The crystal structure of nechelyustovite, ideally Na4Ba2Mn1.5☐2.5Ti5Nb(Si2O7)4O4(OH)3F(H2O)6, a 5.447(1) Å, b 7.157(1) Å, c 47.259(9) Å, α 95.759(4)°, β 92.136(4)°, γ 89.978(4)°, V 1831.7(4) Å3, space group P, Z = 2, Dcalc. 3.041 g cm–3, from Lovozero alkaline massif, Kola Peninsula, Russia, has been solved and refined to R1 = 13.9% on the basis of 1745 unique reflections (Fo > 15σF). Electron microprobe analysis yielded the empirical formula (H20)6.01, Z = 2, calculated on the basis of 42 (O + F) a.p.f.u., H2O and OH are calculated from structure refinement (H2O = 6 p.f.u.; F + OH = 4 p.f.u.). The crystal structure of nechelyustovite is a combination of a TS (titanium silicate) block and an I (intermediate) block. The TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral). The TS block exhibits linkage and stereochemistry typical for Group III (Ti = 3 a.p.f.u.) of Ti-disilicate minerals: two H sheets connect to the O sheet such that two (Si2O7) groups link to the trans edges of a Ti octahedron of the O sheet. There are two distinct TS blocks of the same topology, TS1 and TS2, that differ in the cations of the O sheet, [(Na1.5Mn1☐0.5)Ti] and [(Na2Mn0.5☐0.5)Ti] (4 a.p.f.u.) respectively. The TS1 and TS2 blocks have two different H sheets, H1,2 and H3,4, where (Si2O7) groups link to [5]- and [6]-coordinated (Ti,Nb) polyhedra respectively. There are three peripheral sites, AP(1—3), occupied mainly by Ba (less Sr and K) at 96, 86 and 26% and one peripheral site AP(4) occupied by Na at 50%. There are two I blocks: the I1 block is a layer of Ba atoms; the I2 block consists of H2O groups and AP(3) atoms. TS blocks alternate with I blocks or link through hydrogen bonds (as in epistolite). There is a sequence of four TS blocks and three I blocks per the c cell parameter: TS2 — I1 — TS1 — I2 — TS1 — I1 — TS2.

Jurassic dykes of western Dronning Maud Land (Antarctica) form a minor component of the Karoo large igneous province. An extensive local dyke swarm intrudes Neoproterozoic gneisses and Jurassic syenite plutons on the margins of the Jutulstraumen palaeo rift in the Svedrupfjella region. The dykes were intruded in three distinct episodes (~204, ~176 and ~170 Ma). The 204 Ma dykes are overwhelminglylow-Ti, olivine tholeiites including some primitive (picritic) compositions (MgO >12 wt.%; Fe2O3 >12 wt.%; Cr >1000 ppm; Ni >600 ppm). This 204 Ma event precedes the main Karoo volcanic event by~25 Ma, so anycorrelations to the wider province are difficult to make. However, it mayrecord the earliest phase of rift activity along the Jutulstraumen. The 176 Ma dyke event is more intimately associated with the two syenite plutons. The dykes are alkaline (basanite/ tephrite) and were small-degree melts from an enriched, locallyderived source and underwent at least some degree of interaction with a syenitic contaminant. This ~176 Ma dyke event is widespread elsewhere in the Karoo (southern Africa and Dronning Maud Land). Later-stage (170 Ma) felsic (phonolite–comendite) dykes intrude the 176 Ma basanite–tephrite suite and represent the last phase of magmatic activityin the region.

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.

This paper reports an infrared spectroscopic study of a set of sodalite-group minerals. The specimens have been identified using a combination of X-ray diffraction and microchemical analysis. As expected, the Si/Al ratio is ~1; the extra framework cation content is characterized by a well-defined Na ⇌ (Ca+K) substitution. The lattice parameters of the studied samples range from sodalite (sample LM11) with a = 8.889(2) Å, to haüyne (sample HR3S) with a = 9.1265(2) Å. The specimens, having the SO2– group as a dominant anion, show a clear correlation between the a cell edge and the K content. Singlecrystal FTIR spectroscopy shows that haüyne and nosean typically contain enclathrated CO2 molecules, inadditionto H2O and minor carbonate, while sodalite is virtually CO2-free. Detailed microspectrometric mappings show a non-homogeneous distribution of volatile constituents across the crystals, which may be related to the presence of fractures in the crystals. Because of such zoning, a relatively wide variation is observed when calibrating extinction coefficients on the basis of a bulk analytical method such as CHN elemental analysis.

The crystal structure of tedhadleyite, ideally Hg2+Hg101+O4l2(Cl,Br)2,triclinic, AĪ, a 7.0147(5), b 11.8508(7), c 12.5985(8) Å, α 115.583(5), β 82.575(2), γ 100.619(2)º, V 927.0(2) Å3, Z = 2,was solved by direct methods and refined to an R1 index of 4.5% for 2677 unique reflections. There are six symmetrically distinct Hg sites in tedhadleyite: Hg(1) is occupied by Hg2+ and Hg(2–6) are occupied by Hg+ that forms three [Hg–Hg]2+ dimers with Hg–Hg separations between 2.527 and 2.556 Å. These [Hg–Hg]2+ dimers have strong covalent bonds to O atoms,forming pseudo-linear O–Hg–Hg–O arrangements,and weak bonds to halogen and O atoms at high angles to the dimer axis. The [O–Hg–Hg-O] groups share anions to form four-membered square rings of composition [Hg8O4] that link along [100] via [O–Hg–Hg-O] groups and along [001] via [O–Hg–O] groups, forming rectangular rings of composition [Hg14O8]. The rings form a corrugated layer that interweaves with a symmetrically related layer whereby the [O–Hg(6)–Hg(6)–O] linking groups of one layer pass through the centres of the square [Hg8O4] rings of the other layer to form [Hg11O4] complex slabs parallel to (010) that link through Hg-I and Hg-Br,Cl bonds.

Electron microprobe analyses are presented of chevkinite-group minerals from Canada, USA, Guatemala, Norway, Scotland, Italy and India. The host rocks are metacarbonates, alkaline and subalkaline granitoids, quartz-bearing pegmatites, carbonatite and an inferred K-rich tuff. The analyses extend slightly the range of compositions in the chevkinite group, e.g. the most MgO-rich phases yet recorded, and we report two further examples where La is the dominant cation in the A site. Patchily- zoned crystals from Virginia and Guatemala contain both perrierite and chevkinite compositions. The new and published analyses are used to review compositional variation in minerals of the perrierite subgroup, which can form in a wide range of host rock compositions and over a substantial pressure- temperature range. The dominant substitutions in the various cation sites and a generalized substitution scheme are described.

Concentrations of a series of trace elements of 14 quartz samples from various geological settings (hydrothermal, igneous, metamorphic) in Norway were determined by LA-ICP-MS. FTIR spectroscopy was applied to the same quartz crystals in order to determine the H concentrations and the speciation of H in the quartz lattice. A refined hypothetical charge neutrality equation is suggested, where the atomic ratio of (Al3+ + Fe3+ + B3+) to (P5+ + H+ + Li+ + Na+ + K+) should correspond to 1 for natural quartz crystals. The determined concentrations of Al, Fe, B, P, Li, K and OH- species confirm approximately the charge neutrality equation. The high H/(Li+K+P) ion ratio of igneous quartz compared to hydrothermal and metamorphic quartz, suggests that igneous quartz preferentially incorporates H as OH- in lieu of Li, K and P. The results confirm that the FTIR absorption of the OH- band at 3595 cm-1 is attributed to structural B defects in the quartz lattice. The dominating H impurity in most of the quartz samples is, however, molecular H2O. The molecular H2O is presumably related to waterbearing micro pores and not to visible fluid inclusions, because the spectra were recorded from microscopically clear crystals.

A new mineral, eldfellite, was found among fumarolic encrustations collected in 1990 on the Eldfell volcano, Heimaey Island, Iceland. Associated minerals are ralstonite, anhydrite, gypsum, bassanite, hematite, opal and tamarugite, as well as a presumably new mineral with the composition Na3Fe(SO4)3. Along with opal and tamarugite, eldfellite forms soft and fragile aggregates built of thin, platy crystals of micrometre size. The mineral is yellowish-green to greenish-white, with a white streak. The calculated density is 3.062 g/cm3. Eldfellite is monoclinic, C2/m, a 8.043(4) Å, b 5.139(2) Å, c 7.115(4) Å, β 92.13(2)º, Vuc 293.9(2) Å3, Z = 2 and is isostructural with yavapaiite[KFe (SO4)2]. The strongest lines in the powder diffraction diagram are [d (Å), I (relative to 10)]: 3.72, 8; 3.64, 5; 3.43, 5; 2.77, 10; 2.72, 6; 2.57, 3; 2.370, 6; 1.650, 3. Theche mical analysis and theX-ray diffraction data of eldfellite correspond to those of the synthetic compound NaFe(SO4)2.

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.

Zigrasite, ideally MgZr(PO4)2(H2O)4, is a new secondary phosphate mineral from the giant 1972 gem tourmaline-bearing pocket at the Dunton Quarry, Newry, Oxford County, Maine, USA. It occurs as subhedral blocky grains sometimes exceeding 1 mm in maximum dimension and perched on tourmaline. These grains are complex aggregates ofthree distinct phases, zigrasite and two unnamed phases: the Ca analogue of zigrasite, CaZr(PO4)2(H2O)4, and Zr(PO3OH)2(H2O)4. Zigrasite is associated with tourmaline, microcline, quartz, albite, beryl, amblygonite-montebrasite, childreniteeosphorite and apatite, and crystallized as one of the latest minerals during pocket formation. It is offwhite to pale yellow or light tan, translucent with a white streak and a vitreous lustre, and shows light blue to pale yellow cathodoluminescence. Mohs hardness is 3 and the measured and calculated densities are 2.76(4) and 2.66 g/cm3. The mineral has imperfect cleavage in two directions, parallel to (010) and (001), shows no parting, is brittle and has a hackly fracture. In transmitted light, it is colourless and non-pleochroic, biaxial negative with α 1.597(1), β 1.622 (1), γ 1.635 (1), with 2V(meas) = 65.5(4)º and 2V(calc.) = 71º. Zigrasite is triclinic, P , a 5.3049(2) Å, b 9.3372(4) Å, c 9.6282(5) Å, α 97.348(1)º, β 91.534(1)º, γ 90.512(4)º, V 472.79(5) Å3, Z = 2. The seven strongest lines in the X-ray powder diffraction pattern are as follows: d (Ê), I, (hkl): 9.550, 100, (001); 4.108, 70, ; 4.008, 50, (111); 4.589, 40, (110); 3.177, 40, (112); 3.569, 30, (0 2), 2.660, 30, (200),(11),(130); 3.273, 20, (12). Chemical analysis by electron microprobe gave P2O5 37.59, ZrO2 32.27, HfO2 0.34, FeO 0.20, MgO 10.37, ZnO 0.17, F 0.13, LOI 18.60, less O:F 0.05 = total 99.62 wt.%. The resulting empirical formula is (–)Σ=0.99(Zr0.99Hf0.01)Σ=1.00 P2.00O8(H2O)4 on the basis of12 O atoms with H2O = 4 per formula unit from crystal-structure analysis, and the end-member formula is MgZr(PO4)2(H2O)4.

Cathodoluminescence (CL) spectroscopy in an SEM has been used to investigate the point defect structure of clear natural α-quartz at 295 K. Cathodoluminescence processes and experimental factors that influence the CL spectra from α-quartz are investigated. Electron irradiation may induce changes in the average local crystal micro structure of quartz, locally transforming it to a less dense, amorphized state. The observed CL emissions are identified with a range of native and impurity defect centres including: interstitial molecular O at 0.968 eV; a charge-compensated substitutional Fe3+ impurity centre at —1.65 eV; a non-bridging oxygen hole centre (NBOHC) at 1.9 eV; an NBOHC with OH~ precursor at 1.95 eV; an NBOHC with a non-bridging impurity (e.g. Li+, Na+ or K+) precursor at — 1.9 eV; a radiative recombination of the self-trapped exciton (STE) associated with an E' centre in electron-irradiation-amorphized quartz at 2.3 eV; a radiative recombination of the STE associated with the E1' centre in α-quartz at 2.7 eV; a charge-compensated-substitutional Al3+ impurity centre at 3.3 eV; and a neutral relaxed O vacancy at 4.3 eV. In addition, unresolved contributions from O-deficient defects in electron-irradiation-amorphized SiO2 are likely at —2.7 and 4.3 eV.

Nyerereite and nahcolite have been identified as micro- and nano-inclusions in diamond from the Juina area, Brazil. Alongside them are Sr- and Ba-bearing calcite minerals from the periclase-wiistite series, wollastonite II (high), Ca-rich garnet, spinels, olivine, phlogopite and apatite. Minerals of the periclase- wustite series belong to two separate groups: wustite and Mg-wustite with Mg# = 1.9—15.3, and Fe- periclase and periclase with Mg# = 84.9—92.1. Wollastonite-II (high, with Ca:Si = 0.992) has a triclinic structure. Two types of spinel were distinguished among mineral inclusions in diamond: zoned magnesioferrite (with Mg# varying from 13.5—90.8, core to rim) and Fe spinel (magnetite). Olivine (Mg# = 93.6), intergrown with nyerereite, forms an elongate, lath-shaped crystal and most likely represents a retrograde transformation of ringwoodite or wadsleyite. All inclusions are composed of poly-mineralic solid mineral phases. Together with previously found halides, sulphates and other mineral inclusions in diamond from Juina, they form a carbonatitic-type mineral paragenesis in diamond which may have originated in the lower mantle and/or transition zone. Wustite inclusions with Mg# = 1.9—3.4, according to experimental data, may have formed in the lowermost mantle. The source for the observed carbonatitic-type mineral association in diamond is lower-mantle natrocarbonatitic magma. This magma may represent a juvenile mantle melt, or be the result of low-degree partial melting of deeply-subducted carbonated oceanic crust. This magma was rich in volatiles, such as Cl, F and H, which played an important role in the formation of diamond.

The Saghro Cenozoic lavas form a bimodal suite of nephelinites (with carbonatite xenoliths) and phonolites emplaced in the Anti-Atlas belt of Morocco. Despite the paucity of samples with intermediate composition between the two main types of lava (only one phonotephrite flow is reported in this area), whole-rock major element modelling shows that the two main lithologies can be linked by fractional crystallization. The most primitive modelled cumulates are calcite-bearing olivine clinopyroxenites, whereas the final stages of differentiation are characterized by the formation of nepheline-syenite cumulates. This evolution trend is classically observed in plutonic alkaline massifs associated with carbonatites. Late-stage evolution is responsible for the crystallization of hainite- and delhayelite-bearing microdomains, for the transformation of aegirine-augite into aegirine (or augite into aegirine-augite), and for the crystallization of lorenzenite and a eudialyte-group mineral as replacement products of titanite. These phases were probably formed, either by crystallization from late residual peralkaline melts, or by reaction of pre-existing minerals with such melt, or hydrothermal peralkaline fluid.

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.

Steverustite, ideally Pb52+(OH)5[Cu+(S6+O3S2–)3](H2O)2, is a new supergene mineral from the Frongoch mine dump, Devils Bridge, Ceredigion, Wales. It generally forms fibrous fan-like bundles that occur in small cavities in quartz veins with other supergene species. Crystals are fibrous to acicular, elongated along [010], and are bounded by (h0l) faces too small to index reliably. It is transparent, colourless to white with a white streak, has a vitreous lustre, does not fluoresce under ultraviolet light and is brittle with a splintery fracture. The calculated density is 5.150 g/cm3, and the calculated mean refractive index is 1.94. The mineral is monoclinic, P21/n, a 12.5631(7), b 8.8963(5), c 18.0132(11) Å, β 96.459(1)º, V 2000.5(3) Å3, Z = 4, a:b:c = 1.41217:1:2.02480. The seven strongest lines in the X-ray powder diffraction pattern are as follows: d (Å), I, (h k l): 3.934, 10, (Ī14); 3.934, 8, (Ī11); 3.348, 7, (313); 6.211, 6, (200); 4.797, 6, (211); 3.026, 6, (314); 2.837, 5, (016). Chemical analysis by electron microprobe gave PbO 72.59, SO3 15.78, Cu2O 4.47, S2– 6.32, H2O 4.83, O=S2– –3.15, total 100.84 wt.% where the amount of H2O was determined by crystal-structure analysis. The resulting empirical formula is Pb4.992+Cu0.96+(S6+O3S2–)3.03(OH)4.88(H2O)1.67, based on O + OH + H2O + S2– = 18.67 a.p.f.u. (atoms per formula unit) with H2O = 1.67 a.p.f.u. (from crystal-structure solution and refinement).

The crystal structure of steverustite was solved by direct methods and refined to R1 = 2.7% for 3366 unique (Fo > 4σF) reflections. There are five distinct Pb2+ cations with coordination numbers from [8] to [11], all of which show stereoactive lone-pair behaviour and which form a strongly bonded cluster of composition [Pb5(OH)5]. There is one Cu+ cation triangularly coordinated by three S2– atoms that belong to three thiosulphate groups, forming a Cu+(S6+O3S2–)3 group. The [Pb5(OH)5] units and [Cu(S2O3)3] groups occur at the vertices of interpenetrating 36 nets to form layers of composition [Pb5(OH)5Cu(S2O3)3] parallel to (010) which are linked by weaker bonds. Examination of the stereochemistry of thiosulphate and thionate structures shows that the combination of <S–O> and S–S distances are distinct for these two types of structures.

The dehydration of pure and waste gypsums has been examined using in situ synchrotron angledispersive X-ray diffraction. Pure gypsum was studied under a number of defined environments; various industrial waste gypsums were also studied under a common standard environment. It is found that the dehydration of gypsum to anhydrite proceeds via the hemihydrate and γ-anhydrite phases and the interplay and behaviour of these phases has been determined by full structural ‘Rietveld’ refinement. In the study of the pure gypsum system, the hemihydrate structure is shown to be preserved as water is lost. A ‘zero-water hemihydrate’ is observed before refinement in the higher symmetry γ-anhydrite cell is possible. The waste gypsum materials studied showed significant differences in the temperatures at which key transformation events occurred; these observations raise implications concerning the re-use of by-product gypsum materials. Finally, high temperature data are re-examined in the search for a variation of the anhydrite structure.

The chemical composition oft he natural arsenate-apatite mineral johnbaumite [nominally Ca10(AsO4)6(OH)2] and its alteration product hedyphane [Ca4Pb6(AsO4)6Cl2] have been determined by electron microprobe analysis and the structures ofjohnbaumite and synthetic Sr-, Ba- and Pbarsenate apatites have been studied by As K-edge X-ray absorption spectroscopy and synchrotron X-ray powder diffraction. All samples belong to the holosymmetric apatite space group P63/m with As5+ substituted for P5+ in the tetrahedral structural site. Johnbaumite contains small amounts ofF and Pb (~0.9 and ~4.4 wt.% respectively) and hedyphane has the ideal composition (formula given above); the compositions of these coexisting phases define the two limbs ofa solvus occurring between Ca- and Pb-arsenate apatite end members. The unit-cell parameters and cation–oxygen bond lengths for the arsenate apatites studied are discussed alongside published data for end-member Ca-, Sr-, Ba- and Pbphosphate apatite analogues with (OH), F, Cl or Br as the anions at the centres of the channels in the apatite structure. This discussion rationalizes the relationships between the two structural sites A(1) and A(2) occupied by divalent cations in terms of the size of the A–O polyhedra and the distortion of the A(1)–O polyhedron as measured by the metaprism twist angle [O(1)–A(1)–O(2) projected onto (001)].

The crystal structure of Ba2F2(S6+O3S2–), a natural thiosulphate weathering product of old smelting slags at the Surrender Mill, Yorkshire, England, UK, has been solved to R1 = 0.88% for 399 unique [Fo > 4α F] reflections and 0.91% for all 407 reflections. The compound is monoclinic, C2/m, a 15.3172(5), b 4.5898(1), c 4.6320(2) Å, β 101.449(1)º, V 319.17(2) Å3. The structure of Ba2F2(S6+O3S2–) consists of BaF2Ba layer fragments of the fluorite-type structure of frankdicksonite (BaF2) parallel to (100) alternating with layers of thiosulphate groups. The layer sequence in one unit cell is (S6+O3S2–)-BaF2Ba-(S6+O3S2–)-BaF2Ba. The structure resembles that of grandreefite, Pb2F2SO4.

The first single-crystal structure refinement of aschamalmite (Pb6Bi2S9) from Susa Valley (Piedmont, Italy) is reported. The mineral is monoclinic, C2/m, a = 13.719(1) Å, b = 4.132(1) Å, c = 31.419(3) Å, β = 90.94(1)º, V = 1 780.8(4) A ˚3, Z = 4. The Pb6Bi2S9 compound crystallizes also in an orthorhombic form as heyrovskyite (Cmcm) and our study is focused on understanding the reason leading to a change in symmetry. The aschamalmite structure forms because of ordering between Pb and Bi on the margins of the two octahedral layers that are symmetrically equivalent in heyrovskyite. The two alternate set of octahedral slabs are not related by a crystallographic mirror plane and the symmetry decreases to monoclinic. The cation ordering couples opposite sequences of Pb and Bi octahedra at the margins of slabs. In particular,the succession [Me4A]Bi-[Me5A]Pb-[Me4A]Bi-[Me5A]Pb faced to the series [Me4B]Pb- [Me5B]Bi-[Me4B]Pb-[Me5B]Bi occurs in about 70% of the unit-cells of the crystal,while the contrary sequence ([Me4A]Pb-[Me5A]Bi-[Me4A]Pb-[Me5A]Bi faced to [Me4B]Bi-[Me5B]Pb-[Me4B]Bi-[Me5B]Pb) occurs in the remaining unit-cells. The marginal octahedra have ideal populations (a.p.f.u.): [Me4A]1.40Bi+0.60Pb, [Me4B]1.40Pb+0.60Bi, [Me5A]1.40Pb+0.60Bi, [Me5B]1.40Bi+0.60Pb,in agreement with our structurerefinement results.

The probable site populations for pure heyrovskyite have been proposed,as well as the reasons that prevent the formation of a completely ordered monoclinic phase.

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.