The high-pressure behaviour (up to 30 kbar) of dehydrated analcime, Na[AlSi2O6), has been studied in detail using polarized microscopy and Raman micro-spectroscopy. Samples were compressed using a diamond anvil cell in a quasi-hydrostatic medium (glycerol or water-ice). Two transitions at 3.7 and 11 kbar were observed.

At the first transition, phase II is observed under cross polarized light as a contrasting black zone, moving from the edge to the centre of the sample. At this transition the strong Raman doublet at ∼480 and 500 cm−1 transforms discontinuously to a singlet, which is similar to that of quasi-cubic natural analcime. This transition, with an increase of effective symmetry, seems unusual on increasing pressure.

The analcime framework may be thought of as an array of four-, six-, or eight-membered interconnected rings. Phase transitions in the analcime group are considered in the literature in terms of deformations of the six-membered rings. However, the present work shows that these phase transitions should be associated with deformations of the four-membered rings (as the minimum size secondary building units) by rotation of rigid TO4 units. The strongest Raman band frequency is correlated with the mean T-O-T angle inside the four-membered ring: a rate of 4.5 cm−1/degree was found for analcimes and leucites. Using this correlation, one can estimate from Raman data the possible deformation of four-membered rings at the phase transitions.

The Pandé massif is a small (4.9×63.4 km) subvolcanic complex of the Cameroon Line striking W – E and intrudes a Panafrican granite basement. It comprises a syenite-granite suite, where coarse- to finegrained syenites are predominant and the granites are the product of residual melt after syenite crystallization, and two volcanic (trachyte-rhyolite and trachyte) sequences. Amphibole and pyroxene are the dominant mafic silicates, the first occurring mainly in rhyolites and coarse- to medium-grained syenites, and the second, principally in all syenites, trachytes and granites. Rare biotite flakes are encountered in the coarse-grained or alkaline syenites and fayalite rimmed with oxides occurs in trachyte from the first volcanic sequence (T1). Apatite and zircon are common accessories, whereas some titanite occurs in the medium-grained syenites. The plutonic rocks are drusy, intrude the first volcanic sequence but pre-date the second (T2).

All the mafic minerals are Fe-rich. Detailed studies of amphibole and pyroxene show that their compositions define relatively limited trends, amphibole varying from ferro-richterite to arfvedsonite and pyroxenes along the acmite-hedenbergite join of the Ac-Hd-Di diagram, in both the intrusive suite and volcanic rocks. Where the two minerals coexist, pyroxene crystallized subsequent to amphibole, a situation generally found in late-stage or subsolidus aegirines. The overlap in plutonic and volcanic pyroxene trends suggests their crystallization from magmas of the same composition. However, the presence of quartz and fayalite in T1 and of pure aegirine in T2 and the occurrence of Zr-bearing aegirine (NaZr0.5Fe0.52+Si2O6) in the early crystallizing alkaline syenites evolving towards pure aegirine from medium- to fine-grained quartz syenites and granites, are consistent with changes in oxygen fugacities during magmatic differentiation. Two stages are distinguished: fO2 increasingly decreased from T1 to alkaline syenite emplacement (from 10−16 to 10−24 bracketed by WM and QFM buffers) where a disequilibrium, probably caused by water dissociation with volatile loss (H2) during magma degassing, favoured crystallization of Zr-bearing aegirine; a decrease in amphibole proportions towards medium-grained quartz syenites and an increase in fO2 from the medium-grained quartz syenites to granites and T2 sequence.

The Mg-poor nature of all the mafic silicates, subsolidus origin of amphiboles, crystallization of pyroxene subsequent to amphibole and subsolidus trends defined by pyroxenes are compatible with the parental magma having itself been a late-stage derivative magma, e.g. the last product of an alkaline melt from which the voluminous Mayo Darlé granite bodies crystallized.

Troilite is a sulfide that occurs commonly in meteorites. In the laboratory, it can be synthesized by gas-solid reaction of metallic Fe and H2S-H2 gas mixtures. In this research, the arc-discharge method was used to synthesize troilite. The resulting spherules are up to 2–3 mm in diameter and composed of troilite, pyrrhotite and metallic Fe. Nanometer-sized hollow carbon fibres and balls occur on the surface of the spherules. The features and coexisting relationships of the constituents of the spherules were studied by X-ray diffraction (XRD), energy-dispersive X-ray spectrometry (EDS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the phenomenon of transformation of pyrite (FeS2) into pyrrhotite (Fe1-xS), troilite (FeS) and metallic Fe under arc-discharge reducing conditions were examined.

Rappoldite, the Co-analogue of helmutwinklerite, and zincgartrellite, the Zn-dominant analogue of gartrellite, are two new members of the tsumcorite group. Both minerals are triclinic, their structures are closely related to the parent structure, i.e. the ‘tsumcorite type’ (C2/m, Z = 2). The lower symmetry is caused by two different crystal-chemical requirements. Order phenomena of the hydrogen bonds cause the ‘helmutwinklerite type’ (P1̄, Z= 4), ordering of Cu2+and Fe3+ is responsible for the ‘gartrellite type’ (P1̄, Z = 1).

Rappoldite was found on samples from the Rappold mine near Schneeberg, Saxony, Germany. The new species forms red to red-brown prismatic and tabular crystals up to 1 mm long. Dcalc. = 5.28 g/cm3. 2Vz = 85(5)°, nx = 1.85 (calc.), ny = 1.87(2) and nz = 1.90(2); dispersion is distinct with r > v; orientation is Y ∼∥ [1̄ 20] and X ∼ ∥ c. The empirical formula derived from electron microprobe analyses is (Pb1.01Ca0.01)Σ1.02(Co0.99Ni0.62Zn0.35Fe0.02)Σ1.98[(AsO4)1.99(SO4)0.01]Σ2.00[(OH)0.02(H2O)1.98]Σ2.00 or Pb(Co,Ni)2(AsO4)2·2H2O. Single-crystal X-ray studies showed average C2/m symmetry. Weak superstructure reflections are responsible for triclinic symmetry and enlarged cell metrics (refined from powder data): a= 11.190(2)Å, b= 10.548(2)Å, c= 7.593(1)Å, α = 100.38(1)8, β = 109.59(2)8, γ = 98.96(1)8, V= 807.6 Å3, Z= 4. The superstructure results from the hydrogen-bond scheme, but faint streaks indicate some disorder. All investigated rappoldite crystals are twinned by reflection on (23̄0) which corresponds to the mirror plane of the average C2/m cell. Helmutwinklerite is isotypic with rappoldite and probably also with pure thometzekite; sulphatian thometzekite is monoclinic.

Zincgartrellite forms green-yellow rosette-like aggregates on samples from the Tsumeb mine, Namibia. The Dcalc. = 5.30 g/cm3. 2Vx = 87(5)°, nx = 1.91(2), ny = 1.94 (calc.) and nz = 1.97(2). Electron-microprobe analyses and Mössbauer data yielded the empirical formula (Pb0.97Ca0.04)Σ1.01(Zn0.91Cu0.51Fe0.59Al0.03)Σ2.04[(AsO4)1.96(SO4)0.01]Σ1.97[(OH)0.81(H2O)1.31]Σ2.12 or Pb(Zn,Fe,Cu)2(AsO4)2(H2O,OH)2. The structural formula is Pb(ZnxFe1–x)(ZnxCu1–x)(AsO4)2(OH)1–x(H2O)1+xwith 0.4 < x < 0.8. Gartrellite is defined by x < 0.4. Helmutwinklerite has x near to 1 and is defined by a cell with fourfold volume. Single-crystal X-ray studies of zincgartrellite proved space group P1̄ caused by ordering of Fe3+ and Cu at one atomic site. Cell parameters (refined from powder data): a= 5.550(1)Å, b= 5.620(1)Å, c= 7.621(1)Å, α = 68.59(1), β = 69.17(1), γ = 69.51(1)°, V= 200.1 Å3, Z= 1.

Ion probe data are documented for zircons from tuffs within the early Llandovery, the mid-Caradoc and the Ludlow. 206Pb/238U ages for tuff magmatism have been interpreted using mixture-modelling to distinguish inheritance and Pb loss. Comparisons with the reference zircon SL13 have been improved through a direct determination of the component of secondary ion discrimination caused by changes in target potential.

Interpretation of the SHRIMP data for the Birkhill ash (Scotland, Llandovery) is ambiguous. The more conservative possibility is that most zircons are 439 Ma, in close agreement with the previous isotope dilution ages for the same zircon concentrate. The other is that the 439 Ma group should be split into an inherited population at ˜447 Ma, with a minority at ˜434 Ma that corresponds with the ash volcanism. Although imprecise, the latter is detectably younger than the multi-grain MSID age, which itself might be a composite of the same two ages.

Most zircon analyses from the mid Caradoc Pont-y-ceunant Ash, Wales, fit an age-group at 452.5 Ma, similar to its published 206Pb/238U age by MSID, with a definite older age group at ˜476 Ma but none showing Pb loss. By contrast, those from the Millbrig bentonite (Virginia) of the same age mainly fall in a well-defined post-eruption age group at 435 Ma, while the remainder give 456 Ma. Most zircon analyses from the Kinnekulle bentonite, Sweden, fall into an apparent 464 Ma group which exceeds other estimates for the mid-Caradoc magmatism. It is interpreted to be a composite age, caused by an inability to resolve it into a younger magmatic and older inherited group owing to the larger analytical errors of the Kinnekulle data. The best SHRIMP estimate for the mid-Caradoc volcanism is 452.6±1.7 Ma found by combining the ages for the three volcanic units. During unmixing of the combined ages, the Kinnekulle ages are redistributed and the 464 Ma ‘group’ vanishes. Precambrian grains are present in all the above volcanics.

The original and new zircon analyses from the Laidlaw Volcanics (Canberra, Australia) of Ludlow age, are dominated by three groups of inherited zircons at ˜436 Ma, ˜450 Ma and ˜476 Ma, which makes it unfavourable for time-scale definition using zircons. The youngest zircon age group is 417.5 Ma (˜30%), but this is not associated with overgrowths on older grains or with wholly younger grains. Instead, it is composed of sporadic low ages within older grains suggestive of Pb loss rather than magmatic zircon growth. Nevertheless, the age for volcanism is 420.7±1.1 Ma based on published Rb-Sr and K-Ar dating, so that the youngest zircon group does appear to be associated with volcanism.

One zircon U-Pb age for the Frasnian by MSID is much older than a precise age by other decay schemes, and another for the Lochkovian is significantly older than a recent SHRIMP age for the same Stage. By small changes in the common Pb composition, both MSID ages can be changed from single volcanic ages affected by Pb loss to an inherited and younger volcanic age, which removes the conflict with the other determinations.

A zircon-based geological time-scale is constructed from the Ordovician to the Carboniferous using the time-points presented and discussed in Parts I and II of this paper.

At high temperature, MgAl2O4 spinel is stabilized by disorder of Mg and Al between octahedral and tetrahedral sites. This behaviour has been measured up to 1700 K in recent neutron experiments, but the extrapolation of subsequently fitted thermodynamic models is not reliable. First principles simulation of the electronic structure of such minerals can in principle accurately predict disorder, but would require unfeasibly large computing resources. We have instead parameterized on-site and short-ranged cluster potentials using a small number of electronic structure simulations at zero temperature. These potentials were then used in large-scale statistical simulations at finite temperatures to predict disordering thermodynamics beyond the range of experimental measurements. Within the temperature range of the experiment, good agreement is obtained for the degree of order. The entropy and free energy are calculated and compared to those from macroscopic models.

Mineralogical, geochemical and fluid inclusion investigations of a representative suite of fissure vein mineralizations in the Rheinisches Schiefergebirge, NW Germany indicate a link to the latest stage of the Variscan orogenic evolution. Model P-T-conditions during initiation of fibrous fissure vein quartz growth are in the range 370–420°C at 0.2–0.7 kbar. The dataset suggests significant fluid cooling during evolution of the vein systems. Minimum temperatures at the end of fibrous quartz growth lie in the range 140–190°C, with conductive heat transfer and heat consumption during interaction with wallrock believed to be the main mechanisms responsible. Wallrock alteration is characterized by leaching and mobilization of most of the dominant vein components (quartz, albite, apatite), notably Si, Na and P. The principal stage of vein formation is, on the basis of available data, believed to relate to a process of intra-formational redistribution or lateral secretion. However, part of those elements deposited both in wallrock and fissure veins were probably supplied directly by the external fluid. Rates of fissure opening and material deposition were in equilibrium during the principal growth stage of fibrous quartz. However, this situation evolved due to a slowing down of material supply and deposition coupled with an increased rate of fissure opening to produce open fissures and formation of idiomorphic quartz crystals within them. Deposition depths were in the range of 0.6–2.1 km, appreciably lower than estimations of overburden. We believe therefore that formation of the fissure vein systems took place along the retrograde late–orogenic exhumation path, in a transitional stage between Variscan collision and a late- to post-orogenic extensional regime. Fluid composition characteristics also strongly suggest a relationship to the latest stages of the Variscan mineralization cycle in which low–salinity brines dominate. Development of fissure vein systems during the latest stages of continental collision, identified here from the Variscan orogeny, can be considered analogous with similar phenomena in the Alpine orogenic belt.

The 590±2 Ma Ben Vuirich Granite was intruded into late Proterozoic Dalradian rocks prior to the Grampian orogeny, during which it was affected by upper amphibolite facies regional metamorphism. Spotted cordierite and andalusite (chiastolite) hornfelses at the granite margin were altered to kyanite-and garnet-bearing assemblages during regional metamorphism. From the inferred mineralogy of the hornfels, together with the normative Qz–Ab–Or values of the granite and the application of a simple cooling model, we conclude that the country rocks immediately adjacent to the granite were hornfelsed at T = ∼600°C and P ≤ 2 kbar.

The hornfelsed rocks were subsequently metamorphosed during the regional D2 event to form an equilibrium mineral assemblage of muscovite + biotite + garnet + plagioclase + quartz + kyanite (after chiastolite). Garnet which grew during this event shows unusual reversed chemical zoning, with Ca increasing systematically from core to rim as Fe, Mg and Mn decrease. A study of element partitioning between coexisting phases in equilibrium (including zoned garnets), and use of an internally consistent thermodynamic dataset, suggest that isothermal (T = 577±42°C) compression (from P = 6.2±1.6 kbar to 9.0±1.9 kbar) occurred during crustal thickening. K-feldspar-plagioclase-quartz veinlets found in the hornfels close the granite contact are demonstrated to be of igneous origin.

The technique of investigating 3-dimensional interconnections and the shapes of crystals in a rock by X-ray computerized tomography (CT) and image analysis was developed using a graphic granite specimen as an example. Fifty 2-dimensional tomographic images (slices) of the graphic granite were obtained ‘non-destructively’ using a medical X-ray CT scanner. Since a CT value of the specimen was decreased with increasing cross-sectional sample area by the effect of beam-hardening, the CT value was corrected using the area of each slice. Binary images of the slices were made comparing one of them with a thin-section of the slice. Using the binary images, connection analysis of quartz rods in the graphic granite specimen was performed on the basis of percolation theory (cluster labelling). This analysis showed that at least 89.9% of the quartz rods were connected in three dimensions. Furthermore, the 3-dimensional shape of the quartz rods was analysed using the 2-point correlation function calculated from the binary images. The average shape of the quartz rods was obtained by fitting an ellipsoid to the high-value region of the 2-point correlation function. The elongation axis of the ellipsoid agreed well with the crystallographic c-axes of the quartz rods.

The isothermal equation of state (EoS) of phase E, Mg1.96(7)Fe0.072(5)Si1.04(5)H3.7(8)O6, has been determined using high-pressure single-crystal X-ray diffraction. A third-order Birch Murnaghan EoS fit to pressue-volume data collected from room pressure and temperature to 6.7 GPa reveals that phase E has the lowest bulk modulus, KT = 92.9(7) GPa, and highest pressure derivative of the bulk modulus, K' = 7.3(2), for any dense hydrous magnesium silicate (DHMS) yet measured. A parameterized third-order Birch-Murnaghan EoS was also fit to the unit-cell parameters which display significant curvature with increasing pressure. This analysis shows that the c-axis (Kc = 89.1(10) GPa) is 6% more compressible than the a-axis (Ka = 94.8(6) GPa), with little of the anisotropy commonly observed in other layered structures. The high K' is indicative of the similarity to layers of the brucite structure. The introduction of interlayer cation polyhedra to the structure serves to reduce both the anisotropy, by reducing the compressibility perpendicular to the sheets, and the ability to shear, by increasing the coherence between layers.

Replacement phenomena in amblygonite–montebrasite in rare-element pegmatites from the Karibib-Usakos area, Namibia, have been investigated using the electron microprobe. The first African occurrence and analysis of the very rare mineral natromontebrasite NaAl(PO4)(OH,F) is reported from the Daheim pegmatite. In the Okatjimukuju pegmatite, montebrasite has been replaced by a number of phases including crandallite CaAl3(PO4)2(OH)5·H2O and brazilianite NaAl3(PO4)2(OH)4. In one example, montebrasite has been almost completely replaced by brazilianite which has also been found to contain not only crandallite but also its solid solution analogues: goyazite SrAl3(PO4)2(OH)5·H2O and gorceixite BaAl3(PO4)2(PO3OH)(OH)6. Apatite is common at the contacts with montebrasite and associated minerals and texturally is intimately intergrown with crandallite, goyazite and gorceixite at Okatjimukuju. The occurrence of these minerals offers insight into the chemistry of post-magmatic fluids in these pegmatites.

An olivine grain from peridotite nodule 9206 (Udachnaya kimberlite) was heated in air at 700°C for 9 h. It was investigated by EMPA, by IR and UV spectroscopy and by TEM. The TEM examination reveals hexagon-like inclusions up to several hundred nm in size with a core and rim structure. The AEM data show that the inclusions contain only Mg, Fe and Si as cations. The rims have almost the same composition as the olivine matrix whereas the cores are enriched in iron and depleted in Mg. Electron diffraction data, SAED and CBED, indicate that the rims are composed of a ‘secondary’ olivine while the cores are composed of coexisting feroxyhite FeOOH, bernalite Fe(OH)3 and β-cristobalite SiO2. The presence of nm-sized inclusions in minerals is expected to influence the interpretation of spectroscopic results if spectroscopy is carried out without knowledge of the microstructure.

It is speculated that the complex microstructure of the inclusions is a result of a solid state transformation of a precursor phase, probably a hydrous magnesian silicate, during the experimental heating and oxidation.

To date, Fe-Li micas have been defined differently from other micas. The purpose of this paper is to reinterpret the actual Fe-Li mica series with new concepts of ‘essential replacement’ (the evolution direction) and ‘composition track’ (the sequence of mica varieties). Two hundred and fifty-eight analyses from the literature are used for this study in the form of eight data groups. The common compositional and substitutional characters of Fe-Li micas have been reinterpreted in light of principal component analysis and a geometric frame of ideal Fe2+-Al-Li micas in space with (Si, AlIV, AlVI, Fe2+, Li, ☐VI, K)-coordinates.

In our new interpretation, the actual Fe-Li micas are essentially neither AlIV- nor AlVI-, but ☐VI-constant. The actual Fe-Li micas are the weakest fluctuant relative to the Annite-Polylithionite-Trilithionite-Siderophyllite (APTE) plane. About 90% of variations of actual Fe-Li micas range from the trioctahedral trend described as a sequence along the segment K2Al2Fe5/22+Li☐1/2Si6Al2O20(OH,F)4+x[AlFe−22+Li3SiAl−2] (−1/3≤ x≤5/8). The substitution AlFe−22+Li3SiAl−2 (i.e. 2AlIV +4Fe2+ → 2Si +AlVI +3Li) is the main mechanism that keeps actual Fe-Li micas trioctahedral. More than 8% of variations arise from the dioctahedral trend involving created AlVI- and ☐VI-increasing replacement. The actual Fe-Li mica series comprises the composition trend from Fe2+-biotite to lepidolite. This series is not on the siderophyllite-polylithionite join, but can be expressed ideally as K2Al1+xFe4−4x2+Li1+3x(Si6+2xAl2−2x) O20(OH,F)4 (−1/3 ≤x≤1).

The crystal structure of the high-pressure phase-II of cristobalite has been solved by neutron diffraction (space group P21/c, a = 8.3780(11) Å, b = 4.6018(6) Å, c = 9.0568(13) Å, β = 124.949(7)°, at P = 3.5 GPa). This phase corresponds to a distortion of the high-temperature cubic β-phase, rather than of the ambient temperature and pressure tetragonal α-phase.

The dehydroxylation of Ca-, K-, Mg- and Na-saturated Wyoming montmorillonite has been studied by thermogravimetry (TG), infrared (IR) spectroscopy and X-ray diffraction (XRD). Samples saturated with either Ca2+ or Mg2+ show a predominantly diffusion-controlled reaction step, whereas Wyoming montmorillonite with Na+ and K+ in the interlayer exhibit control closer to first order. The activation energy of dehydroxylation is not significantly correlated to the type of interlayer cation present, in turn demonstrating that the role of vacancy location in the octahedral sheet is more significant a control on dehydroxylation.

Metasediments of the Tayvallich Subgroup of the Dalradian at Kinnairds Head, Fraserburgh are metamorphosed to sillimanite + K-feldspar grade and form part of the classic high-T low-P Buchan metamorphic terrain. Pelitic samples constrain peak-metamorphic conditions to 615±13°C and 2.2±0.2 kbar. At or close to the metamorphic peak, irregular garnetiferous aplites and autopegmatite bodies intruded the metasediments. Thin marble bands within the sequence are dominated by calcite with diopside, and equilibrated with relatively CO2-rich, internally buffered fluids. Where these are in close proximity to granitoid pegmatites, wollastonite dominates the matrix, and fractures and veins running through the rock contain concentrations of grossular and vesuvianite. With increasing distance from the pegmatite, vesuvianite and then grossular disappear, and wollastonite is only patchily developed. Such occurrences require a flushing of the marble by metasomatic (siliceous and aluminous) aqueous fluids which were derived from the de-watering of the adjacent pegmatite as it crystallized. The large quantities of dissolved silica led to pervasive wollastonite formation for several metres. The smaller quantities of Al reacted to form Ca-Al-silicates which were confined to the fractures.