I will consider mainly geothermobarometry in medium-grade pelitic rocks, including the garnet-biotite (GB) geothermometer, the Grossular-Al silicate-plagioclase (GASP) geobarometer, and the muscovite-almandine-biotite-sillimanite (MABS) geobarometer. For GB (Holdaway, 2000) experimental data and estimated biotite ΔWTi were used to optimize two exchange parameters and four biotite Margules parameters. Using stepwise linear regression, experimental vs. calculated T were constrained to lie on a line with slope of one and intercept of zero, maximizing r2. The best model involves experiments by Ferry and Spear (1978) and Perchuk and Lavrent’eva (1983), suggesting minimal viAl in the Ferry and Spear product biotite. For GASP (Holdaway, 2001), end-member experimental data do not adequately constrain the equilibrium. I used the GB model above, and allowed the end-member curve to rotate about the best-constrained part of the GASP end-member data. The end-member curve was further constrained with the kyanite-sillimanite (K-S) boundary using published chemical data on 76 pelitic schist samples from 11 localities, rejecting Low-Grs and low-An samples. The Fuhrman and Lindsley (1988) plagioclase model gives the best results. For MABS, work in progress involves 61 samples from the 11 localities which have muscovite analyses. Biotite Margules parameters were based on the GB model and McMullin et al. (1991). The MABS end-member curve was calibrated by comparison of P values determined using trial MABS data and GASP results. The P values for the 61 samples agree well with the K-S boundary, and sillimanite-bearing rocks of west-central Maine all fall in the sillimanite field. Preliminary biotite values are: GAnn = –5149198 – 412.05 T, WAlFe = –14023 + 28.14 T, WAlMg = –259582 + 308.44 T, WTiFe = 124842 – 98.67 T, WTiMg = –186148 + 271.72 T. For geobarometry, the Berman (1988, revised 1992) database was used with adjustable H and S of grossular for GASP and H and S of annite for MABS. The accuracy of currently available databases, activity models and mole fraction models is not adequate for good geothermobarometry, without further refinement. Adjustable parameters tend to compensate for error in activity models, mole fraction models and databases.

The Assynt Culmination of the Moine Thrust Belt, in the northwest Scottish Highlands, contains a variety of Caledonian alkaline and calc-alkaline intrusions that are mostly of Silurian age. These include a significant but little-studied suite of dykes and sills, the Northwest Highlands Minor Intrusion Suite. We describe the structural relationships of these minor intrusions and suggest a classification into seven swarms. The majority of the minor intrusions can be shown to pre-date movement in the Moine Thrust Belt, but some appear to have been intruded during the period of thrusting. A complex history of magmatism is thus recorded within this part of the Moine Thrust Belt. New geochemical data provide evidence of a subduction-related component in the mantle source of the minor intrusions.

The Palaeogene Slieve Gullion Igneous Complex comprises a layered central intrusion surrounded by a slightly older ring dyke. The ring dyke contains two major intrusive rock types. About 70% of the ring dyke is occupied by porphyritic granophyre and 30% by porphyritic felsite. Locally complex relationships between the two lithologies are observed. Major and trace element compositions suggest that there are two distinct chemical groups within each lithology: a Si-rich felsite, concentrated in a ~1 m wide zone at the outer margins of the dyke which grades into a less Si-rich felsite towards the interior. Similarly, a Si-rich granophyre, concentrated in the centre of the intrusion grades outwards into a Si-poor granophyre facies.

These rock relationships and geochemical variations suggest that a complex magma chamber hosted a stratified granitic magma body and various wall/floor magma facies. Low density, high-Si felsite magma from the top of the chamber was tapped first, followed by less Si-rich felsite magma as evacuation proceeded. The granophyres probably originate from the chamber walls/floor, representing more mushy equivalents of the felsite magma. Little granophyre magma was tapped during the early stages of the evacuation sequence. As evacuation continued, probably aided by trap-door caldera collapse, the ‘granophyre magmas’ intruded the already emplaced and slightly cooled felsite, forming the complexly zoned structure of the Slieve Gullion ring intrusion.

Sedimentary basins developed along the European margin during the earliest, Permian, stage of proto-Atlantic rifting, during a phase of high heat flow. The proximity of some basins to Caledonian thrusts has implied that rifts locally utilized the basement fabric. New mineralogical and palaeomagnetic data show that thrust planes in the Moine Thrust Zone channelled a pulse of hot fluid in Permian time. The fluids precipitated kaolin in fractures in the thrust zone, and with decreasing intensity away from the zone. The high-temperature polytype dickite is largely confined to major thrust planes. Stable H and O isotope analyses indicate that the parent fluid included meteoric water involved in a hydrothermal system. Coeval hydrothermal hematite has a chemical remanence that dates the fluid pulse as Permian. This is direct evidence for post-orogenic activity in the thrust zone, in which the thrusts vented excess heat during regional crustal extension. The example from the European margin exemplifies the importance of deep-seated structures in the release of heat, and the value of kaolinite polytype mapping as a tool to record anomalous palaeo-heat flow.

The low-frequency mechanical properties of pure and Ca-doped lead orthophosphate, (Pb1–xCax)3(PO4)2, have been studied using simultaneous dynamical mechanical analysis, X-ray diffraction (XRD), and optical video microscopy in the vicinity of the first-order ferroelastic phase transition. Both samples show mechanical softening at T > Tc, which is attributed to the presence of dynamic short-range order and microdomains. Stress-induced nucleation of the low-temperature ferroelastic phase within the hightemperature paraelastic phase was observed directly via optical microscopy at T ≈ Tc. Phase coexistence is associated with rapid mechanical softening and a peak in attenuation, P1, that varies systematically with heating rate and measuring frequency. A second peak, P2, occurs ≈3–5°C below Tc, accompanied by a rapid drop in the rate of mechanical softening. This is attributed to the change in mode of anelastic response from the displacement of the paraelastic/ferroelastic phase interface to the displacement of domain walls within the ferroelastic phase. Both the advancement/retraction of needles (W walls) and wall translation/rotation (W′ walls) modes of anelastic response were identified by optical microscopy and XRD. A third peak, P3, occurring ≈ 15°C below Tc, is attributed to the freezing-out of local flip disorder within the coarse ferroelastic domains. A fourth peak, P4, occurs at a temperature determined by the amplitude of the dynamic force. This peak is attributed to the crossover between the saturation (high temperature) and the superelastic(low temperature) regimes. Both samples display large superelastic softening due to domain wall sliding in the ferroelastic phase. Softening factors of 20 and 5 are observed in the pure and doped samples, respectively, suggesting that there is a significant increase in the intrinsic elastic constants (and hence the restoring force on a displaced domain wall) with increasing Ca content. No evidence for domain freezing was observed down to −150°C in either sample, although a pronounced peak in attenuation, P5, at T ≈ −100°C is tentatively attributed to the interaction between domain walls and lattice defects.

Both samples show similar high values of attenuation within the domain-wall sliding regime. It is concluded that the magnitude of attenuation for ferroelastic materials in this regime is determined by the intrinsic energy dissipation caused by the wall-phonon interaction, and not by the presence of lattice defects. This will have a large impact on attempts to predict the effect of domain walls on seismic properties of mantle minerals at high temperature and pressure.

The Koktokay No. 3 granitic pegmatite, Altai, northwestern China, is a strongly zoned rare-element granitic pegmatite, where the petrographic zones were distinguished into two groups: outer zones (I to IV) and inner zones (V to IX). Nb-Ta oxides and zircon are investigated in this paper by using quantitative electron-microprobe analyses (EMPA) and backscattered-electron (BSE) imaging. Columbite-tantalite and zircon occur in most textural zones, whereas tapiolite and uranmicrolite are mainly restricted to zone VII. Manganocolumbite and zircon from the outer zones (zones II and IV) are homogeneous except for a few exceptions, whereas manganotantalite and hafnian zircon from the inner zones (V–VII) are obviously heterogeneous and strongly zoned. Chemically, Ta/(Nb+Ta) in columbite-tantalite and Hf/(Zr+Hf) in zircon increase from the outer to the inner zones on one hand, and from core to rim in single zoned crystals on the other hand. Observations of intra-zonal variations of the chemical composition of Nb-Ta oxides and zircon in the Koktokay No. 3 granitic pegmatite may suggest that the outer zones crystallize under magmatic conditions, whereas the inner zones crystallize under fluid-rich magmatic conditions, and locally under hydrothermal conditions. The extreme enrichments of columbite-tantalite in Ta, and of zircon in Hf, as well as the occurrence of uranmicrolite and tapiolite, indicate an elevated evolution of the Koktokay No. 3 granitic pegmatite.

Mineralogical-chemical techniques (XRD, SEM/EDX, WDXRF) and a sequential selective extraction procedure were applied to mine-waste materials and stream sediments from the Baccu Locci stream catchment (Sardinia, Italy) affected by serious As contamination as a consequence of past mining. Results indicate that solid-state speciation of As is mainly dominated by the presence of Fe(III) hydroxides (arsenical ferrihydrites with various Fe/As molar ratios) occurring as coatings of silicate grains, in which As is contained as sorbed or co-precipitated species. Scorodite (FeAsO4·2H2O) is common too, whereas arsenopyrite is generally subordinate but, owing to its relatively rapid oxidation, environmentally significant. Moreover, some unidentified arsenates of Ca-Fe or K-Fe were also detected. Arsenic contained in these phases is slowly, but continuously, released in relatively small amounts through three main mechanisms: (1) oxidation of residual arsenopyrite to scorodite; (2) decomposition of scorodite into a hydroxide or oxide of Fe(III); (3) desorption/release from Fe(III) hydroxides. Decomposition of the unidentified arsenates is also probable, e.g. Ca-Fe arsenate → calcite + Fe(III) hydroxide + As release. The flotation tailings are widely scattered and distributed in the middle–lower Baccu Locci stream catchment, and represent the most dangerous As-generating contamination source in the study area.

We report micro-Raman spectroscopic studies of FeS2 pyrite in the diamond-anvil cell under hydrostatic and non-hydrostatic conditions to 55 GPa at room temperature. Four out of five Ramanactive modes are resolved with helium as a pressure-transmitting medium to highest pressures. The fifth mode, Tg(2) [377 cm-1], is weak and unresolved lying ∼2 cm-1 from the intense Ag mode [379 cm-1] at 1 bar. We observe an increase in the separation of the Eg [344 cm-1] and Tg(1) [350 cm-1] modes under compression. All observed frequencies increase continuously with increasing pressure showing no evidence for a structural phase transition in accord with both X-ray diffraction and shock-wave studies. The Ag and Tg(1) modes gain significantly in intensity relative to the Eg mode with increasing pressure probably resulting from Raman resonance effects. The Tg(3) mode [430 cm-1] broadens unusually compared to the other pyrite modes with pressure. The Raman data are consistent with a contraction of the S-S and Fe-S bonds under pressure. The main effect of non-hydrostatic conditions on the Raman modes is a strong pressure-induced broadening; the pressure-dependence of the frequencies and relative intensities are not affected within the error of the measurements.

The magnetic susceptibility of ordered and partially disordered manganogrunerites (composition and ) has been measured between room temperature and 5 K. The influence of disordering of metal cations over the M(1,2,3) sites of the octahedral ribbon in these amphiboles is to dilute Fe2+ within the ribbon. We observe a reduction in both θp and TN as a function of both increased Mg/(Mg+Fe) and metal cation disorder, linked to a reduction in the strength of magnetic coupling between and within the one-dimensional chains of the structure.

Feldspars from the Karkonosze pluton (SW Poland) display many features compatible with magma mixing. The mixing hypothesis has been tested using a geochemical mass balance law resulting in two possible paths of magma hybridization. Based on the results of the geochemical calculation, feldspar samples have been chosen along both mixing lines for cathodoluminescence (CL) investigation which was used as the main tool for the reconstruction of their crystallization path. Changes in the conditions of nucleation and crystallization of the feldspars as well as their movement within the magma chamber have been recognized due to different luminescence characteristics. These changes in the conditions of crystallization obtained by CL allow a precise determination of the genetic affinity of the samples to more mafic or more felsic environments.

The results of the present study proved CL to be a valuable tool for the study of crystal-growth morphologies in a dynamic, turbulent environment and also as a geochemical tool for the reconstruction of various petrogenetic mechanisms (e.g. magma hybridization). Accordingly, the combination of CL with geochemical modelling provides corresponding information about magma evolution in an open system.

Petewilliamsite, ideally (Ni,Co)30(As2O7)15, monoclinic, space group C2, a = 33.256(5), b = 8.482(1), c = 14.191(2) Å, ß = 104.145(3)°, V = 3881.6(11) Å3, a:b:c = 3.9209:1:1.6731, Z = 2, is a new mineral found on a single nickeline-veined quartz specimen from Johanngeorgenstadt, Saxony, Germany. The mineral possesses a pronounced subcell-supercell: a (subcell) = 1/5 a (supercell); b (subcell) = b (supercell); c (subcell) = 1/3 c (supercell), and the strongest six lines of the X-ray powder-diffraction pattern are [d in Å (I) (hkl)]: 4.235(30)(020) ; 3.118(100)(513, 023); 3.005(60); 2.567(50); 1.637(50)(536 ); 1.507(30b)(553, ). It occurs predominantly as scattered patches of mm-sized aggregates which are intimately associated with varicoloured xanthiosite; additional associations include bunsenite, aerugite, rooseveltite, native bismuth, paganoite and two undefined arsenates. Subhedral equant crystals with rounded faces are intimately intergrown in 1 mm-sized aggregates and individual grains do not exceed 0.5 mm in maximum diameter. The average crystal size is variable from 20 μm to 0.3 mm. The colour varies from dark violet-red to dark brownish-red and the streak is pale reddish-brown to pale purplish-brown. Crystals are translucent, brittle, vitreous, and do not fluoresce under ultraviolet light. The mineral shows neither twinning nor cleavage, has an uneven fracture, and the calculated density (for the empirical formula) is 4.904 g/cm3. Electron-microprobe analyses gave NiO 19.45, CoO 18.39, CuO 3.40, CaO 0.17, FeO 0.04, As2O5 60.32, total 101.77 wt.%. The empirical formula, derived from crystal-structure analysis and electron-microprobe analyses, is (Ni14.662+Co13.822+Cu2.412+Ca0.17Fe0.032+)Σ31.09(As1.975+O7)15, based on O = 105 atoms per formula unit (a.p.f.u.). In reflected plane-polarized light in air, petewilliamsite is dark grey with orange to spectral (multicoloured) internal reflections and no obvious bireflectance, anisotropy or pleochroism. Measured reflectance values in air are tabulated; the index of refraction calculated at 589 nm is 1.88. The mineral name honours Professor Peter (‘Pete’) Allan Williams of the University of Western Sydney, New South Wales, Australia, for his contributions to the study of secondary minerals.

The crystal structure of petewilliamsite has been solved by direct methods and refined on the basis of F2 using 9212 unique reflections measured with Mo-Kα X-radiation on a diffractometer equipped with a CCDbased detector. The final R1 was 7.68%, calculated for 1273 observed reflections. The structure contains 15 symmetrically distinct As5+ cations, each of which is tetrahedrally coordinated by four O atoms, and pairs of these AsO4 tetrahedra share a vertex which results in As2O7 pyroarsenate groups that are in layers parallel to (010). The structure also has 16 distinct transition-metal M (M: Ni,Co) sites of which there are one tetrahedral, four square bipyramidal, and 11 octahedral arrangements. Adjacent pyroarsenate groups are linked through bonds to M cations. The structure of petewilliamsite is not closely related to other naturally occurring arsenates and it is the first pyroarsenate mineral.

Aurivilliusite, ideally Hg2+Hg1+OI, is monoclinic, C 2/c, with unit-cell parameters refined from X-ray powder data: a= 17.580(6), b= 6.979(1), c= 6.693(3)Å, β = 101.71(4)°, V = 804.0(5)Å3, a:b:c= 2.5190:1:0.9590,Z = 8. The strongest six lines of the X-ray powder-diffraction pattern [din Å (I )(hkl)] are: 8.547(70)(200), 3.275(100)(002), 2.993(80)(21), 2.873(80)(600), 2.404(50b)(02, 421, 22) and 1.878(50)(23). This extremely rare mineral was collected from a small prospect pit near the longabandoned Clear Creek mercury mine, New Idria district, San Benito County, California, USA. It is intimately intermixed with another new undefined Hg-O-I phase (‘CCUK-15’), and is also closely associated with native mercury, cinnabar and edgarbaileyite in a host rock principally composed of quartz and magnesite. Aurivilliusite occurs in a cm-wide quartz vein predominantly as irregular-shaped thin patches ‘splattered’ on the quartz surface; patches vary in size from 10–20 μm up to 0.5 mm. The only known subhedral platy brightly reflecting crystal fragment, with major ﹛100﹜ form and distinct ﹛100﹜ cleavage, did not exceed 0.2 mm in longest dimension. The mineral is dark grey-black with a dark red-brown streak. Physical properties include: metallic lustre; opaque; non-fluorescent; brittle; uneven fracture; calculated density 8.96 g/cm3 (empirical formula), 8.99 g/cm3 (ideal formula). In polished section in plane-polarized reflected light, aurivilliusite resembles cinnabar, is extremely light sensitive, shows twinning and no internal reflections, and exhibits an unusual ‘red light’ coalescing phenomena. Averaged and corrected results of electron-microprobe analyses yielded HgO 40.10, Hg2O 38.62, I 22.76, Br 0.22, Cl 0.06, sum 101.76, less O = I + Br + Cl –1.46, total 100.30 wt.%, corresponding to Hg1.002+Hg1.001+ O1.01(I0.97Br0.01Cl0.01)Σ0.99, based on O + I + Br + Cl = 2 atoms per formula unit (a.p.f.u.). The original value for Hg, 74.27 wt.%, was partitioned in a HgO:Hg2O ratio of 1:1 after the discovery of the crystal-structure paper dealing with the synthetic equivalent of aurivilliusite. The mineral name is in honour of the late Dr Karin Aurivillius (1920 –1982), chemistcrystallographer at the University of Lund, Sweden, for her significant contributions to the crystal chemistry of Hg-bearing inorganic compounds. Aurivilliusite is related chemically to terlinguaite, Hg2+Hg1+OCl, but has a different structure and X-ray characteristics.

We demonstrate the potential of X-ray photo-emission electron microscopy (XPEEM) to reveal valence-state images of the spatial distribution and relative concentration of metals in specific oxidation states. Additionally, XPEEM allows X-ray absorption spectra to be extracted from chosen pixel areas of the images. Using an in-house-built XPEEM instrument we show an application of the method in providing valence-state images of complex mineral intergrowths. The image resolution achieved with this instrument of simple design was ∼5 μm and reasonable quality X-ray absorption spectra were extracted from areas of ∼5×5 μm. These initial results suggest that by using commercial XPEEM instruments on 3rd generation, high-brightness synchrotron sources a spatial resolution of 100 nm or better could be achieved, with the ability to extract high-quality X-ray absorption spectra from areas of 0.1 μm2. Given that standard thin sections or polished blocks can be studied by XPEEM, and that each XPEEM image records ∼1000 μm2, XPEEM can be used in conjunction with other analytical methods such as EMPA and TEM-EELS/PEELS.

Several small bodies of massive to banded amphibolite occur within plagioclase-quartz-biotite hornblende gneiss at or close to its boundary with a quartz diorite pluton in the Neoproterozoic terrain of southern Israel. Entrapped within the amphibolite are nodules consisting mainly of calcite+talc, and rare banded marble. Remnant laminae and certain geochemical features such as the negative Ce anomaly and depleted δ13C of the nodules sugggest that they initially formed as stromatolites. The local geological setting of the amphibolites together with the presence of the enclosed meta-carbonates favoured an origin as sediments, although some of the geochemical data point to a basaltic precursor and some of the carbonates have a puzzlingly high (>1000 ppm) Ni content. The origin of the amphibolites is thus enigmatic.

The major- and trace-element chemistry of pyrite and arsenopyrite from the mesothermal Roudný gold deposits was studied by electron microprobe and laser ablation ICP-MS techniques. In total, four generations of pyrite and two of arsenopyrite were distinguished. The pyrite is enriched in As through an Fe (AsxS1–x)2 substitution mechanism. The As-rich zones of pyrite-2 (up to 4.5 wt.% As) are also enriched in gold (up to 20 ppm), lead (commonly up to 220 ppm, exceptionally up to 1500 ppm) and antimony (commonly <600 ppm, rarely up to 1350 ppm). Positive correlation of As and Au in the studied pyrites is not coupled with an Fe deficiency, in contrast to Au-rich As-bearing pyrites in Carlintype gold deposits. The As-rich pyrite-2 coprecipitated with the Sb-rich (1 –4.2 wt.%) and Au-rich (40 –150 ppm) arsenopyrite-1. The younger arsenopyrite-2 is significantly less enriched in these elements (0 –70 ppm of Au).

The chemical zonality of pyrites in the Roudný gold deposits reflects the chemical evolution of orebearing fluids that are not observed in any other mineral phases. The data available suggest relatively high activity of sulphur and low activities of arsenic and gold during crystallization of the older pyrite generation (pyrite-1). Later, after particular dissolution of pyrite-1, Au-rich As-bearing pyrite-2 and arsenopyrite precipitated. These facts suggest a marked increase in the arsenic and gold activities in ore-bearing fluids. The As-content of pyrite-2 decreases in an oscillatory manner from the core to the rim, reflecting changes in the As activity or/and in the P-T conditions. The As-bearing pyrites were formed at temperatures of at least 320–330°C, based on arsenopyrite thermometers and fluid inclusion data.

Hydrothermal synthesis produced the new compound SrCo2(AsO4)(AsO3OH)(OH)(H2O). The compound belongs to the tsumcorite group (natural and synthetic compounds with the general formula M(1)M(2)2(XO4)2(H2O,OH)2; M(1)1+,2+,3+ = Na, K, Rb, Ag, NH4, Ca, Pb, Bi, Tl; M(2)2+,3+ = Al, Mn3+, Fe3+, Co, Ni, Cu, Zn; and X5+,6+ = P, As, V, S, Se, Mo). It represents (1) the first Sr member, (2) the until now unknown [7]-coordination for the M(1) position, (3) the first proof of (partially) protonated arsenate groups in this group of compounds, and (4) a new structure variant.

The crystal structure of the title compound was determined using single-crystal X-ray diffraction data. The compound is monoclinic, space group P21/a, with a = 9.139(2), b = 12.829(3), c = 7.522(2) Å, β = 114.33(3)°, V = 803.6(3) Å3, Z = 4 [wR2 = 0.065 for 3530 unique reflections]. The hydrogen atoms were located experimentally.

Exsolved garnet, sometimes associated with exsolved amphibole and zoisite, is abundant in aluminous clinopyroxene of garnet clinopyroxenite and clinopyroxenite xenoliths in the early Cretaceous dioriticmonzodioritic intrusions from the Xuzhou region, ∼100 km west of the Sulu ultrahigh-pressure (UHP) metamorphic terrane in eastern China. In addition to the mineral exsolutions, intergranular fine-grained garnet, zoisite, titanite, and sometimes amphibole are also present around the primary clinopyroxene grains. Clinopyroxene shows compositional gradients, with decreasing Al and increasing Si and Mg, adjacent to the garnet lamellae and intergranular garnet. In contrast, the exsolved and intergranular garnet is homogeneous in composition and typically more grossular-rich and pyrope- and almandinepoor than the coarse-grained primary garnet. The estimates of P and T for the precursor assemblage and garnet exsolution suggests a decrease of temperature from ∼950—1100ºC down to 620—780°C, and a nearly constant pressure from ∼15—20 kbar to 18 kbar, which are comparable with the metamorphic conditions of the associated eclogites. Therefore, garnet exsolution in garnet clinopyroxenite and clinopyroxenite xenoliths could be caused by high-pressure (HP) metamorphism. SHRIMP zircon U-Pb dating for the associated eclogite and gneiss xenoliths and Sm-Nd whole rock-garnet dating for the same eclogite demonstrate that parts of lower crust on the southeastern margin of the North China craton might be involved in the Triassic HP metamorphism due to the deep subduction of the Yangtze craton.

Metabasites in the Dalradian Argyll and Southern Highland Groups experienced multiphase deformation and coeval Barrovian-type prograde and retrograde metamorphism during the Caledonian Grampian orogeny. Metamorphic Ca-amphiboles crystallized with plagioclase,epidote,chlorite and quartz, and sometimes with garnet and clinopyroxene. The minor changes in metabasite mineral assemblages and systematic mineral-chemical variations in Ca-amphibole confirm the classical concept of increasing metamorphic grade in metapelitic Chlorite to Sillimanite zones. In the Chlorite zone, high-Ti brown amphibole enclosed by green Ca-amphibole is interpreted as a magmatic relic. In the Chlorite, Biotite,Garnet and Andalusite zones, Ca-amphibole displays zonation with actinolite in cores and magnesio-hornblende to tschermakite in rims. Poor amphibole zonations occur in the Kyanite and Sillimanite zones. Ca-amphibole zonations are best described in terms of IVAl, VIAl and Ti which semiquantitatively monitor temperature and pressure changes. Maximal IVAl in amphibole increase with metamorphic grade. Empirically calibrated amphibole equilibria enabled us to reconstruct coherent prograde P-T paths and maximal P and T from the mineral zones; with Tmax of 680±50°C in the Sillimanite zone and Pmax of 8±1.2 kbar in the Kyanite zone. Prograde P-T paths indicate that elevated geothermal gradients should be considered even at the beginning of the Grampian Barrovian metamorphism.

The original structure determination of asisite, nominally Pb7SiO8Cl2, has been re-evaluated in the light of electron-diffraction data (TEM) on the original sample material. Electron diffraction patterns indicate a super-structure based upon a metrically tetragonal 26-cation-site super-sheet motif (14x14x23 Å). Given the strong ordering of elements substituting for Pb in closely-related litharge-based oxychlorides (parkinsonite, symesite, kombatite, schwartzembergite), the asisite superstructure is inferred to be due to strong ordering of Si within the PbO sheet. The original chemical analyses of asisite given by Rouse et al. (1988) are shown to be consistent with such a super-structure, which has a 12Pb:1Si cation ratio. A new formula for asisite is proposed that is based upon this superstructure: Pb12(SiO4)O8Cl4 (Z = 8). The structure of asisite determined by Rouse et al. (1988) is that of the average Pb/Si-disordered tetragonal sub-cell (I4/mmm: 4x4x23 Å) and belies the highly ordered real state. The structure of the tetragonal sub-cell has been re-determined here: R = 5.6% for 178 unique Fo > 4σFo and an anisotropic model. A significantly reduced 72% occupancy of the Pb(2) site was found that implies the nominal formula Pb7SiO8Cl2, thus confirming the findings of Rouse et al. (1988). Comparisons with kombatite and symesite support the assignment of Si to Pb(2) and imply that Si in asisite is also likely to be in tetrahedral coordination, with the apical oxygen cross-linking PbO sheets. However, because most of the key information relating to the location of Si is provided by the super-lattice reflections, the inability of X-ray diffraction to register these reflections introduces a significant ambiguity into the interpretation of Pb/Si ordering behaviour in this mineral.