The residual melts that remained after the consolidation of the Jálama batholith crystallized to form a group of intra-granitic pegmatite dykes, which are hosted by its outermost facies (the External Unit), and the most evolved residual melts migrated through fractures to form the Cruz del Rayo field of pegmatite dykes, which are hosted by pre-Ordovician low-grade metasedimentary rocks. The increasing activity of phosphorus as magmatic differentiation took place led to the crystallization of primary phosphates, including members of the triplite–zwieselite and the amblygonite–montebrasite series. A strong albitization of the granitic and pegmatite rocks led to the replacement of the primary assemblage by other phosphates such as alluaudite. The influx of post-magmatic hydrothermal fluids, produced quartz veins, gave rise to the crystallizationof ore minerals and triplite, and altered the granites, aplites and pegmatites, replacing some of the phosphate minerals and feldspars and depositing goyazite, montebrasite and childrenite–eosphorite. The interaction of the residual hydrothermal fluids with those from the surrounding metamorphic rocks during later alteration events resulted in the influx of large quantities of Ca and Mg, and produced phosphate assemblages enriched in those elements. Finally, late goyazite, hydroxylapatite and an unidentified Fe-rich phosphate were formed as a result of supergene alterationby percolating meteoric waters, which added Ca, Sr and other elements into the system, and increased fO2.

Magnesium hydroxyfluoride, Mg(OH)F, has been synthesized by a subcritical hydrothermal route from a 1:1 molar mixture of brucite, Mg(OH)2, and sellaite, MgF2 with a rutile type structure, in excess water. Using a combination of synchrotron X-ray and time-of-flight neutron powder diffraction, the structure of Mg(OH)F has been solved in the diaspore space group Pnma with a = 10.116(3), b = 4.6888(10) and c = 3.0794(7) Å at ambient conditions. The most intense diffraction lines are [dobs (hkl) Iobs]: 2.291 (211) 10, 4.253 (101) 7, 1.747 (212) 7, 2.229 (401) 6 and 1.480 (610) (4) Å, with the largest d-spacing at 5.058 Å. Sharp infrared stretching bands are located at 3679 and 3645 cm–1, with a broader band at 3535 cm–1. The topology of the structure is intermediate between that of the OH and F endmembers, being derived through notional shearing nearly normal to the sheets of octahedra of the CdI2/Mg(OH)2-type structure. Further similar shearing at an interval 1/2a would lead to a Cd(OH)F-type structure, which is also related to the rutile structure type. The observations and model presented here indicate a close correlation between the structural properties of the endmembers and Mg(OH)F.

Natrotitanite, ideally (Na0.5Y0.5)Ti(SiO4)O, is a new mineral from the Verkhnee Espe rare-element deposit at the northern exo-contact of the Akjailyautas granite massif in the northern part of the Tarbagatai mountain range, Eastern Kazakhstan. Both the mineral and the name have been approved by the Commission on New Minerals, Nomenclature and Classification of the International Mineralogical Association (IMA 2010-033). Star-shaped aggregates of small short prisms of yellow or yellowish white (Na,Y,REE)-bearing titanite rimmed by thin (∼2 μm) rims of natrotitanite are embedded in yttrium-bearing fluorite and replace narsarsukite. Associated minerals are microcline, albite, quartz, riebeckite, aegirine, biotite, astrophyllite, rutile, zircon and elpidite. Natrotitanite is milky white to yellowish grey, transparent to translucent, and has a white streak and a vitreous lustre. It shows pale orange cathodoluminescence but does not fluoresce under ultraviolet light. It shows no cleavage or parting, and is brittle; the calculated density is 3.833 g cm–3. The indices of refraction, measured with the Bloss spindle stage for the wavelength 590 nm using a gel filter, are α = 1.904, γ = 2.030, and these values are in accord with the mean refractive index, 1.988, calculated from the Gladstone-Dale relation. Natrotitanite is monoclinic, C2/c, a = 6.5691(2), b = 8.6869(3), c = 7.0924(2) Å, β = 114.1269(4)°, V = 369.4(2) Å3, Z = 4, a:b:c = 0.7562:1: 0.8164. The seven strongest lines in the X-ray powder diffraction pattern [in the order d (Å), I, (hkl)] are as follows: 2.597, 10, (130); 3.248, 8, (11); 2.994, 6, (200); 1.641, 4, (330); 4.941, 3, (110); 1.498, 3, (400); 2.273, 3, (11). Chemical analysis by electron microprobe gave Nb2O5 1.28, SiO2 27.83, TiO2 35.00, SnO2 0.57, V2O3 0.36, Fe2O3 0.23, Y2O3 7.87, Ce2O3 0.83, Sm2O3 0.26, Gd2O3 0.46, Tb2O3 0.17, Dy2O3 2.45, Ho2O3 0.16, Er2O3 2.24, Tm2O3 0.50, Yb2O3 2.53, Nd2O3 0.35, Lu2O3 0.28, MnO 0.33, CaO 8.16, Na2O 5.55, F 1.52 O ≡ F –0.64, sum 98.71 wt.%. The resulting empirical formula is (Na0.39Ca0.32Y0.15Dy0.03Yb0.03Er0.03Ce0.01Ho0.01Tm0.01Gd0.01Nd0.01)Σ1.00(Ti0.95Nb0.02Sn0.01Fe3+0.01Mn0.01V0.01)Σ1.01Si1.01O4.00(O0.83F0.17), calculated on the basis of 3 cations per formula unit. The general formula is written as (Na,Ca,Y,REE)TiSiO4(O,F), and the endmember formula is (Na0.5Y0.5)Ti(SiO4)O.

The crystal structure of a composite optically continuous crystal of natrotitanite and (Na, Y)-bearing titanite was mounted on a Bruker D8 three-circle diffractometer equipped with a rotating anode generator (MoKα radiation), a multi-layer optics incident-beam path and an APEX-II CCD detector. The crystal structure was refined in space group C2/c to a final R1 index of 1.8%. Natrotitanite is isostructural with titanite, (Na + Y + REE) replacing Ca at the Ca site in the titanite structure.

Davidlloydite, ideally Zn3(AsO4)2(H2O)4, is a new supergene mineral from the Tsumeb mine, Otjikoto (Oshikoto) region, Namibia. It occurs as elongated prisms (∼10:1 length-to-width ratio) that are flattened on {010}, and up to 100 × 20 × 10 μm in size. The crystals occur as aggregates (up to 500 μm across) of subparallel to slightly diverging prisms lying partly on and partly embedded in fine-grained calcioandyrobertsite. Crystals are prismatic along [001] and flattened on {010}, and show the forms {010} dominant and {100} subsidiary. Davidlloydite is colourless with a white streak and a vitreous lustre; it does not fluoresce under ultraviolet light. The cleavage is distinct on {010}, and no parting or twinning was observed. The Mohs hardness is 3 – 4. Davidlloydite is brittle with an irregular to hackly fracture. The calculated density is 3.661 g cm–3. Optical properties were measured with a Bloss spindle stage for the wavelength 590 nm using a gel filter. The indices of refraction are α = 1.671, β = 1.687, γ = 1.695, all ±0.002; the calculated birefringence is 0.024; 2Vobs = 65.4(6)°, 2Vcalc = 70°; the dispersion is r < v, weak; pleochroism was not observed. Davidlloydite is triclinic, space group P1, with a = 5.9756(4), b = 7.6002(5), c = 5.4471(4) Å, α = 84.2892(9), β = 90.4920(9), γ = 87.9958(9)°, V = 245.99(5) Å3, Z = 1 and a:b:c = 0.7861:1:0.7167. The seven strongest lines in the X-ray powder diffraction pattern [listed as d (Å), I, (hkl)] are as follows: 4.620, 100, (011, 10); 7.526, 71, (010); 2.974, 49, (200, 01); 3.253, 40, (021, 120); 2.701, 39, (10, 002, 1); 5.409, 37, (001); 2.810, 37, (210). Chemical analysis by electron microprobe gave As2O5 43.03, ZnO 37.95, CuO 5.65, H2O(calc) 13.27, sum 99.90 wt.%. The H2O content and the valence state of As were determined by crystal structure analysis. On the basis of 12 anions with H2O = 4 a.p.f.u., the empirical formula is (Zn2.53Cu0.39)Σ2.92As2.03O8(H2O)4.

The crystal structure of davidlloydite was solved by direct methods and refined to an R1 index of 1.51% based on 1422 unique observed reflections collected on a three-circle rotating-anode (MoKα radiation) diffractometer equipped with multilayer optics and an APEX-II detector. In the structure of davidlloydite, sheets of corner-sharing (As5+O4) and (ZnO4) tetrahedra are linked by ZnO2(H2O)4 octahedra. The structure is related to that of parahopeite.

Rickturnerite, which has the ideal formula Pb7O4[Mg(OH)4](OH)Cl3, is a new mineral from Torr Works (Merehead) quarry, near the village of Cranmore in Somerset, United Kingdom. It occurs as pale emerald green to grey porous aggregates of disordered interwoven minute fibrous crystals with mereheadite, cerussite, calcite, aragonite, mimetite, hydrocerussite, “plumbonacrite” and an uncharacterized lead oxychloride, in cavities inside a manganite and pyrolusite pod. The crystals are typically less than 5 μm wide and 200 μm long, but they can reach 40 × 100 μm in cross-section and over 1 mm in length. The mineral is translucent with a vitreous lustre and each needle is brittle with an indistinct cleavage, breaking with a splintery fracture. The streak is white, the Mohs hardness ∼3 and the density calculated using the empirical formula 6.886 g cm–3. Electron microprobe analyses yielded PbO 87.7, MgO 1.79, CuO 0.14, Cl 6.62 wt.%; H2O was calculated on the basis of structural considerations as 2.27 wt.% totalling 97.02 wt.%. A charge-balanced formula, based on 12 anions, is Pb7.16Mg0.81Cu0.03Cl3.40H4.60O8.60. Rickturnerite is orthorhombic Pnma, with a = 5.8024(6), b = 22.717(2), c = 25.879(3) Å, V = 3411.2(6) Å3 and Z = 8. The diffraction pattern contains strong reflections that define a subcell with a = 5.8034(5), b = 11.3574(9), c = 12.939(2) Å, V = 852.9(6) Å3 (space group Pmm2 which is related to the real unit cell by the transformation matrix [100/020/002]), and weak reflections that correspond to doubled b and c parameters. Since the difference between the large and small cells is only in a number of split and low-occupancy positions in the disordered region of the structure we provide the description of the subcell structure. The five strongest lines in the X-ray powder diffraction pattern [listed as dobs (Å), Iobs, (hkl)] are as follows: 6.474, 100, (400); 3.233, 73, (107); 2.867, 57, (705); 5.636, 44, (011); 3.112, 31, (802). The crystal structure was solved by direct methods and refined using 1318 unique reflections to R1 = 0.063. The structure is composed of a fully ordered part consisting of double [O2Pb3]2+ chains of oxocentred [OPb4] tetrahedra extended along the b-axis, which together with Cl– ions form 2-dimensional blocks parallel to (001). In between these blocks, there is a disordered region containing ordered [Mg(OH)6]4– octahedra and low-occupancy Pb and OH sites with a slight degree of ordering; these produce the weak supercell reflections.

Carlosbarbosaite, ideally (UO2)2Nb2O6(OH)2·2H2O, is a new mineral which occurs as a late cavity filling in albite in the Jaguaraçu pegmatite, Jaguaraçu municipality, Minas Gerais, Brazil. The name honours Carlos do Prado Barbosa (1917–2003). Carlosbarbosaite forms long flattened lath-like crystals with a very simple orthorhombic morphology. The crystals are elongated along [001] and flattened on (100); they are up to 120 μm long and 2–5 μm thick. The colour is cream to pale yellow, the streak yellowish white and the lustre vitreous. The mineral is transparent (as individual crystals) to translucent (massive). It is not fluorescent under either long-wave or short-wave ultraviolet radiation. Carlosbarbosaite is biaxial(+) with α = 1.760(5), β = 1.775(5), γ = 1.795(5), 2Vmeas. = 70(1)º, 2Vcalc. = 83º. The orientation is X || a, Y || b, Z || c. Pleochroism is weak, in yellowish green shades, which are most intense in the Z direction. Two samples were analysed. For sample 1, the composition is: UO3 54.52, CaO 2.07, Ce2O3 0.33, Nd2O3 0.49, Nb2O5 14.11, Ta2O5 15.25, TiO2 2.20, SiO2 2.14, Fe2O3 1.08, Al2O3 0.73, H2O (calc.) 11.49, total 104.41 wt.%; the empirical formula is (□0.68Ca0.28Nd0.02Ce0.02)Σ=1.00[U1.44□0.56O2.88(H2O)1.12](Nb0.80Ta0.52Si0.27Ti0.21Al0.11Fe0.10)Σ=2.01 O4.72(OH)3.20(H2O)2.08. For sample 2, the composition is: UO3 41.83, CaO 2.10, Ce2O3 0.31, Nd2O3 1.12, Nb2 O5 14.64, Ta2O5 16.34, TiO2 0.95, SiO2 3.55, Fe2O3 0.89, Al2O3 0.71, H2O (calc.) 14.99, total 97.43 wt.%; the empirical formula is (□0.67Ca0.27Nd0.05Ce0.01)Σ=1.00[U1.04□0.96O2.08(H2O)1.92] (Nb0.79Ta0.53Si0.42Ti0.08Al0.10Fe0.08)Σ=2.00O4.00(OH)3.96(H2O)2.04. The ideal endmember formula is (UO2)2Nb2O6(OH)2·2H2O. Calculated densities are 4.713 g cm-3 (sample 1) and 4.172 g cm-3 (sample 2). Infrared spectra show that both (OH) and H2O are present. The strongest eight X-ray powder-diffraction lines [listed as d in Å (I)(hkl)] are: 8.405(8)(110), 7.081(10)(200), 4.201(9)(220), 3.333(6)(202), 3.053(8)(022), 2.931(7)(420), 2.803(6)(222) and 2.589(5)(040,402). The crystal structure was solved using single-crystal X-ray diffraction (R = 0.037) which gave the following data: orthorhombic, Cmcm, a = 14.150(6), b = 10.395(4), c = 7.529(3) Å, V = 1107(1) Å3, Z = 4. The crystal structure contains a single U site with an appreciable deficiency in electron scattering, which is populated by U atoms and vacancies. The U site is surrounded by seven O atoms in a pentagonal bipyramidal arrangement. The Nb site is coordinated by four O atoms and two OH groups in an octahedral arrangement. The half-occupied tunnel Ca site is coordinated by four O atoms and four H2O groups. Octahedrally coordinated Nb polyhedra share edges and corners to form Nb2O6(OH)2 double chains, and edge-sharing pentagonal bipyramidal U polyhedra form UO5 chains. The Nb2O6(OH)2 and UO5 chains share edges to form an open U—Nb—φ framework with tunnels along [001] that contain Ca(H2O)4 clusters. Carlosbarbosaite is closely related to a family of synthetic U–Nb–ϕ framework tunnel structures, it differs in that is has an (OH)-bearing framework and Ca(H2O)4 tunnel occupant. The structure of carlosbarbosaite resembles that of holfertite.

Granitic pegmatites are exceptional igneous rocks and the possible role of an immiscibility process in their origin is strongly debated. To investigate metal and metalloid behaviour in hydrous peraluminous systems (aluminium saturation index, ASI >1), we analysed 15 quartz-hosted primary melt and fluid inclusions from pegmatites in the Ehrenfriedersdorf Complex (Erzgebirge, Germany) and 26 primary melt inclusions from leucogranites of the Ehrenfriedersdorf district (Germany), Kymi (Finland) and Erongo (Namibia) by femtosecond laser ablation inductively coupled plasma quadrupole mass spectrometry. The results presented here for 32 elements provide evidence for metal and metalloid fractionation between two types of immiscible melts (A and B) and NaCl – HCl-rich brine in the pegmatite system. No evidence for the boundary layer effect was observed in the 40 – 500 μm size melt inclusions that were investigated. The data on the Ehrenfriedersdorf pegmatites allow quantification of the metal and metalloid partitioning between natural NaCl-rich brine and the two types of melt (e.g. KAsbrine/type-A,B melts = 0.01 – 1.7; KSbbrine/type-A,B melts = 10 – 285; KZnbrine/type-A,B melts ≥ 50; KPbbrine/type-A melt ≥ 50; KAgbrine/type-A melt = 46). These data are in accord with existing natural and experimental data on equilibrium fluid – melt partitioning as well as spectroscopic data on the metal and metalloid complexation in hydrous aluminosilicate melts and NaCl – HCl-rich fluids.

Natural onyx agate from Mali was investigated in an integrated mineralogical and chemical study to reveal the origin of the unusual black colouration. Detailed studies by polarizing microscopy, scanning electron microscopy and micro-Raman spectroscopy showed that the colour of the dark bands is related to the incorporation of small particles of carbon (low-crystalline graphite) up to 200 nm in size into the cryptocrystalline silica matrix. The dark bands have carbon contents of 1.88 wt.%. The location of the graphite particles is closely related to the primary structural banding in the chalcedony. Cathodoluminescence data shows that the banding is interrupted by small fissures containing secondary hydrothermal quartz. The carbon isotope composition (δ13C value of –31.1±0.2‰) of the carbonaceous material points to an organic precursor. Both the direct hydrothermal formation of graphite from methane under elevated temperature and the graphitization of organic precursors by secondary hydrothermal or metamorphic overprint are possible explanations for the colour of the dark bands. The graphitization of organic precursors results in an intense electron spin resonance line at geff = 2.0026.

The elastic and structural behaviour of dehydrated analcime in compression in a non-penetrating medium up to 3 GPa was studied in a diamond anvil cell using in situ synchrotron powder diffraction. A first-order phase transition at 0.4–0.7 GPa is accompanied by a symmetry change from monoclinic (I2/a) to pseudo-rhombohedral (R3) due to trigonalization of the aluminosilicate framework. This is due to the migration of cations to new positions close to the 6-membered rings forming the channels. The reduction of the mean aperture of the structure-forming 6- and 8-membered rings, as a result of tetrahedral tilting, leads to a 7.5% reduction in volume at the phase transition. The bulk modulus values are 38(2) GPa for the low pressure (LP) phase [fitted with a Murnaghan equation of state, K' = 4 (fixed)] and 11(4) GPa for the high pressure (HP) phase [fitted with a third-order Birch–Murnaghan equation of state, K' = 9(1)]. The elastic behaviour of the LP phase is anisotropic, with compressibilities βa:βb:βc in the ratio 1:4:2; the most compressible direction b coinciding with the orientation of empty 8-membered rings. The compressibility of the HP phase is isotropic. Trigonalization appears to be the most effective (and probably unique) mechanism of radical volume contraction for the ANA structure type.

A pink-purple diamond crystal from the Internatsional'naya kimberlite pipe (Siberia) was studied by single-crystal X-ray diffraction techniques using an area detector. Direct indexing of the diffraction pattern suggested a primitive hexagonal unit cell [ahex = 2.513(4), chex = 6.172(11) Å], instead of the well known face-centred cubic unit cell (acub ∼3.567 Å). Theoretical considerations and diffraction pattern simulation showed that the hexagonal diffraction pattern is the result of the superposition of two diffraction patterns with cubic symmetry due to spinel-law twinning along (111). These data are in good agreement with previous analyses of deformation microtwins in natural pink-purple diamonds using electron paramagnetic resonance spectroscopy and optical microscopy. The results suggest that natural epigenetic plastic deformation of diamonds occurs not only by dislocation slipping but also as a result of mechanical twinning.

The partitioning of Sr, Ba and Rb between alkali feldspar and melt has been determined at 0.1 GPa water vapour pressure, mainly on one Na-rich series and one K-rich series within the system nepheline-kalsilite-quartz. Experiments were also carried out with small amounts of the anorthite molecule or peralkaline components (Na, K metasilicates). The compositions of the alkali feldspars and coexisting quenched glasses were determined by electron microprobe analysis. Except for some peralkaline compositions, the crystal/liquid partition coefficients for Sr and Ba are always >1; the crystal/liquid partition coefficient for Rb is always <1. For sodic alkali feldspars DSr > DBa and for potassic feldspars DSr < DBa. Partition coefficients for Sr and Ba increase: (1) with decreasing temperature; (2) with increasing Or content of feldspar; (3) with increasing silica-undersaturation of the melt; (4) with decreasing peralkalinity. The variation in the value of DRb is less clear, but it is higher for K-rich feldspars. Multiple linear regression equations are fitted to correlate ln(D) with independent compositional and physical variables. Where rock/groundmass major-element data are available for felsic natural rocks, equations are recommended for obtaining reliable alkali feldspar partition coefficients for modelling fractional crystallization processes. The structural properties of silicate melts and crystal chemical relations are used to rationalize trends in partition coefficients.

Sodalites and sulfatic sodalites in holocrystalline K-feldspar-rich ejecta from the Somma Vesuvius volcanic complex, Italy, have been characterized by combined chemical, structural and spectroscopic analyses. Sodalite has a relatively homogeneous chemical composition, with the ubiquitous presence of CO32– and H2O/OH–. The sulfatic sodalites are isomorphous and have cage structures which can contain a wide variety of anions, molecular species and cations. Molecular CO2 and H2O/OH– are present in sulfatic sodalites, instead of the CO32– anions that are present in sodalite sensu stricto. The cell dimensions of the all of the studied sodalite samples are very similar, the sulfatic sodalite cell dimensions are more variable. Structure refinement of a distinctly green sample confirms the P3n space group. Metasomatic magma-derived fluids that are rich in H2O, CO2, Cl and S are believed to be responsible for the genesis of the relatively late-stage phases which form the ejecta containing the sodalite-group minerals.

Preliminary geological work on samples from Davdar in China indicate that emerald occurs in quartz veins hosted within upper greenschist grade Permian metasedimentary rocks including quartzite, marble, phyllite and schist. Fluid inclusion studies indicate highly saline fluids ranging from approximately 34 to 41 wt.% NaCl equivalent, with minimal amounts of CO2 estimated at a mole fraction of 0.003. Fluid inclusion, stable isotope and petrographic studies indicate the Davdar emeralds crystallized from highly saline brines in greenschist facies conditions at a temperature of ∼350°C and a pressure of up to 160 MPa. The highly saline fluid inclusions in the emeralds, the trace-element chemistry and stable isotope signatures indicate that the Davdar emeralds have some similarities to the Khaltaro and Swat Valley emerald deposits in Pakistan, but they show the greatest similarity to neighbouring deposits at Panjshir in Afghanistan.

Atomic force microscopy (AFM) enables in situ observations of mineral fluid reactions to be made at a nanoscale. During the past 20 years, the direct observation of mineral surfaces at molecular resolution during dissolution and growth has made significant contributions toward improvements in our understanding of the dynamics of mineral fluid reactions at the atomic scale. Observations and kinetic measurements of dissolution and growth from AFM experiments give valuable evidence for crystal dissolution and growth mechanisms, either confirming existing models or revealing their limitations. Modifications to theories can be made in the light of experimental evidence generated by AFM. Significant changes in the kinetics and mechanisms of crystallization and dissolution processes occur when the chemical and physical parameters of solutions, including the presence of impurity molecules or background electrolytes, are altered. Calcite has received considerable attention in AFM studies due to its central role in geochemical and biomineralization processes. This review summarizes the extensive literature on the dissolution and growth of calcite that has been generated by AFM studies, including the influence of fluid characteristics such as supersaturation, solution stoichiometry, pH, temperature and the presence of impurities.