A Mössbauer investigation has been carried out on garnets from the Ivrea-Verbano zone and the results are compared with those obtained on the same samples by X-ray absorption spectroscopy (XAS). The problem addressed is the precise structural characterisation of the local environment of iron in garnets with Fe/Ca ratio variable between ∼3.0 and ∼18.0. Ferric iron is octahedrally coordinated and ferrous iron is in the dodecahedral site in all the samples. Mössbauer results are in agreement with those obtained by XAS and show that, at least in the compositional range of the garnets examined (0.1-0.5 calcium atoms p.f.u.), the iron environment is not significantly modified by the larger calcium cations sharing the same dodecahedral site. It is confirmed that the Mössbauer technique is more sensitive than XAS in detecting low percentages of iron, especially when the cation is present in more than one oxidation state and coordination number.

Three types of mafic granulites, namely two pyroxene-plagioclase granutite (MG), two pyroxeneplagioclase-garnet granulite (GMG) and spinel-olivine-plagioclase-two pyroxene granulite (SMG) are exposed at Sunkarimetta, Eastern Ghats belt, India. The marie granulites exhibit a foliation concordant with that in associated granulite facies quartzofeldspathic gneisses. Textural characteristics and mineral chemical data suggest the following mineral reactions: olivine + plagioclase = spinel + orthopyroxene + clinopyroxene (SMG), orthopyroxene + plagioclase = garnet + quartz (GMG), clinopyroxene + plagioclase = garnet + quartz (GMG) and plagioclase + hemoilmenite + quartz = garnet + ilmenite + 02 (GMG). Geothermobarometry indicates maximum P-T conditions of metamorphism at c. 8.5 kbar, 950°C The marie granulites later suffered nearly isobaric cooling to c. 7.5 kbar, 750°C Bulk compositional characteristics suggest that SMG is of cumulate origin. The protoliths of the mafic granulites, emplaced at c. 32 km depth, are probably responsible for thermal perturbation causing granulite facies metamorphism of the enclosing rocks.

A carbonatite dyke from the Sarnu-Dandali alkaline complex, Rajasthan, India, contains a remarkable suite of rare earth, strontium-rich minerals with spectacular primary textures.

Sr, Mn-rich calcite in the outer 5 mm of the dyke contains exsolved lamellae of carbocernaite, (Ca,Na)(Sr,Ce,Ba)(CO3)2, orientated parallel to its twin and cleavage planes. The amount of exsolved carbocernaite increases away from the dyke margin as the Sr content of the calcite increases to a maximum 13 wt.%. Sr levels as high as this in calcite have previously been recorded only in experimental work. The carbocernaite exsolution suggests that Sr-rich calcium carbonate can be a host for major amounts of REE in carbonatite magma.

Separated by a sharp internal boundary, is a complex possibly cotectic intergrowth of carbocernaite and Sr-rich calcite with late Ca-rich strontianite (19 wt.% CaO). Other minerals in the dyke include baryte, pyrrhotite, alabandite, sphalerite and occasional bastnäsite-(La) and thorite. Bands of late britholite-(Ce) traverse the dyke.

The host rock for the dyke is fenitized melanephelinite which is itself traversed by narrow, <1 mm, carbonatite veins beleived to predate the carbonatite dyke. Allanite, britholite-(Ce) and rare monazite-(Ce), developed at the boundary between the carbonatite dyke and the fenite, may have been produced by a reaction between the dyke and the wall rock, or may be related to the later britholite mineralisation.

The textures and mineral compositions indicate primary crystallisation. They are unique amongst rare earth-rich carbonatites which are usually late-stage phenomena with signs of secondary alteration.

Comparison with experimental data available for the calcite-strontianite system suggests conditions of 500°C and 2 kbar for coexisting Sr-rich calcite and Ca-rich strontianite. A smaller scale intergrowth of calcite containing only 2.9 wt.% SrO and coexisting Ca-strontianite may correspond to a further unmixing at 350°C and 2 kbar. Since no experimental data are available for a calcite-carbocernaitestrontianite system, mineral chemistries and the interpreted sequence of crystallisation have been used to construct a hypothetical phase diagram.

Na-poor, Fe-bearing high sanidine from a lamproite near Cancarix (Spain) has 2Vα‖(010) = 37-43° and C2/m, a = 8.598(15), b = 13.050(26), c = 7.209(17) Å, β = 116.00(18)° V = 727(2) Å3. Rims of sanidine crystals against vugs contain up to 60 mole % KFeSi3O8 and up to 10 at.% Si and 6 at.% K above the stoichiometric requirement; otherwise, they have up to 4 mole % □Si4O8 and 3 mole % K2O.Si4O8 in solid solution. Their MgO content may reach 0.46 wt.%. The skeletons of mm sized blocky crystals (Baveno habit) indicate formation under moderate undercooling at temperatures not much above 725°C Feldspar formation was facilitated by a high diffusion rate due to low viscosity in a highly perpotassic melt, supersaturated by pressure release and diopside fractionation, upon extrusion of a huge volume of lava in a crater. After titanian potassium-richterite largely filled the interstices in the sanidine fabric, crystals of dalyite (K2ZrSi6O15) and Fe-rich rims of sanidine and amphibole crystals were formed from an increasingly hydrous, silicic, ferric, and peralkaline residual melt. High rate nonequilibrium crystallisation caused the incorporation of excess SiO2 and K2O in the defect structure of the sanidine. Retrograde boiling initiated the escape of volatiles, causing the quenching, by which the disordered structural state and the nonstoichiometric composition of the sanidine were preserved.

Musgravite, Be(MgFeZn)2Al6O12, is associated with norbergite and minor chlorite in a Precambrian calcite marble within the gneissic basement in an internal part of the Caledonian mobile belt in Dove Bugt, North-East Greenland. It commonly occurs as vitreous black, idioblastic crystals (<7 mm in size) with combined rhombohedral and basal pinacoid forms. XRD data show that its space group is R3m and its unit cell dimensions are a 5.687 ± 0.002 Å and c 41.16 ± 0.02 Å. Electron microprobe and ICP-MS analyses have yielded BeO 5.51 wt.% and ranges in abundance (wt.%): Al2O3 68.74-70.63; Tot, Fe as FeO 6.76-7.89; MgO 12.17-13.98; and ZnO 3.22-4.47. ICP-MS analysis also revealed significant trace amounts of V 249 ppm, Cr 740 ppm and Ga 178 ppm. The crystallographic parameters and composition are broadly in accord with those of musgravite from the two other recorded occurrences, in Precambrian high-grade terrains in Australia and Antarctica, although mineral and rock associations in these localities differ from those in Dove Bugt. The source of beryllium in each of the musgravite occurrences is uncertain, although a metasomatic source related to granite emplacement is favoured for the occurrence in North-East Greenland.

The structure refinement of a hastingsite (Cl 0.91 p.f .u.) from West Ongul Island, Ltitzow-Holm Bay, East Antarctica, has been carried out in order to characterise the effect of CI on the crystal structure. The composition of the Cl-rich hastingsite is K0.69Na0.26Ca1.99Mg1.09Fe2+2.71Fe3+0.92Mn0.04Ti0.10−Al2.31Si5.83O22OH0.99Cl0.91F0.10 with unit cell parameters a 9.962(3), b 18.283(7), c 5.572(1) Å and β 104.87(3)°.

In the Cl-rich hastingsite, A1, Fe3+ and Ti occupy only the M(2) site, and Fe2+ strongly prefers the M(1) and M(3) sites to the M(2) site with respect to Mg. The Mg-Fe2+ distribution suggests that the Mg-CI avoidance is realised in the intracrystalline exchange reaction among the octahedral sites in the Cl-rich hastingsite. The individual position of CI and OH was refined and the effective ionic radius of Cl in fourfold coordination is determined as 1.79 Å. Substitution of Cl for OH expands the sizes of the M(1) and M(3) sites and extends the double chains in comparison with hydroxy calcic amphiboles. Cl especially, is close to the 0(6) and 0(7) oxygens beyond the minimum distance calculated from effective ionic radii. Therefore, the Cl-rich hastingsite is considered to be deformed locally by Cl.

A partly destabilised Na-richterite has been found in an olivine-nephelinite from Morocco. The riehterite crystal (600 × 420 μm) is surrounded by a reaction zone (400-700 μm) of K- and Si-rich glass containing small (<50 μm) olivine (Fo80-83%) and endiopside crystals. Outwards, another zone is formed of normal magmatic minerals and circumscribes the original crystal, indicating that the destabilisation event took place at the end of the crystallisation sequence. Estimated ascent time of about 100 hours would have completely decomposed an isolated richterite crystal, which suggests that the amphibole was originally included in a xenolith. A mass-balance calculation shows that the fichterite isovolumic decomposition was accompanied by exchanges with the magma. The loss of Na from the reaction zone and the gain of AI from the magma allowed the precipitation of an analcime-rich zone observed around the destabilised amphibole and the concentration of K in the reaction zone glass. Compositional variations, Fe and Ti increase and Mg, Ca and F decrease at the richterite edge are interpreted as the result of a diffusion process. No alkali gradients are observed. The diffusion phenomenon lasted less than 100 hours and ceased to be operative at a temperature of 900-950°C i.e. just below the solidus temperature. Diffusion coefficients for the amphibole are proposed: e.g 10−9 cm2 s−1 for K2O and 10−10 for FeO at 900°C

Uranyl-silicates are widespread minerals in oxidised parts of various uranium deposits, and they frequently contain associations of the polymorphic forms of uranophane. In several recent works devoted to the study of uranium deposits as natural analogues of high-level nuclear waste repository (HLNWR), uranophane is frequently mentioned but without determination of the exact polymorphic species. The existence of two polymorphs presenting different stabilities has to be taken into account when considering the long-term behaviour of these minerals and the use of thermodynamic models for predicting the radionuclide migration in HLNWR. We present here new crystallographic data on betauranophane, and preliminary results of synthesis experiments of uranyl silicates. XRD patterns and calculated parameters of beta-uranophane from a Mexican U-deposit are presented. Synthesis experiments succeeded in crystallising uranophane (alpha form) at different pH, Si-, Ca- and Na activities, but beta-uranophane was never obtained. The controlling physico-chemical parameters responsible for the occurrence of these two polymorphic forms are still unknown.

The Or-rich part of optically blebby to lamellar mesoperthite crystals from an Adirondack granulite has been shown by TEM to be a lamellar cryptoperthite, composed dominantly of tweed orthoclase. A fluid-absent, two-stage thermal history is proposed to explain the coarse and fine textures, with the cryptoperthite forming by coherent exsolution below ∼350°C probably during uplift. The mechanism was most probably homogeneous coherent nucleation rather than spinodal decomposition. However, cutting the orthoclase cryptoperthite are thin (<1 μm) seams of tartan microcline with sharp boundaries, often defined locally by {110} planes, and micropores. The microcline has replaced orthoclase by solution-redeposition along narrow planes infiltrated by fluid during minor retrogression at T < 350°C Solution-redeposition is a common process in feldspars at T < 500°C potentially accompanied by 18O exchange, because release of elastic strain energy in coherent perthite lamellar boundaries and twin-domain walls, followed by Si, Al ordering, provide driving forces for dissolution and reprecipitation of unstrained, more ordered phases.

Gatehouseite is a new manganese hydroxy phosphate from Iron Monarch, South Australia. The new mineral occurs as radiating clusters of pale yellow, and yellow to pale brownish orange bladed crystals up to 100 ~tm in length. The crystals are elongated along [010] and the principal forms are {102}, {110} and {001}. Gatehouseite also occurs as overgrowths on prismatic arsenoclasite crystals. Associated with gatehouseite are baryte, shigaite, manganoan ferroan calcite, hausmannite and hematite. Gatehouseite appears to have formed at low temperature by the interaction of phosphorus-rich fluids on hausmannite in carbonate-rich fractures in the hematite ore. Electron microprobe analysis yielded: MnO 64.42, FeO 0.19, CuO 0.03, ZnO 0.03, PbO 0.05, Al2O3 0.10, P2O5 22.18, V2O5 0.38, As2O5 3.58, H2O (6.44%). These data gave an empirical formula of Mn5.09Fe0.01Al0.01(P1.75As0.17-V0.02)∑1.94O8(OH)4.00, calculated on the basis of 12 oxygen atoms. The simplified formula is Mn5(PO4)2(OH)4. The mineral is transparent with a pale yellow streak, an adamantine lustre and an estimated Mohs hardness of 4. The crystals exhibit a distinct cleavage on {010} and have a splintery fracture. The strongest lines in the X-ray powder pattern are (dobs, Iobs, hkl) 4.48 (10) (004); 4.03 (10) (104); 2.900 (100) (11.5); 2.853 (70) (106); 2.801 (50) (021); 2.702 (80) (303); 2.022 (15) (322); 1.608(15) (330). These data were indexed on an orthorhombic cell, with a = 9.097(2), b = 5.693(2), c = 18.002(10) Å and a volume of 932.4(8) Å3; the space group is probably P212121. For Z = 4 and using the empirical formula, the calculated density is 3.74 g/cm3. Optical properties could not be determined in full; two refractive indices are 1.74(1) and 1.76(1) (white light); pleochroism is distinct from brown to near colourless. The crystals are length slow with parallel extinction. The name is for Dr. Bryan Michael Kenneth Cummings Gatehouse (1932-), crystal chemist of Monash University, Melbourne, Australia.

Serpentinised ultramafic bodies containing zoned chromite grains occur in the Cordillera Frontal Range, western Argentina. Chromites show Zn-rich Al-chromite cores (4.04 wt.% ZnO) surrounded by ferritchromite rims (1.3 wt.% ZnO) and outer Cr-magnetite rims. In intensely altered chromites which are spatially related to sulphide mineralisation, the primary chromite cores have been replaced by Zn-rich ferritchromit (7 wt.% ZnO) and they are rimmed by Cr-magnetite. In the Al-chromites the mean [Cr/(Cr + Al] ratio is 0.53 and the [Mg/(Mg + Fe)] ratio is 0.53; they plot in the field of Alpinetype intrusions. Ferritchromit has a mean [Cr/(Cr + Al)] ratio of 0.93 and [Mg/(Mg + Fe)] ratio of 0.4. In Cr-magnetites the mean [Cr/(Cr + Al) is 0.98 and the [Mg/(Mg + Fe)] ratio is 0. Ferritchromit is always surrounded by a Cr-magnetite rim and it was formed as a reaction product owing to the irreversible dissolution of primary chromite cores. The dissolution of these cores provided the essential components for ferritchromit growth. Zn was introduced into the chromite cores and ferritchromit rims during the formation of the latter. Step-scan profiles have shown that the Zn content in the cores increases from the centre to their outer border, where they show the highest Zn values. It is suggested that Zn was introduced by the fluid phase involved in the alteration process that affected the cores and lead to the formation of the zoned chromite grains. This alteration process was also responsible for the changes in [Cr/(Cr + Al)] and [Mg/(Mg + Fe)] ratios.

The kinetics and reaction mechanisms of chlorite breakdown have been studied in a series of experiments at conditions similar to those achieved during contact metamorphism (T = 600-725°C P = 1 kbar). Cores of chlorite schist were used as starting material in order to simulate natural metamorphic systems and preserve reaction textures. Reaction products were analysed by electron microprobe, scanning- and transmission-electron microscopy (SEM, TEM). Although the texture of the original chlorite was preserved in experiments run below 680°C talc had replaced chlorite. Olivine and spinel formed along grain boundaries, indicating long-range diffusion of aluminium. Above 680°C the chlorite was replaced by patches of disordered, aluminous pyroxene. Olivine and spinel grew both within the pyroxene and along what are believed to be former chlorite grain-boundaries. Reactions relevant to the observed textures and assemblages are:

Thermodynamic calculations show that both of these reactions are metastable in the FeO-MgO-Al2O3-SiO2-H2O system in the P-T range of our experiments. In addition, previous experimental studies and our calculations indicate that the stable reaction is:

The absence of cordierite in the run products, and the formation of talc and orthopyroxene while thermodynamically metastable, show that the ease of nucleation of these phases controlled the reaction mechanisms in the early stages.

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 crystal structure of antimonian asbecasite in an ejectum of hypabyssal origin occurring at Tre Croci near Vetralla, Vico volcanic complex, Roman potassic province, Latium, Italy, has been refined to R = 0.042, and is compared to the original crystal structure determination carried out on the Sb-free asbecasite of hydrothermal metamorphic origin from the type-locality, Cherbandung in Binna valley, Monte Leone nappe, Switzerland. New electron microprobe analyses of samples from both localities demonstrate crystal-chemical features that permit distinction between asbecasites from the two occurrences, so far the only known localities for this mineral.

The crystal structure of KBSi3O8 (orthorhombic, Pnam, with a = 8.683(1), b = 9.253(1), c = 8.272(1) Å,, V = 664.4(1) Å3, Z = 4) has been determined by the direct method applied to 3- dimensional rcflection data. The structure of a microcrystal with the dimensions 20 × 29 × 37 μm was refined to an unweightcd residual of R = 0.031 using 386 non-zero structure amplitudes. KBSi3O8 adopts a structure essentially different from recdmergneritc NaBSi3O8, with the low albite (NaAlSi3O8) structure, and isotypic with danburite CaB2Si2Os which has the same topology as paracelsian BaAl2Si2O8. The chenfical relationship between this sample and danburitc gives insight into a new coupled substitution; K+ + Si4+ = Ca2+ + B3+ in the extraframework and tetrahedral sites. The present occupancy refinement revealed partial disordering of B and Si atoms which jointly reside in two kinds of general equivalent points, T(1) and T(2) sites. Thus the expanded crystal-chemical formula can be written in the form K(B0.44Si0.56)2(B0.06Si0.94)2O8

The systematic trend among crystalline compounds with the M+T3+T4+3O8 formula suggests that they exist in one of four structural types; the feldspar structures with T3+/T4+ ordered and/or disordered forms, and the paracelsian and the hollandite structures.

Twenty-four apatite (Ap) samples mainly from carbonatite and alkaline rocks were studied by electron microprobe, IR spectroscopy and X-ray powder diffraction. The crystal structures of six were refined using single crystal X-ray diffraction data to R = 1.7-2.5%. The generally high Si content of Ap from carbonatite and alkaline rock has been related to the presence of characteristic Si-O absorptions in IR spectra. Bands, whose intensities change with Si content, were observed at 520, 650, 930 and 1160 cm-1. The IR absorption features of v3 CO3 mode of Ap from carbonatite are different from those of v3 CO3 mode of Ap from sedimentary rock. This phenomenon is probably due to the different effects of F and OH on the CO3 substitution for PO4. The structural refinements yield more information on the CO3=PO4 substitution, which is now supported also by the geometrical evolution of the tetrahedron with increasing CO3 content: the tetrahedral size decreases and the angle distortion increases with C-content. It is likely that the triangular planar CO3 group is disordered on the four faces of PO43-tetrahedron. It was observed also that Ap from early-stage carbonatite is OH-dominant with considerable LREE, Si, CO3 and negligible Mn, Fe, Mg, K, S and C1 contents. They have high Sr/Mn, Si/S and C/S ratios.

The crystal structure of the rare lead hydroxychloride paralaurionite [PbCI(OH), monoclinic, space group C2/m, a = 10.865(4), b = 4.006(2), c = 7.233(3) Å, β = 117.24(4)°] has been refined to R = 0.062, Rw = 0.048. Its Order-Disorder (OD) character and its OD relationships with the orthorhombic polytpe of PbCI(OH), laurionite, are discussed. Laurionite and paralaurionite represent the two MDO structures within a family of OD structures built up by two different kinds of layers. The structures of paralaurionite and laurionite are compared thoroughly. The first coordination of the various atoms in the two polytypes is the same, however, remarkable differences exist in the connection between adjacent Pb-centred polyhedra.