Electron microprobe analyses of almandine-spessartine garnets from pegmatites and aplites from the Hub Kapong batholith and Phuket Island in peninsular Thailand show three types of zoning. Garnets from pegmatites show extreme zoning, with Mn-rich cores (⋍ 80 % spessartine) and Mn-poor rims (⩾ 40 % spessartine), whereas those from aplites are either unzoned (35–40% spessartine) within the limits of detection, or have Mn-enriched rims (cores 45 %, rims 55 % spessartine). The origin of the three types of zoning is considered to reflect different crystal growth histories in each case. The pegmatitic garnets grew under conditions favourable for the development and preservation of marked concentration gradients—low nucleation density, rapid growth rate and slow cation diffusion rates for the crystal and rapid diffusion rates for the pegmatitic liquid. The aplitic garnets had a more complex growth history, with slower growth rates and faster diffusion rates for the crystal, coupled with slower diffusion rates within the aplite magma, tending to prevent the formation and preservation of concentration gradients. Subsequent resorption of aplitic garnets at lower temperatures gave rise to Mn-rich rims because of the preferential retention of Mn by the garnet; lower cation diffusion rates within the crystal permitted these marginal concentration gradients to be preserved.

The compositions of feldspar pairs crystallized from stoichiometric alkali feldspar gels with water at PH2O ≈ 1 kbar in runs of up to 3000 hours' duration vary with Na:K in the starting material. This is because, for most bulk compositions, rapid nucleation in the gel leads to growth of one feldspar phase outside the solvus. The composition of this initial feldspar phase can be thought of as reflecting the configuration of the liquidus-solidus curves in the system Ab-Or. In general, the attainment of the stable equilibrium solvus (binodal) requires that one phase approach the binodal from outside; for compositions with < 30 mole % Or this phase becomes more potassic with time, with > 30 mole % Or, more sodic. Homogeneous gels of bulk composition Ab70Or30 initially crystallize feldspar pairs inside the binodal, which rapidly (< 17 hours) unmix to define a solvus-like curve (probably the spinodal, with an apparent critical point at 602 °C and 31 mole % Or) and then unmix slowly, giving a solvus after 3000 hours with a critical point at 657 °C and 36 mole % Or.

Because this curve has been approached from two directions it is the best approximation to the binodal (metastable only with respect to Al-Si order) obtained. It is similar to the 2 kbar ‘peralkaline’ solvus of Orville, 1963, provided an adjustment for pressure of 16 °C/kbar is made. Differences between solvi determined by Luth and Tuttle (1966) for ‘non-stoichiometric’ bulk compositions may reflect differences in initial crystallization behaviour, as may the breaks in the solvus limbs suggested by Luth et al. (1974).

The maghemitization process, by which magnetic minerals with spinel structure become progressively oxidized but remain single phase spinels, seems to be an important feature of submarine weathering. Whether the process takes place by the minerals acquiring oxygen from the sea-water or by the sea-water leaching out iron, the controlling process is the diffusion of Fe2+ in the spinel structure. Magnetic studies have suggested that during maghemitization the availability for oxidation of Fe2+ in the tetrahedral (A) sites of the spinel structure is much less than that in octahedral (B) sites. In this study the Fe2+-containing spinels FeAl2O4, FeCr2O4, FeGa2O4, and Fe2GeO4, in which Fe2+ is predominantly in either A or B sites were prepared, and the diffusion of Fe2+ was studied by (1) interdiffusion experiments with the Mg2+ counterparts and (2) oxidation experiments in air. Fe2GeO4 (Fe2+ in B sites) was found to be associated with a higher interdiffusion coefficient and lower activation energy than FeAl2O4 (75% Fe2+ in A sites). Oxidation/diffusion activation energies of 0.27 and 0.71 eV were assigned to Fe2+ in B and A sites respectively. The experiments thus provide support for the maghemitization model in which Fe2+ in B sites is preferentially oxidized.

The modern analytical SEM, which can provide high-quality imaging facilities together with quantitative elemental analysis using an energy-dispersive spectrometer, is finding wide application in the investigation of archaeological problems. Many of these investigations involve the study of silicate and carbonate-based artefacts which may be relatively unmodified from their original geological parent raw materials so that mineralogically based interpretations are often appropriate. In this paper we present a series of examples illustrating the role of the analytical SEM in the mineralogical investigation of archaeological problems, including the characterization and provenancing of geological raw materials, the elucidation of the processes used to transform those raw materials into useful objects and the recognition and characterization of changes which archaeological artefacts may have undergone during burial or during storage.

Lithium mineralization is common in the Central Iberian Zone and, to a lesser extent, in the Galizia-Trás-OsMontes Zone of Spain and Portugal, occurring along a ∼500 km-long NNW-SSE striking belt. There are different styles of Li mineralization along this belt; they are mainly associated with aplite-pegmatite bodies and, to a much lesser extent, with veins of quartz and phosphate. Lithium mineralization in the Central Iberian Zone may be classified into four types: aplite-pegmatite dykes occurring in pegmatitic fields, Li mineralization associated with leucogranitic cupolas, beryl-phosphate pegmatites and quartz-montebrasite veins. The main Li minerals of these bodies include Li-mica, spodumene and/or petalite in the pegmatitic fields and leucogranitic cupolas; triphylite–lithiophilite in the beryl-phosphate pegmatites, and amblygonite–montebrasite in the quartz-montebrasite veins. The origin of these different styles of mineralization is considered to be related to differentiation of peraluminous melts, which were generated by partial melting of metasedimentary rocks during the Variscan orogeny. On the basis of paragenesis and chemical composition, the pegmatitic fields and Li mineralization associated with granitic cupolas record the highest fractionation levels, whereas the beryl-phosphate pegmatites and quartz-montebrasite veins show lower degrees of fractionation. There are a number of textural and mineralogical indicators for Li exploration in the Central Iberian Zone and in the Galizia-Trás-Os-Montes Zone, with the highest economic potential for Li being in the pegmatite fields.

Mafic lamprophyre dykes in northern England were emplaced soon after the final closure of the Iapetus Ocean at the end of the Caledonian orogeny. High Mg/(Mg+Fe) ratios and Cr and Ni contents are consistent with equilibrium with mantle peridotite. Incompatible trace element abundances suggest that the mantle sources were metasomatized prior to the melting events. Three components are recognized in the lamprophyre chemistry: (i) a depleted mantle source, taken to be that overlying the subducting lithosphere; (ii) a H2O-rich subduction zone component, related to the dehydration of the subducting oceanic crust; and (iii) a CO2-rich phase thought to result from the degassing of the mantle after ocean closure. This multi-component origin may be applicable to other lamprophyres of calc-alkaline affinity.

By measuring the integrated line intensity on a Philips' X-ray diffractometer in place of the peak intensity and by paying due regard to the ease with which aragonite converts to calcite during cleaning and grinding operations, the proportion of calcite and aragonite in a pure calcium carbonate shell can be determined to within 1% of the total in less than 30 minutes.

The understanding of biogeochemical processes at the interface between geosphere, hydrosphere and biosphere is of paramount importance for many questions related to global climate and environmental change at very different time and spatial scales. In addition, soils are the principal resource for food production and the understanding of soil formation processes and biological interactions within soils is indispensable for the development of sustainable land-use strategies. In this contribution we present a research initiative, the multidisciplinary ‘BigLink’ Project, aiming at a better understanding of the links between weathering, soil formation and ecosystem evolution and how these biosphere-geosphere interactions are influenced (and themselves influence) climate and environmental change.

A natural Mg-Al-Fe spinel from the Balmuccia peridotite (Italian Western Alps) was annealed at T between 650 and 1150°C, under controlled oxygen activity, and quenched in H2O. Twenty-three cation distributions were calculated from XRD structural refinements in tandem with microprobe analysis, and verified by Mössbauer spectroscopy in the case of unheated samples.

Unheated crystals showed essentially ordered distribution of Fe3+ in octahedral and Fe2+ in tetrahedral sites, the only intracrystalline disorder being represented by ∼0.12 atoms per formula unit of [4]Al and [6]Mg. Thermal runs and quenching maintained substantially ordered distribution of Fe2+ and Fe3+ up to ∼990°C and produced continuous [4]Mg-[6]Al exchange. Between 990 and 1150°C, the previous order of Fe2+-Fe3+ appeared to change slightly, [6]Fe2+ reaching ∼0.04 afu and [6]Mg ≅ [4]Al ≅ 0.24 afu at the highest T. After quenching from this temperature, Fe2+ still resided mainly in the T site. Some previously heated crystals underwent reordering on lowering of the temperature.

Experimental data, integrated with existing literature, enabled cation-oxygen distance in this structure to be improved. Results from annealed samples allowed the formulation of an experimental thermometric function based on Mg-Al intracrystalline disorder.

X-ray powder methods have been used to study the room-temperature structures of the synthetic sodalites: Li8(Al6Si6O24)Cl2, K7.6Na0.4(Al6Si6O24)Cl2, and Na8(Al6Si6O24)I2. Natural sodalite was also studied and the atomic coordinates show satisfactory agreement with those determined from the single-crystal data of Löns and Schulz (1967). The LiCl- and KCl- as well as the NaCl-sodalites refined in the expected sodalite space group P3n, but the NaI-sodalite fitted 13m better. The resulting structural data reveal shortcomings in the previous computer models for sodalite structures and an improved computer modelling procedure is devised which successfully predicts atomic coordinates, starting from the experimental a value and an estimate of the cationanion distance. The method incorporates the experimental result that the average T-O distance (T = Al, Si) throughout the samples is ∼ 1.678 Å, and Si-O and Al-O are set at 1.618 and 1.738 Å, respectively. Although T-O remains little changed throughout the samples, the data confirm the inverse relationship between ∠ T-O-T and the tetrahedron tilt angle ϕ, in which ∠ T-O-T approaches ∼ 160° as ϕ → 0° and the sodalite cage becomes fully expanded.

Free energies of formation of liebigite, Ca2UO2 (Co3)3·10H2O, swartzite, CaMgUO2(Co3)3·12H2O, bayleyite, Mg2UO2(CO3)3·18H2O, and andersonite, Na2CaUO2(CO3)3·6H2O have been determined from solution studies at various temperatures. ΔGf(298.2K)° values for the above minerals are −6226±12, −6607±8, −7924±8 and −5651±24 KJ mol−1 respectively. ΔH0f(298.2K) values respectively are −7037±24, −7535±20, −9192±20, and −5916±36 kJ mol−1. These results have been used to construct the stability diagram for the four minerals shown in fig. I. Andersonite can only form when the activity of the sodium ion, aNa+, is relatively high and aCa2+ and aMg2+ are small. The interconversions of the sodium-free species are defined. When aMg2+/aCa2+ < 0.32 liebigite is the stable phase. If aMg2+/aCa2+ > 7.94, bayleyite forms preferentially. One might therefore expect the bayleyite-andersonite association to be more common than liebigite-andersonite, but this is entirely dependent upon the relative concentrations of Mg2+(aq) and Ca2+(aq) in the solutions from which the minerals form.

A modification of the rules for the cMeulation of C.I.P.W. norms when no normative quartz is present is suggested.

Pyrochlore group minerals have the general formula A16–xB16O48Z8–y·nH2O, with A mainly Na, Ca, Sr, REE, Th, U; B mainly Nb, Ta, Ti and Z being O, F, OH. In this study, pyrochlore specimens were examined from carbonatites at Argor, Carillon Dam, Chilwa Island, Fen, Lueshe, Oka, Mbeya, Meech Lake and Verity. Primary features include a background with little compositional variation, from core to rim, upon which are commonly superimposed narrow oscillatory zones, parallel to {111}. These zones are usually characterized by high Ta, in many cases coupled with U (here Argor, Meech Lake and Verity specimens), but Chilwa Island and Fen pyrochlores have little Ta and zonation is mainly by enrichment in Ce and Nb. Primary zonation may persist through high-temperature metamorphism (Meech Lake and Verity) and metamictization (Meech Lake). Oscillatory zones were generated by a disequilibrium system that cooled under tranquil conditions, signalling absence of magma turbulence and, in many cases, the end of crystal growth. Some fresh crystals (Oka, Fen) have no oscillatory zones, possibly the product of magma turbulence in space or time. Low-temperature effects may mimic those of primary high temperature and are especially characterized by replacement rims, pyrochlore-inpyrochlore veinlets and low A-ion totals (Carillon Dam, Lueshe, Myeba).

Lodran is a unique meteorite consisting of roughly equal amounts of metal, olivine, and pyroxene with minor amounts of sulphide, chromite, phosphide, chrome-diopside, and a new phase with a composition close to (K,Na)AlSi5O12. Zähringer reported planetary-type rare gases in both the metal and silicates, suggesting a primitive nature. The pyroxene composition is Fs13.8 with little variation. Olivine composition averages Fa12.6, but varies at least ±20 % both among grains and zoned within single grains; only the Fe-rich olivine is in equilibrium with the pyroxene. The metal probably cooled rapidly (700 K/Myr) at high temperatures and slower (30 K/Myr) at lower temperatures. Two compositional populations of chromite are found.

A model for the formation of Lodran includes three steps: Formation of large olivine, pyroxene, and metal grains, with the trapping of small olivine inclusions in pyroxene and pyroxene in olivine. Equilibration and recrystallization of olivine, pyroxene, and metal, loss of alkalis and Ca; this probably occurred in a parent-body setting. And incorporation of reducing materials and mild reheating sufficient to produce the zoning in the olivine but not enough to re-equilibrate the pyroxene.

Phase compositions and rare-gas concentrations in ureilites are similar to those in Lodran. In some respects Lodran appears to be a metal-rich ureilite, but the higher Fe/(Fe+Mg) ratios in the latter (Fa 21 olivine) suggest origin on separate parent bodies.

The Harvard University meteorite is a mesosiderite and not closely related to Lodran.

The rock association of minette with silicic lavas and intrusions (granites, syenites, dacites) is a common geologic feature in both collisional and extensional tectonic settings. Considerable doubt exists as to whether a genetic link exists between these mafic and silicic rocks. We describe a Miocene sill from NW Colorado which is a clear example of a mixed magma consisting of originally-liquid inclusions of minette in a silicic trachydacite host. Chemical and Sr, Nd and Pb isotopic data are consistent with derivation of the silicic host magma of the sill dominantly by fractional crystallization of the minette magma. Correlations between the elemental compositions of the rock types and their Sr and Nd isotopic ratios imply minor assimilation of continental crust with relatively low values of both 87Sr/86Sr and 143Nd/144Nd, concomitantly with fractional crystallization. The parental minette magma was probably derived by partial melting of subcontinental lithospheric mantle. While the sill was emplaced in a rift-like tectonic setting, the chemical and isotopic composition of the lithosphere-derived minette magmas (and hence the silicic fractionates) was largely independent of this setting, but dependent upon the composition and age of the lithospheric mantle and crust.

The solubility and incorporation mechanisms of H and various trivalent and divalent cations in synthetic rutile have been investigated. Experiments performed using different bulk Fe2O3 contents demonstrate that Fe3+ substitutes onto the main Ti site, charge-balanced by oxygen vacancies. Under more reducing conditions in Fe-poor systems, the concentration of Ti interstitials in rutile is increased, resulting in a decrease in H solubility. Variation in the solubility of different oxides in rutile as a function of ionic radius implies substitution onto the main Ti site, probably charge-balanced by oxygen vacancies. To a lesser degree, substitution of trivalent and divalent cations is locally charge-balanced by H incorporation. Variation in OH-stretching frequencies in infrared spectra as a function of composition implies that octahedral defects and structurally-incorporated H are coupled. However, in all samples, some of the H is also decoupled from substitutional impurities, as is evident from an OH-absorption band at 3279 cm–1. This band corresponds to the main OH band seen in spectra of many natural rutiles, implying that in most rutiles, H defects are decoupled from substitutional defects.

Otoliths, the earbones of teleost (bony) fish, are constructed from alternating layers of aragonite and protein. Laser ablation inductively coupled plasma mass spectrometry and proton-induced X-ray emission are used to obtain spatially well-resolved trace element line-scans that show trace-element concentrations are correlated with the annular structure. Zoned Sr and Zn signatures are common whereas other elements such as Cu, Pb, Li and Cs can be related to the proximity of mineral deposits. Aragonite in otoliths can incorporate a wide range of trace elements at the low-ppm level including alkali- and alkaline-earth elements and base metals; Se has also been detected in proximity to coal mines. These trace elements, in combination with the annular structures, are an important archive for recording information on environments occupied by fish, environmental change and exposure to pollutants.

The layered agpaitic nepheline syenites (kakortokites) of the Ilímaussaq complex, South Greenland, host voluminous accumulations of eudialyte-group minerals (EGM). These complex Na-Ca-zirconosilicates contain economically attractive levels of Zr, Nb and rare-earth elements (REE), but have commonly undergone extensive autometasomatic/hydrothermal alteration to a variety of secondary mineral assemblages. Three EGM alteration assemblages are recognized, characterized by the secondary zirconosilicates catapleiite, zircon and gittinsite. Theoretical petrogenetic grid models are constructed to assess mineral stabilities in terms of component activities in the late-stage melts and fluids. Widespread alteration of EGM to catapleiite records an overall increase in water activity, and reflects interaction of EGM with late-magmatic Na-, Cl- and F-rich aqueous fluids at the final stages of kakortokite crystallization. Localized alteration of EGM and catapleiite to the rare Ca-Zr silicate gittinsite, previously unidentified at Ilímaussaq, requires an increase in CaO activity and suggests post-magmatic interaction with Ca-Sr bearing aqueous fluids. The pseudomorphic replacement of EGM in the kakortokites was not found to be associated with significant remobilization of the primary Zr, Nb and REE mineralization, regardless of the high concentrations of potential transporting ligands such as F and Cl. We infer that the immobile behaviour essentially reflects the neutral to basic character of the late-magmatic fluids, in which REE-F compounds are insoluble and remobilization of REE as Cl complexes is inhibited by precipitation of nacareniobsite-(Ce) and various Ca-REE silicates. A subsequent decrease in F– activity would furthermore restrict the mobility of Zr as hydroxyl-fluoride complexes, and promote precipitation of the secondary zirconosilicates within the confines of the replaced EGM domains.

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 structures of synthetic 7 Å and 10 Å manganates, synthetic birnessite and buserite, substituted by mono- and divalent cations were investigated by X-ray and electron diffractions. The monoclinic unit cell parameters of the subcell of lithium 7 Å manganate, which is one of the best ordered manganates, were obtained by computing the X-ray powder diffraction data: a = 5.152 Å, b = 2.845 Å, c = 7.196 Å, β = 103.08°. On the basis of the indices obtained by computing the X-ray diffraction data of Li 7 Å manganate, monovalent Na, K and Cs and divalent Be, Sr and Ba 7 Å manganates were interpreted as the same monoclinic structure with β = 100–103° as that of Li 7 Å manganate, from their X-ray diffraction data. In addition, divalent Mg, Ca and Ni 10 Å manganates were also interpreted as the same monoclinic crystal system with β = 90–94° The unit cell parameters, especially a, c and β, change possibly with the type of substituent cation probably because of the different ionic radius, hydration energy and molar ratio of substituent cation to manganese. However, these diffraction data, except for those of Sr and Ba 7 Å and Ca and Ni 10 Å manganates, reveal only some parts of the host manganese structure with the edge-shared [MnO6] octahedral layer. On the other hand, one of the superlattice reflections observed in the electron diffractions was found in the X-ray diffraction lines for heavier divalent cations Sr and Ba 7 Å and Ca and Ni 10 Å manganates. The reflection presumably results from the substituent cation position in the interlayer which is associated with the vacancies in the edge-shared [MnO6] layer and indicates that the essential vacancies are linearly arranged parallel to the b-axis. Furthermore, the characteristic superlattice reflection patterns for several cations, Li, Mg, Ca, Sr, Ba and Ni, manganates were interpreted that the substituent cations are regularly distributed in the interlayer according to the exchange percentage of substituent cation to Na+. In contrast, the streaking in the a-direction observed strongly in the electron diffractions for heavier monovalent cations, K and Cs, manganates probably results from the disordering of their cations in the a-direction in the interlayer.