Monazite-(Ce) from a dolomite carbonatite at Kangankunde, Malawi, is sector-zoned with variation in La2O3 of up to 6.0 wt.% and in Nd2O3 of up to 3.9 wt.% between sectors. Single crystal X-ray diffraction, backscattered electron imaging and microprobe analysis have been used to establish the relationship between the morphology and sector chemistry of this low-Th monazite, (Ce,La,Nd)PO4. Uptake of La by {011} sector surfaces is enhanced relative to that of and {100} sectors; Ce shows no partitioning differences; and uptake of Nd is more easily facilitated on and {100} surfaces relative to {011}. There appears to be a distinct relationship between the size of the REE ion and the probability of uptake via the different growth surfaces. Interpretation of this uptake behaviour, based on theories involving ‘protosites’, involves an investigation of the possible kink site geometries at edge-steps during growth. Part-formed kink sites with small entrance sizes are calculated to occur with higher frequency on relative to {011}, and this correlates with an increase in the smaller-sized REE (Nd) uptake by growth surfaces. The overall morphology and sector growth is suggested to be a function of uptake chemistry.

Cathodoluminescence (CL) microscopy and spectroscopy combined with SHRIMP ion probe measurements were carried out on detrital zircons from the Cretaceous Weferlingen quartz sand (Germany) to distinguish and characterize different zircon populations.

Investigations by CL microscopy, SEM-CL and BSE imaging show that there are three main types of zircons (general grain sizes of 100–200 µm): (1) apparently weakly zoned, rounded grains with relict cores, (2) well rounded fragments of optically more or less homogeneous zircon grains showing CL zoning predominantly parallel to the z-axis, and (3) idiomorphic to slightly rounded zircon grains typically showing oscillatory euhedral CL zoning. A fourth type of low abundance is characterized by well-rounded grain fragments with an irregular internal structure showing bright yellow CL.

High-resolution CL spectroscopic analyses reveal that blue CL is mainly caused by an intrinsic emission band centered near 430 nm. Dy3+ is the dominant activator element in all zircons, whereas Sm3+, Tb3+, Nd3+ have minor importance. Yellow CL (emission band between 500 and 700 nm) is probably caused by electron defects localized on the [SiO4] groups (e.g. related to oxygen vacancies) or activation by Yb2+ generated by radiation. Variations of the integral SEM-CL intensity are mainly controlled by the intensity of the broad bands and the Dy3+ peaks.

SHRIMP analysis provides in situ high-resolution U-Pb dating of single zircon grains and confirms different ages for the evaluated different zircon types. The measurements show that the U-Pb ages of the zircons from Weferlingen scatter over a wide range (340 to 1750 Ma), backing up earlier conclusions that the quartz sand from Weferlingen is quite heterogeneous in terms of provenance.

Primary almandine and spessartine-rich garnet and zinnwaldite phenocrysts occur along with feldspar (plagioclase and sanidine) phenocrysts, in the rhyolite of Profitis Ilias, which is located on the SE coast of the island of Chios, Greece. The distinctive mineralogical composition of this rhyolite is described. Although formed in the back-arc tectonic environment of the Aegean volcanic arc, the Profitis llias rhyolite shows significant trace element compositional differences when compared with typical arc or back-arc volcanic rocks of the area. It shows extreme depletion in Sr and Ba and enrichment in Nb and Mn, and has much more affinity with A-type granites and particularly Li-mica granites.

Apparently, both zinnwaldite and spessartine-rich garnet can be generated as primary phases from a granite melt enriched in volatile constituents at low P–T. This granite melt could be the residual product of an un-exposed, earlier formed, typical back-arc granite of the area, enriched in volatile constituents from a subcrustal source above the active mantle of the eastern Aegean area.

The extensive and deep faulting in the broad eastern Aegean lithosphere section would have facilitated the rapid ascent of that volatile-enriched granite melt, the parent of the Profitis Ilias rhyolite.

Otavite-calcite solid solutions have been synthesized to investigate the factors which control the patterns of compositional zoning. The equilibrium partitioning of otavite between the aqueous and the solid phase can be described by means of a function X CdCO3 (X Cd,aq)eq, which relates the solid mole fraction and the aqueous activity fraction of Cd. According to this function, there is a strong preferential partitioning of Cd towards the solid. A set of experiments starting with parent solutions with different Cd2+/Ca2+ ratios was carried out. In these experiments nucleation takes place at high supersaturations and the Cd2+ and Ca2+ ions tend to be laid down in a ratio which deviates from the equilibrium distribution. Experimental nucleation data can be fitted to a curve X CdCO3 (X Cd,aq)ef of the same functionality as that for equilibrium.

After nucleation, supersaturation decreases as the crystals grow. During this process, substituting ions are not incorporated into the solid in the same stoichiometric proportion as in the aqueous solution. Therefore, crystal and fluid compositions tend to vary as growth proceeds and this evolution is registered as a compositional zoning. The curves X CdCO3 (X Cd,aq)eq and X CdCO3 (X Cd,aq)ef confine the reaction path corresponding to the growth process. Here, these curves are used to account for the observed zoning patterns.

We have performed O self-diffusion experiments in synthetic diopside single crystals along the b-axis at temperatures ranging from 1473–1643 K, under controlled O partial pressure (10−11–10−2 atm). The 18O tracer diffusion was imposed by solid/gas exchange between 16O in diopside and 18O2-enriched argon-hydrogen-H2O gas mixture. Diffusion profiles of 18O were measured by Nuclear Reaction Analysis 18O (p,α) 15N. The diffusion coefficients are described by , with log D0(m2/s)=−9.2 ± 1.0 and E 310 ± 30 kJ/mol.

Our results are in agreement with Ryerson and McKeegan's (1994) data and Farver's (1989) data along a direction perpendicular to the c direction. Experiments performed in a wide pO2 range show that D is independent of pO2.

We observe no change in the diffusion regime up to 1643 K (i.e. 22 K prior to melting temperature). This result differs from the diffusion study of Ca in diopside by Dimanov and Ingrin (1995), where a strong enhancement of Ca mobility, attributed to an excess disorder in the Ca-sublattice, was observed above 1523 K. We conclude that O diffusion in diopside is not affected by this premelting phenomenon.

Ludwigite from B-bearing iron ores in the Bergslagen area of central Sweden and in the coastal area north of Stockholm has been studied using chemical and single-crystal diffraction techniques. Structure refinements, completed for three crystals showing slightly different Al contents, in the space group Pbam (agreement factor: 2.42 ≤ R ≤ 2.79) indicate that: (1) octahedral M1, M2 and M3 bond distances are similar, although the calculated site population suggests that M1 and M2 are nearly completely occupied by Mg whereas M3 also contains Fe2+ and Fe3+; (2) in the M4 octahedron Fe3+ and Al dominate over Mg (and Fe2+); and (3) the distortion parameter, BLD, indicates that M3 is the most regular, whereas M4 is the most distorted octahedron.

Secondary ion mass spectrometry (SIMS) techniques have been used to study the variation of C isotope ratio and N abundance within selected diamonds in relation to their crystal growth zones. The growth zones are seen in cathodoluminescence (CL), and include both octahedral and cuboid zones within typical diamonds of external octahedral morphology. Compositions were determined by use of a primary 133Cs+ ion beam and measurement of 12C−, 13C, and 12C14N− secondary ions at high mass resolution on a Cameca ims-4f ion microprobe at Edinburgh University.

In each of the diamonds, different growth zones have marked differences in N abundance, which are as great as 0–1400 ppm within one diamond. Changes of several hundred ppm N are common across both octahedral and cuboid growth zones, and appear sharp and abrupt at the boundaries of the growth zones. In general for the common blue CL, luminescence increases with N abundance. The changes in N abundance across fine scale (∼100 µm) growth zones show that the total N contents determined by IR spectroscopy may show great variations of abundance. In contrast, within detection limits, δ13C appears constant across many growth zone boundaries. Thus the factors controlling uptake of N from the fluid/melt reservoir in which natural diamonds grow often do not influence δ13C. No evidence of progressive variation or fractionation of C isotopes during growth was found.

Some original variation in C isotope composition may have been eliminated by diffusion of C atoms subsequent to growth, because of the storage of natural diamonds over millions of years in the Earth's mantle at temperatures of 950–1250°C. Such atomic mobility does not homogenize N distribution because of the proven tendency of N to form aggregates of atoms. A survey of experimental estimates of single atom (C) diffusion parameters, suggests that diffusion distances of ∼100 µm are likely at high temperatures (∼1100°C) over long time periods (∼1.0 Ga). Therefore, with refinement of the diffusion parameters and measurements, the extent of C isotope homogenization in natural diamonds, as well as N aggregation state, might provide quantitative evidence of their time-temperature history under mantle conditions.

The Coire Dhuinnid fault zone contains emerald green chromian illite-ankerite-quartz rocks that are similar in appearance to the fuchsite(or mariposite)-carbonate-quartz parageneses that are commonplace in Archaean greenstone belts but which are rather rare in Phanerozoic rocks. The chromian illite contains 2.3 wt.% Cr2O3, low K2O (7.1–7.6 wt.%) and high H2O+ (5.7 wt.%), and it is a 1M polytype with ≤10% of an illite/smectite interstratification indicative of a formation temperature of c. 175–200°C. The host rocks contain high concentrations of Ni and Cr, and show low concentrations of Ti, Nb, Y and Zr, suggesting a former primitive mafic protolith (boninitic magma?); they are considered to be retrograde remnants of Lewisian rocks. The latter, and the associated rocks of the Moine Series, have been affected by CO2 metasomatism that was accompanied by the addition of Ca(+Sr), Fe and Mg, and by the removal of Na from, and the addition of H2O to the Moine metasediments. Radiogenic isotope studies of mineral separates and whole rock from sample no. 43 yielded ages of 483±2 Ma (Ar-Ar dating on Cr illite), 413±12 Ma (K-Ar dating on Cr illite), and 322±9 Ma (Rb-Sr dating on minerals and whole rock); the significance of this discrepant pattern is discussed.

The cathodoluminescence (CL) characteristics of plagioclase phenocrysts in water-quenched lavas from the 1983 eruption of Etna have been investigated to examine the application of plagioclase CL to the study of magmatic processes. The phenocrysts have a green luminescent inner zone that is sharply bounded by a blue luminescent outer zone, with the boundary often coinciding with a concentric zone of glass inclusions.

Strong compositional differences between the green (An70–An75) and blue (An50–An60) luminescent areas are interpreted as the result of two phases of growth under differing conditions. The green luminescent cores are considered to be anorthite-rich cumulate crystals from a basic magma which have been disrupted by the injection of a more evolved melt, resulting in heterogeneous nucleation and crystallization of the outer blue luminescent zone. The relationship between the CL and the trace element contents of the plagioclase crystals is discussed.

Small (<2 km diameter), ultramafic intrusive complexes in the Andriamena region of Madagascar contain zones with disseminated chromite and sulphides which carry high concentrations of platinum-group elements (PGE). Assay of drill core from one complex, designated UM2, revealed three zones showing consistently high PGE grades. Mineralogical investigation of the UM2 core reveals that a small number of low reflecting, Pd-bearing platinum-group minerals (PGM) are present — always in association with a poorly characterized Pd stibio-arsenide [Pd3(Sb,As)] phase — in the shallowest of the three zones. Electron microprobe analysis of these PGM indicates the presence of oxygen and that at least two species exist. The resulting stoichiometries suggest that at least one species could be a hydrated form of palladinite [PdO.(H2O)n]. The other phase could be a hydroxide [Pd(OH)2] or a less strongly hydrated form of palladinite. Textural evidence suggests that the Pd-O species formed via the replacement of a precursor Pd-rich PGM, with only a limited removal of Pd, rather than via precipitation of a Pd-O PGM from a fluid that was Pd-bearing. The limited thermal stability of hydrated Pd oxides and the apparent restriction of the Pd-O phases to a shallow zone which is affected by the seasonal movement of groundwater, suggests that they may have formed at low temperatures via the leaching and replacement of other elements from a precursor Pd-rich PGM by oxygen and water during alternating water-saturated and dry conditions. If this is the case, the water table interface might be another environment, in addition to the surface, in which to look for the development of PGE oxides.

Loparite-(Ce) is a ubiquitous accessory mineral in modally diverse albite-rich metasomatic rocks of the Burpala alkaline complex, Siberia. Compositionally, the mineral approaches the ideal formula NaREETi2O6 (REE = Ce > La > Nd > Pr > Sm), and contains minor CaTiO3 (<4.8 mol.%), SrTiO3 (<4.7 mol.%) and NaNbO3 (<6.4 mol.%), The mineral is pseudocubic [a p = 3.8815(3) Å], and produces an XRD pattern similar to that of synthetic NaCeTi2O6 [Pnma, a = 5.4517(4), b = 7.7058(9), c = 5.4333(6) Å]. The atomic coordinates and isotropic thermal parameters of synthetic NaCeTi2O6 refined from an XRD powder pattern using the Rietveld method, are given. At Burpala, loparite precipitated from an alkaline REE-rich fluid during the metasomatic alteration of earlier-formed intrusive rocks. In some parageneses, loparite was replaced by ‘metaloparite’ during the final stages of metasomatism. ‘Metaloparite’ has the empirical formula REETi2O6-x (OH,F)x ·nH2O, and shows minor enrichment in Ca and depletion in Sr, compared to co-existing loparite. The formation of ‘metaloparite’ involved cation leaching, hydration and ion-exchange between loparite and a fluid. ‘Metaloparite’ is metamict at room temperature, but some samples regain the perovskite-type structure upon heating.

Several K-Fe sulphide minerals have been described from natrocarbonatite lavas erupted from the Tanzanian volcano Oldoinyo Lengai but uncertainty remains about their exact identity. They do not appear to be any of the established K-Fe sulphides according to Dawson et al. (1995) and Mitchell (1997). Here, we describe yet another variant which is a Mn- and F-bearing variety of rasvumite. It appears to have formed by reaction of Fe alabandite grains with natrocarbonatite magma and occurs as minute rims on the alabandite. Its formula is: (K0.94Na0.06)(Fe1.91Mn0.13Ca0.01Sr0.01)(S2.06F0.24Cl0.04).

Blueschist-facies metabasite rocks from the Tavşanlı Zone of northwest Turkey have been found to contain an abundance of lawsonite displaying oscillatory zoning. Lawsonite normally adheres to the ideal composition of CaAl2[Si2O7](OH)2.H2O. In two samples from the Tavşanlı Zone, Al3+-Cr3+ substitution has occurred. The Cr3+ was probably present in the protolith as magmatic chromite, became incorporated into lawsonite during subduction, and is a metamorphic feature resulting from quantities of Cr in the protolith and local fluid conditions.

Cobaltite-cemented pyrite framboids are reported from the base of the Kupferschiefer in the Lubin-Sieroszowice mining district in southern Poland. In the framboids, cobaltite occurs interstitial to the pyrite crystals. The cobaltite-cemented framboids are confined to within a few cm either side of the boundary between the Weissliegendes sandstone and the Kupferschiefer laminated organic-rich shales. Textural relations and distribution of the cobaltite is interpreted as indicating that the framboids acted as a site of preferred cobaltite precipitation and that the cobaltite precipitated in response to the changing chemical environment at the Weissliegendes/Kupferschiefer contact. It is proposed that the texture may have formed as a result of desorption of Co and/or As which had been adsorbed onto the monosulphide precursors to the framboidal pyrite. Desorption during the transition to pyrite resulted in cobaltite saturation within the framboid and subsequent precipitation. The source of the Co and As was probably oxyhydroxides which exist in the upper oxic part of the Weissliegendes.

Natural and synthetic scheelite are investigated by time-resolved laser-induced luminescence to detect and ascribe various luminescence lines to a variety of REE. The selectivity of detection is possible by using different time delays after excitation, different gate widths and different excitation wavenumbers and allowed to detect REE in samples where they are hidden by intrinsic luminescence and not visible in the steady-state spectra as well as by cathodoluminescenee. Luminescence of Pr3+, Er3+ and Tm3+ are detected even with low concentrations and in the presence of Tb3+, Dy3+ and Sm3+. Luminescence of Ho3+ and Yb3+ is firstly detected in natural scheelites and luminescence of Eu2+ and Ce3+ is preliminary suggested.

Diamonds from George Creek, Colorado, preserve complex intergrowth textures between two major growth generations: homogeneous diamond with yellow-buff cathodoluminescence (CL); and diamond with blue-green CL and local growth zonation. Secondary-ion mass spectrometry (SIMS) has revealed large variations in N concentration and C isotope composition within these diamonds. Even within single stones, N contents and δ13C values can vary from 0 to 750 ppm and 0 to −20‰ respectively. These variations are similar to those recorded elsewhere for entire diamond suites. The CL characteristics correlate directly with N: diamond with yellow-buff CL has uniform N contents, whereas the zoned diamond has bright blue CL bands with high N (50–750 ppm) and dark blue or green CL bands with low N (0–20 ppm). These bands are too narrow (10–5 µm) for analysis by IR spectroscopy. δ13C also varies between the two growth generations in any one diamond plate, and to a lesser extent within these generations, but shows no consistent correlations with either CL or N. The George Creek stones preserve evidence of extreme temporal and/or spatial variations in both δ13C and N concentrations during the period of diamond growth, but the factors controlling N content during diamond growth did not control δ13C.

Raman spectra of synthetic ‘braggite’ ((Pd,Pt,Ni)S) vary systematically with changes in Pt/Pd ratios, but this change is less pronounced than in ‘cooperite’ ((Pt,Pd,Ni)S). Compared to ‘vysotskite’ (ideally PdS), the incorporation of Pt leads to broadening of bands but the spectra of ‘vysotskite’ and ‘braggite’ are similar, and spectra of ‘cooperite’ and the ‘braggite/vysotskite’ solid-solution series are sufficiently different to facilitate distinction of these platinum group minerals by Raman spectroscopy.

Micro-FTIR (MFTIR) measurements were carried out on the natural recrystallized quartz in Ryoke granites from Mt. Takamiyama. The recrystallized quartz always shows a very strong IR absorption band at 3596 cm–1 (2.10 abs. cm–1 (normalized absorbance) under unpolarized conditions at room temperature). However, naturally deformed quartz does not show this absorption band, but only a characteristic broad band centred at 3400 cm–1. This shows that the predominant forms of H-related species in the recrystallized quartz are different from those in naturally deformed quartz. The 3596 cm–1 band is not affected by room-temperature X-ray irradiation or by annealing at temperatures of up to 600°C, and shows broadening and a positive peak shift with temperature in in situ high temperature measurements. Polarized-MFTIR measurement shows that the band has a strong polarization; the OH dipole is oriented at 35° to the a-axis in the plane and is isotropically distributed in the (0001) plane. From the stability of the band at high temperatures and against irradiation and its sharpness, the band is considered to be due to the Al(H) type point defect with no alkali which might occupy a structural position in the quartz structure.

The hydroxy-sulphide yushkinite from the type deposit has been re-examined by electron probe microanalysis and reflectance measurement. The EPMA indicates minor Cu (up to 1.5 wt.%) and confirms an excess of V. Taking into account its composite structure (brucite-like hydroxide layer alternating with a berndtite-type sulphide layer) the proposed structural formula is, with the addition of minor intercalated Cu: [(Mg0.71Al0.36V0.03)Σ1.10(OH)2.18O0.02]Cu0.02 [VS2]. At the crystal scale, some crystal edges give a variable excess of Si and Al (in the 1/1 ratio), indicating a late topotactic intergrowth with a layered alumino-silicate (or a composite silicate-sulphide). New specular reflectance data are given in air and oil from 400 to 800 nm, with the polarization plane parallel or perpendicular to the elongation. The refractive index n and absorption coefficient k are given; no absorption band exists in the perpendicular position, with constant n close to 1.9, and k to 0.3. In a parallel position, a pseudo-transparency window is centred around 500–520 nm (∼2.4 eV). The main absorption band, centred around 730 nm (∼1.7 eV), corresponds probably to a transition t2g → eg related to intra-layer V-V bonding. Charge transfer from the brucite-type layer to the VS2 one, strictly controlled through H-bonding, induces a mean formal valency of V close to 3.6. Yushkinite is compared with other synthetic layered hydroxy-sulphides, as well as brucite-type intercalated compounds.

A major disadvantage of the electron microprobe is its inability to determine Li, which may make up an essential component in micaceous minerals. Correct classification of micas and proper calculation of their formulae require alternative methods. One of these is the indirect estimation of the lithium concentration by empirical approaches based on element correlations. Relationships between Li2O and SiO2 have long been used for this purpose; however, they are valid only for a limited range of mica compositions (i.e. Li-rich, Mg-poor varieties).

In this paper we report the results from a renewed study of the correlation between Li2O and MgO contents in trioctahedral micas. It is demonstrated that the relations between both oxides are strongly dependent upon the geological environment in which the mica was formed. It is necessary to distinguish a ‘normal group’, which comprises micas from ‘common’ S- and I-type magmatic rocks and most metamorphic rocks , a ‘low Li-Mg group’, to which belong Fe-rich micas from non-alkaline rocks of A-type affinity, and a ‘high Li-Mg group’ which includes micas from either peraluminous or peralkaline igneous rocks and Mg-enriched wall-rocks. These wall rocks supplied additional magnesium to the mica-forming environment. We offer empirical expressions relating Li2O and MgO contents for these three types which, in many cases, allow a sufficiently good estimation of the lithium content in trioctahedral micas of widely varying compositions.