Understanding the deformation mechanisms that may operate in pyrite (FeS2) across a range of P-Tconditions is important in deciphering the history of deformed ore deposits. Pyrite has frequently been considered a hard mineral, which deforms by cataclastic flow or diffusive processes, if at all, at temperatures <425°C. However, utilizing SEM-based orientation-contrast (OC) imaging and electron-backscatter diffraction (EBSD) techniques, plastic deformation can now be readily identified within pyrite grains. In this study, a series of pyrite-rich polymetallic ore deposits, deformed at low temperature metamorphic conditions (∼200—420°C), have been investigated. Results indicate that pyrite grains in all the ore deposits preserve internal lattice ‘distortion’ or ‘bending’ and therefore plastic deformation mechanisms have operated. Many pyrite grains in the ore deposits also contain low-angle (∼2°) sub-grain boundaries or ‘dislocation walls', indicating that both dislocation glide and creep have been the dominant deformation mechanisms at peak metamorphic conditions within the pyrite grains. These results suggest that the brittle-ductile transition in pyrite occurs at temperatures potentially as low as ∼200°C, far lower than implied from previous studies or the current pyrite deformation-mechanism map.

Perovskite compositions are used to investigate the relationship between the minor components (i.e. LREE, Fe3+ and Nb) and the oxygen fugacity (fo2) of perovskite in four different kimberlite lithofacies from the Dutoitspan pipe, Kimberley, South Africa, which range from diamondiferous to barren. The perovskite textures and chemical variations provide insight into magmatic and eruptive processes. Some crystals display cores with rims separated by a sharp boundary. The cores contain larger Na and LREE contents relative to the rims, which show a large increase in Fe3+ and Al. The mid-grade and barren kimberlites have bi-modal cores, reflected in the mineral chemistry, signifying multiple batches of magma and magma mixing. The fo2 of the magma is determined by an Fe-Nb oxygen barometer. The most diamondiferous kimberlite has the greatest Fe3+ content and highest fo2 (NNO –3.6 to –1.1). The kimberlite containing large diamonds has the smallest Fe3+ content and lowest fo2 (NNO –5.2 to –3.0). The barren and mid-grade kimberlites display a wide range of fo2,(NNO –5.3 to –1.5) as a result of perovskites forming in different melts and subsequently mixing together. Chemical and petrological evidence suggests that the volatile content, degassing, decompression and rate of crystallization can influence the rate at which the magma is erupted. One possibility is that the most oxidized magma, containing the highest volatile content, is therefore erupted much more rapidly, preserving diamond as a consequence.

The composite Eskdalemuir dyke was formed by the intrusion of rhyolitic magma into partly crystallized basaltic magma, the proportion of the silicic component increasing towards the dyke centre. The less silicic parts were effectively supercooled and crystallization was halted when the residual melt quenched to rhyolitic glass which constitutes up to 50% of the dyke's centre. Pyroxene compositions in the mixed magma rocks include augite, pigeonite and orthopyroxene of very variable composition. Individual crystals in the matrix as small as 200 μm can contain compositions occupying a considerable part of the Di-Hd-En-Fs quadrilateral. Pyroxene crystallization took place under extreme disequilibrium conditions, as shown by highly variable zonation patterns; apparently opposite zoning trends can occur in adjacent grains. Small-scale variations in melt composition were probably the dominant control over the compositional and textural complexity in the pyroxenes.

Ca-poor and typically Na-rich feldspar megacrysts are common associates of spinel lherzolitic and pyroxenitic xenoliths in Scottish alkalic basalts. Associated megacrysts and composite megacrysts and salic xenoliths include apatite, magnetite, zircon, biotite, Fe-rich pyroxene(s) and corundum. The salic xenoliths and related megacrysts are referred to collectively as the ‘anorthoclasite suite': the majority of the samples are inferred to derive from the disaggregation of coarse-grained, typically Na-rich, syenitic protoliths at depth. Rare occurrences of euhedral anorthoclase megacrysts, together with zircon dating, imply that the suite crystallized at, or very shortly before, their entrainment by the basaltic host magmas. Some evidence suggests that the anorthoclasite suite protoliths lie within ultramafic (pyroxenitic) domains in the deep crust. The latter are inferred to be pegmatites, crystallized from carbonated trachytic magmas with widely variable Ca, Na, K, Ba and trace-element contents, and to have ranged from metaluminous to peraluminous. Crystal zonation and resorption textures within the salic xenoliths imply that the crystallization of the parent magmas was complex. Confirmation of this comes from cathodoluminescence studies of the feldspars showing that early ('primary’) anorthoclases and potassian albites exhibit partial replacement by a more potassic feldspar. A third generation of potassic feldspar (enriched in an assortment of trace elements and deduced to have crystallized from a carbonated high-K melt) forms transecting zoned veins in which carbonate fills the axial zone.

Whereas most of the anorthoclasite suite materials are inferred to have grown from metaluminous magmas, the occurrence of magmatic corundum in salic xenoliths indicates crystallization from magmas that were peraluminous. The corundum-bearing samples also contain Nb-rich oxide minerals and their associated feldspars have the highest rare-earth element (REE)contents. Accordingly, the peraluminous trachyte magmas are deduced to have been specifically enriched in high field-strength trace elements. It is proposed that formation of the anorthoclasite suite protoliths is a phenomenon closely related to that of salic glass ‘pockets', well known from spinel lherzolite xenoliths around the world. Not only are there compositional affinities, but both sets of phenomena appear to have closely pre-empted the ascent of alkali basalt (host) magmas. We propose that the two sets of phenomena are linked and that the anorthoclasite suite derived from coarse-grained sheets, generated by the aggregation of salic melt fractions rising from the shallow mantle and heralding the onset of basaltic magmatism.

The presence of structural OH in amphiboles in excess of the usual two OH per formula has been debated for over 40 years (Gier et ah,1964; Leake et ah,1968). However, the reality of the excess-OH phenomenon is still an open question, because accurate water analyses of amphiboles are rarely available. In this study, we review the data available on the chemically simple synthetic system Na2O—MgO-SiO2-H2O (NMSH) and present new results from NMR, infrared spectroscopy, and X-ray-diffraction that allow re-interpretation of previous studies of NMSH amphiboles along the pseudobinary join between the two end-member compositions Na2Mg6Si8O22(OH)2 and Na3Mg5Si8O21(OH)3.

We show that there is extensive solid solution involving excess H at 650—750°C, but also document the presence of a wide miscibility gap below 600°C. This miscibility gap is defined by amphiboles very close to the end-member composition Na3Mg5Si8O22(OH)3 coexisting with amphiboles with compositions near the ‘normal’ Na2Mg6Si8O22(OH)2 end member.

We also report the characterization of triple-chain silicates (TCS) in the NMSH system and their phase relations with NMSH amphiboles. The upper thermal stability field of the key TCS Na2Mg4Si6O16(OH)2relative to its decomposition to two NMSH amphiboles with a combined equivalent composition has been determined and a pronounced backbend of the transformation boundary documented. Phase relations observed in synthesis experiments suggest that at 550—650°C all TCSs have compositions close to Na2Mg4Si6Oi6(OH)2. Infrared spectroscopy indicates that the TCS synthesized on this composition, studied in detail here, vary from end-member Na2Mg4Si6Oi6(OH)2 to binary solid solutions with less than ∼6 mol.% clinojimthompsonite component. No clear spectroscopic evidence for a ‘Drits’ component NaMg4Si6Oi5(OH)3 (Drits et al.,1975) has been found. Analysis of H2O by vacuum extraction and Karl-Fischer titration indicates large excesses of H2O in all the TCSs studied here that clearly exceed the amounts expected from (OH) groups alone. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) indicate that this excess H2O is structural. We propose that the excess H2O is likely to be molecular H2O located in the ^4-site channels. The observed backbend of the triple-chain decomposition curve is in agreement with a reaction involving dehydration and loss of this molecular H2O. However, the absolute amount of analysed molecular H2O exceeds that expected from the change in Clapeyron slope alone.

While demonstrating the reality of excess OH in amphiboles, the evidence presented in this paper also points to interesting avenues for future research on both amphiboles and TCSs, such as understanding the dynamics and enhanced crystal chemistry of excess OH and molecular H2O in pyriboles.

Many evolved peraluminous granite plutons contain either andalusite (Al2SiO5) or topaz (Al2SiO4(OH,F)2), but some plutons contain both of these A/NK [mol. Al2O3/(Na2O+K2O)] = ∞ phases. We present the results of experiments conducted to locate the andalusite-topaz boundary in water-saturated peraluminous haplogranite melts in T-P-Xspace, where T = 700—650°C, P = 200 MPa. andX(A/NK = 1.1, 1.2, 1.3, 1.4, and F = 0, 1, 2, 4 wt.%).The starting materials are synthetic K-Na-Al-Si gels, with added H2O and AgF, with seeds of natural andalusite and topaz, and with run times of 5—7 days. Phase identification is by electron microprobe. All experimental run products contained quartz. For all values of bulk A/NK, F concentrations ⩽ 1 wt.% favour andalusite stability, whereas F concentrations ⩾ 1 wt.% favour topaz stability. For bulk A/NK ⩽ 1.2 and intermediate F concentrations, no A/NK = phase is present; for bulk A/NK ⩾ 1.3, quench or metastable mullite formed. Topaz reaction rims on naturally occurring andalusite, frequency of naturally occurring assemblages, general chemical considerations, and experimental evidence all suggest that some topaz is the product of a peritectic reaction between an early primary magmatic andalusite and a late F-enriched melt. The appearance of such topaz is an important mineralogical expression of F activity in the melt, and may be an indicator for high field-strength Sn-W-U-Mo polymetallic mineralization.

An electron microprobe study of Y-REE-Th phosphate, silicate and Nb-Ta-Y-REE accessory-mineral assemblages revealed the compositional variations and evolution in post-orogenic, hypersolvus Permian A-type metagranite from Turčok, in the Gemeric Unit, of the Western Carpathians, eastern Slovakia. Prismatic zircon I and allanite-(Ce) are primary magmatic phases. However, the late-magmatic to early-subsolidus processes led to the formation of a more complex younger assemblage: bipyramidal zircon II, xenotime-(Y), thorite, gadolinite-hingganite-(Y), Nb-Ta-Y-REE oxide phases [fergusonite-(beta)/ samarskite-(Y), aeschynite/polycrase-(Y), and Nb-rich rutile?] and possibly monazite-(Ce). However, monazite-(Ce) and the partial alteration of allanite-(Ce), xenotime-(Y) and the Nb-Ta-Y-REE minerals are probably connected with a younger Alpine metamorphic overprint of the granite. Thorite appears as a solid solution in the thorite-xenotime-zircon series; it is also enriched in Al. Fergusonite-(beta)/ samarskite-(Y) and especially aeschynite/polycrase-(Y) show increased P, Si and Al contents.

Dalnegroite, ideally Tl4Pb2(As12Sb8)Σ20S34, is a new mineral from Lengenbach, Binntal, Switzerland. It occurs as anhedral to subhedral grains up to 200 μm across, closely associated with realgar, pyrite, Sb-rich seligmanite in a gangue of dolomite. Dalnegroite is opaque with a submetallic lustre and shows a brownish-red streak. It is brittle; the Vickers hardness (VHN25) is 87 kg mm-2 (range: 69—101) (Mohs hardness ∼3—3½). In reflected light, dalnegroite is highly bireflectant and weakly pleochroic, from white to a slightly greenish-grey. In cross-polarized light, it is highly anisotropic with bluish to green rotation tints and red internal reflections.

According to chemical and X-ray diffraction data, dalnegroite appears to be isotypic with chabournéite, Tl5-xPb2x(Sb,As)21-xS34. It is triclinic, probable space group P1, with a = 16.217(7) Å, b = 42.544(9) Å, c = 8.557(4) Å, α = 95.72(4)°, β = 90.25(4)°, γ = 96.78(4)°, V = 5832(4) Å3, Z = 4.

The nine strongest powder-diffraction lines [d(Å) (I/I0) (hkl)] are: 3.927 (100) ( 10 0); 3.775 (45) (22); 3.685 (45) (60); 3.620 (50) (440); 3.124 (50) (2); 2.929 (60) (42); 2.850 (70) (42); 2.579 (45) (0 2); 2.097 (60) (024). The mean of 11 electron microprobe analyses gave elemental concentrations as follows: Pb 10.09(1) wt.%, Tl 20.36(1), Sb 23.95(1), As 21.33(8), S 26.16(8), totalling 101.95 wt.%, corresponding to Tl4.15Pb2.03(As11.86Sb8.20)S34. The new mineral is named for Alberto Dal Negro, Professor in Mineralogy and Crystallography at the University of Padova since 1976.

Holtite, approximately (Al,Ta,□)Al6(BO3)(Si,Sb3+,As3+)Σ3O12(O,OH,□s)Σ3, is a member of the dumortierite group that has been found in pegmatite, or alluvial deposits derived from pegmatite, at three localities: Greenbushes, Western Australia; Voron'i Tundry, Kola Peninsula, Russia; and Szklary. Lower Silesia, Poland. Holtite can contain >30 wt.% Sb2O3, As2O3, Ta2O5, Nb2O5, and TiO2 (taken together), but none of these constituents is dominant at a crystallographic site, which raises the question whether this mineral is distinct from dumortierite. The crystal structures of four samples from the three localities have been refined to R1 = 0.02—0.05. The results show dominantly: Al, Ta, and vacancies at the Al(l) position; Al and vacancies at the Al(2), (3) and (4) sites; Si and vacancies at the Si positions; and Sb, As and vacancies at the Sb sites for both Sb-poor (holtite I) and Sb-rich (holtite II) specimens. Although charge-balance calculations based on our single-crystal structure refinements suggest that essentially no water is present, Fourier transform infrared spectra confirm that some OH is present in the three samples that could be measured. By analogy with dumortierite, the largest peak at 3505-3490 cm-1 is identified with OH at the O(2) and O(7) positions. The single-crystal X-ray refinements and FTIR results suggest the following general formula for holtite: Al7-[5x+y+z]/3 (Ta,Nb)x□[2x+y+z]\3,BSi3-y(Sb,As)yO18-y-z(OH)z, where x is the total number of pentavalent cations, y is the total amount of Sb + As, and z ⩽ y is the total amount of OH. Comparison with the electron microprobe compositions suggests the following approximate general formulae Al5.83(Ta,Nb)0.50□0.67BSi2.50(Sb,As)0.50O17.00(OH)0.50 and Al5.92(Ta,Nb)0.25□0.83BSi2.00(Sb,As)1.00O16.00(OH)1.00 for holtite I and holtite II respectively. However, the crystal structure refinements do not indicate a fundamental difference in cation ordering that might serve as a criterion for recognizing the two holtites as distinct species, and anion compositions are also not sufficiently different. Moreover, available analyses suggest the possibility of a continuum in the Si/(Sb + As) ratio between holtite I and dumortierite, and at least a partial continuum between holtite I and holtite II. We recommend that use of the terms holtite I and holtite II be discontinued.