed: Ca → Ba → Ce → Pb → Sr → Nd. Sulphur also shows a zoned but more complicated distribution, while the distribution of Fe is rather variable. A possible source of REE is bastnaesite from the parent rock. More than twelve crandallite type cells can be identified in a single ‘crandallite’ grain. (4) Alteration of stoichiometric zircon and xenotime with the formation of metamict solid solution of zircon and xenotime: altered zircon rims also bear large amounts of Sc (up to 3.5 wt.%), Fe, Ca and Al in the form of as yet unidentified inclusions of 1–2 µm. Monazite seems to be the least altered mineral of the profile.

In the parent rock, an unknown mineral of the composition (wt.%): ThO2 – 54.8; FeO – 14.6; Y2O5 – 2.3; CaO – 2.0; REE – 1.8; SiO2 12.2; P2O5 – 2.8; total – 94.2 (average from ten analyses) was determined. In bauxite, another mineral was found, which has the composition (wt.%): ThO2 – 24.9; FeO – 20.5; Y2O5 – 6.7; CaO 2.0; – ZrO – 17.6; SiO2 – 8.8; P2O5 – 5.4; total – 89.3 (F was not analysed; average from nine analyses). Presumably, the second mineral is the result of weathering of the first one. Although the Th content is very high, the mineral is almost free of Pb. However, intergrowths of galena and pyrite are observed around the partially decomposed crystals of the mineral. Another generation of galena is enriched in chalcophile elements such as Cu, Cd, Bi etc., and is related to epigenetic alteration of the profile, as are secondary apatite and muscovite.

An ‘Al-thermometer’ was applied to agate samples of volcanic parent rocks to provide information about the temperature of agate formation. The temperatures were calculated from concentrations of [AlO4]0 centres determined by electron paramagnetic resonance (EPR) measurements. The calculations for agate bands in some cases yield temperatures of up to 655°C, which are assumed to be invalid; they are thought to be artifacts resulting from non-equilibrium crystallization processes. In contrast, the formation temperatures (60–198°C) estimated for associated quartz incrustations within the agate geodes are in good accord with those calculated from oxygen isotope data. Direct estimation of the formation temperatures of agates is problematic. The best results will be obtained by analyses of associated phanerocrystalline quartz incrustations.

Crystal growth experiments in the system BaO–Al2O3 yielded single crystals of a new Ba oxo-aluminate with composition Ba4Al2O7. The title compound is orthorhombic, with cell parameters a = 11.3126(5), b = 11.7045(9), c = 27.1850(14) Å, space group Cmca. The structure was solved by direct methods followed by difference Fourier synthesis from X-ray single crystal diffraction data (R1 = 0.048 for 1213 independent observed reflections and 135 parameters). The main building units of tetrabarium aluminate are Al3O10 trimers and isolated AlO4 tetrahedra. Seven crystallographically different Ba sites crosslink between the tetrahedral groups and are co-ordinated by six to nine oxygen ligands. The structure is closely related to the mineral kilchoanite (Ca6[SiO4][Si3O10]) and the first representative of an unbranched oligo-aluminate with triple tetrahedra.

More than 19,000 analytical data mainly from the literature were used to study statistically the distribution patterns of F and the oxides of minor and trace elements (Ti, Sn, Sc, V, Cr, Ga, Mn, Co, Ni, Zn, Sr, Ba, Rb, Cs) in trioctahedral micas of the system phlogopite-annite/siderophyllite-polylithionite (PASP), which is divided here into seven varieties, whose compositional ranges are defined by the parameter mgli (= octahedral Mg minus Li). Plots of trace-element contents vs. mgli reveal that the elements form distinct groups according to the configuration of their distribution patterns. Substitution of most of these elements was established as a function of mgli. Micas incorporate the elements in different abundances of up to four orders of magnitude between the concentration highs and lows in micas of ‘normal’ composition. Only Zn, Sr and Sc are poorly correlated to mgli. In compositional extremes, some elements (Zn, Mn, Ba, Sr, Cs, Rb) may be enriched by up to 2–3 orders of magnitude relative to their mean abundance in the respective mica variety. Mica/melt partition coefficients calculated for Variscan granites of the German Erzgebirge demonstrate that trace-element partitioning is strongly dependent on the position of the mica in the PASP system, which has to be considered in petrogenetic modelling.

This review indicates that for a number of trace elements, the concentration ranges are poorly known for some of the mica varieties, as they are for particular host rocks (i.e. igneous rocks of A-type affiliation). The study should help to develop optimal analytical strategies and to provide a tool to distinguish between micas of ‘normal’ and ‘abnormal’ trace-element composition.

The construction of zirconium (Zr) budgets for metamorphic reactions in high-grade rocks provides new insight into zircon growth during metamorphism. In this study we target reactions involving garnet, as they enable zircon growth to be related to known pressure and temperature conditions. Two reactions involving the breakdown of Zr-bearing garnet from Rogaland, SW Norway have been investigated in detail, showing contrasting behaviour of Zr, with zircon formation being subject to the solubility of Zr in product phases. In the decompression reaction garnet + sillimanite + quartz → cordierite, Zr released during garnet breakdown cannot be incorporated into the cordierite structure, resulting in zircon nucleation and growth. In contrast, for the reaction garnet + biotite + sillimanite + quartz → osumilite + orthopyroxene + spinel + magnetite, no new zircon growth takes place, despite the garnet involved containing more than double the Zr concentration of the former reaction. In the latter case, all the Zr released by garnet breakdown can be detected in the product phases osumilite and orthopyroxene, thereby preventing growth of new metamorphic zircon. This study highlights the potential for high resolution geochronology in metamorphic rocks by relating zircon growth to specific metamorphic reactions.

North Motzfeldt is an intrusive igneous centre within the Igaliku (formerly spelt Igaliko) complex, Gardar Province, South Greenland. A detailed field description of the centre is given, with preliminary geochemical and isotopic data. The North Motzfeldt centre is intruded into Ketilidian granitoid basement rocks, and current exposure retains parts of the original roof against earlier Gardar eruptives and clastic sediments of the Eriksfjord formation. The unconformity between the Ketilidian and the overlying Eriksfjord is believed to have been crucial in the siting of the centre. The centre is subdivided into two major units, NM1 and NM2. This was followed by significant peralkaline nepheline microsyenite in sheets, characterized by rare element-rich accessory minerals including rinkite-mł sandrite, pyrochlore and låvenite. A significant microsyenite body is called NM3. A preliminary Rb-Sr isochron of 1226±27 Ma indicates a far younger age for the centre than previously thought (~;1350 Ma). Cross-cutting relationships between North Motzfeldt and rocks of the adjacent Motzfeldt centre require a reappraisal of the chronology of Motzfeldt magmatism. We suggest that rocks previously believed to comprise the Motzfeldt centre represent the products of multiple phases of magmatism from Early- to Mid-Gardar times.

Tausoare Cave is renowned in Romania for its gypsum and mirabilite speleothems. Of interest are the white crystalline speleothems formed on the floor of the ‘Sala de Mese’ (Dining Room) that were previously described as consisting of mirabilite. The samples we collected reveal crystals of two different habits. One shows the characteristic mirabilite fibrous crystals (cotton-like speleothem) while the other formed bladed and short prismatic crystals which comprise the delicate ‘cave flowers’. The mineral association was characterized by means of X-ray analysis, scanning electron microscopy and electron microprobe. Beside thenardite (dehydration product of mirabilite) we also identified three sulphate minerals: leonite [K2Mg(SO4)2·4H2O], syngenite [K2Ca(SO4)2·H2O] and konyaite [Na2Mg(SO4)2·5H2O]. Of these, leonite and konyaite have never been reported in a cave environment. This paper describes the mineralogy of this particular sulphate deposit and offers some viewpoints on the crystallogenesis.

At the top of Mt. Mottarone a thin level of micaschist, covered by soil, rests on granodioritic rocks. Both rock types underwent weathering with generation of new minerals and variation of the original chemical composition. The weathering produced phyllosilicates and Fe- and Al-hydroxides. Mass balance calculations on the basis of Zr immobility indicate that at least As, Bi, Cd, Mo and Sb were added to the micaschist, whereas the other elements were removed; the soil was also enriched in As, Bi, Cd, Mo and Sb during weathering. Dry and wet pollution was responsible for the addition of the elements listed above. On the other hand, Ca, Na, Mo and Sr were surely removed from the granodiorite during weathering, whereas Bi and Cu were added by percolation from the overlying micaschist. The chemical features of a spring issuing from granodiorite agree well with the element budget as deduced from the rock transformation. This is not the case, however, for a spring issuing from the micaschist.

The alteration mineralogy of two outcrops of basaltic lavas in northeast Ireland is studied with respect to the hydrothermal alteration history of basalts. Evidence for contact between basaltic flows and palaeorivers or palaeolakes is reported in both outcrops, which belong to two different formations: the Lower Basaltic Formation (LBF) and the Inter Basaltic Formation (Causeway Tholeiite Member, CTM). The secondary minerals consist of layer silicates (chlorite-smectite, C-S, di- and trioctahedral smectites), zeolites, calcite and silica minerals and there is a repetition of the sequence of alteration mineralogy in each formation. The mineralogy of phyllosilicates from the LBF (C-S) corresponds to hotter conditions of alteration than those of CTM (di/trioctahedral smectites), while the zeolite mineralogy is controlled by the fluid composition. In consequence, the mineralogy and the distribution of alteration minerals suggest that the crystallization of phyllosilicates and zeolites did not develop during burial of lavas a long time after the eruption, but reflects thermal gradients driven by lava heat flow and marked by local perturbation caused by regional water flow through the aquifer zone in the lava during the last cooling of each lava sequence.