ABSTRACT Shakhdaraite-(Y), ideally ScYNb2O8, is a new mineral from the Leskhozovskaya miarolitic granitic pegmatite at the Shakhdara River, southwestern Pamir (Tajikistan). Shakhdaraite-(Y) occurs mainly as grains from 10 to 150 μm in size in a near-miarolitic pegmatite complex in association with quartz, albite, pyrochlore-microlite, fersmite, and an unnamed Sc-Nb oxide; only one large, single, well-shaped crystal 200 μm long was found in a small cavity with quartz, albite, bertrandite, pyrochlore, and jarosite. Shakhdaraite-(Y) is black to dark-brown, streak is brown. Luster is vitreous semi-metallic. It is brittle with conchoidal fracture. Mohs hardness is 5. VHN100 = 436 kg/mm2. Dcalc. = 5.602 g/cm3. In reflected light, it is light gray and its reflective capacity is moderate to low. Anisotropy is distinct, without color effects. Pleochroism was not observed. Internal reflections are red-brown. Reflectance values were measured in air with SiC as reference material [λ(nm), Rmax, Rmin]: 470, 14.6, 13.9; 546, 14.0, 13.4; 589, 13.9, 13.3; 650, 13.8, 13.1. Electron probe microanalysis (WDS mode, 7 points) gives (wt.%): Nb2O5 50.70; Ta2O5 4.52; TiO2 0.08; WO3 0.79; SnO2 1.54; CaO 1.01; Sc2O3 11.35; MnO 1.38; FeO 0.01; Y2O3 12.00; Ce2O3 0.21; Pr2O3 0.04; Nd2O3 0.27; Sm2O3 0.32; Eu2O3 0.07; Gd2O3 0.86; Tb2O3 0.22; Dy2O3 2.07; Ho2O3 0.29; Er2O3 1.33; Tm2O3 0.35; Yb2O3 2.80; Lu2O3 0.32; PbO 0.24; ThO2 1.90; UO2 3.30, total 97.97. The empirical formula of shakhdaraite-(Y) based on O = 8 apfu (atoms per formula unit) is (Nb1.91Sc0.83Y0.53Ta0.10Mn0.10Ca0.09 Yb0.07U4+0.06Dy0.06Sn0.05Th0.04Er0.03Gd0.02W6+0.02Pb0.01Ce0.01Nd0.01Sm0.01Tb0.01Ho0.01Tm0.01Lu0.01Ti0.01)Σ4.00O8, Z = 2. The simplified formula is Sc(Y,Yb)Nb2O8, where Yb is the dominant lanthanoid. Shakhdaraite-(Y) is monoclinic, space group P2/c, a 9.930(2), b 5.6625(11), c 5.2108(10) Å, β 92.38(3)°, V 292.7(5) Å3, Z = 2. The crystal structure was solved by direct methods [R1 = 0.0269, 878 unique reflections (F > 4σF)]. There are three cation M sites: [6]M(1) = Nb2apfu, [6]M(2) = Sc apfu, and [8]M(3) = Y apfu, ideally M = ScYNb2apfu. The M(1) and M(2) octahedra each form a brookite chain along c. The Y-dominant [8]M(3A) polyhedra form a brookite-like kinked chain, and each M(3A) polyhedron of one brookite-like chain shares two edges with the two M(3A) polyhedra from the adjacent brookite-like chain, thus forming a [Y2O8]10– layer. In the structure of shakhdaraite-(Y), M(1A) and M(2) brookite chains and a layer of [8]-coordinated M(3A) polyhedra alternate along a. Shakhdaraite-(Y) is isostructural with samarskite-(Y), ideally YFe3+Nb2O8. Shakhdaraite-(Y) [Russian Cyrillic: шахдараит-(Y)] is named after its type locality: the valley of the Shakhdara River in the southwest of the Pamir Mountains.
ABSTRACT The Jinbaoshan platinum group element-(Cu)-(Ni) deposit in southwest China is a sulfide-poor magmatic platinum-group element deposit that experienced multiple phases of post-magmatic modification. The sulfide assemblages of most magmatic Ni-Cu-platinum-group element deposits in China and elsewhere in the world are dominated by pentlandite-pyrrhotite-chalcopyrite with lesser magnetite and minor platinum-group minerals. However, Jinbaoshan is characterized by (1) hypogene violarite-pyrite 1-millerite-chalcopyrite and (2) supergene violarite-(polydymite)-pyrite 2-chalcopyrite assemblages. The platinum-group minerals are small (0.5–10 μm diameter) and include moncheite Pt(Te,Bi)2, mertieite-I Pd11(Sb,As)4, the atokite Pd3Sn – rustenburgite Pt3Sn solid solution, irarsite IrAsS, and sperrylite PtAs2 hosted mainly by violarite, silicates (primarily serpentine), and millerite. The platinum-group minerals occur in two sulfide assemblages: (1) mertieite-I-dominant (with irarsite, palladium, and Pd-alloy) in the hypogene assemblage and (2) moncheite-dominant (with irarsite, sperrylite, and atokite) in the supergene assemblage. Palladium and intermediate platinum-group elements (Os, Ir, Ru) are concentrated mainly in violarite, polydymite, and pyrite 2. Platinum is seldom hosted by base metal sulfides and occurs mainly as discrete platinum-group minerals, such as moncheite, sperrylite, and merenskyite. Violarite and polydymite in the Jinbaoshan deposit contain more Pb-Ag than pentlandite and pyrrhotite in the Great Dyke and Lac des Iles deposit. The formation of the sulfide assemblages in Jinbaoshan can be interpreted to have occurred in three stages: (1) a magmatic Fe-Ni-Cu sulfide melt crystallized Fe-Ni monosulfide and Cu-rich intermediate solid solutions, which inverted to a primary pyrrhotite-pentlandite-chalcopyrite-magnetite assemblage; (2) an early-secondary hypogene voilarite-millterite-pyrite 1-chalcopyrite assemblage formed by interaction with a lower-temperature magmatic-hydrothermal deuteric fluid; and (3) a late-secondary supergene violarite-polydymite-pyrite 2-chalcopyrite assemblage formed during weathering. Late-magmatic-hydrothermal fluids enriched the mineralization in Pb-Ag-Cd-Zn, which are incompatible in monosulfide solid solution, added Co-Pt into violarite, and expelled Pd to the margins of hypogene violarite and millerite, which caused Pd depletion in the hypogene violarite and the formation of mertieite-I. Supergene violarite inherited Pd and intermediate platinum-group elements from primary pentlandite. Thus, the unusual sulfide assemblages in the Jinbaoshan platinum-group element-(Cu)-(Ni) deposit results from multiple overprinted post-magmatic processes, but they did not significantly change the chalcophile element contents of the mineralization, which is interpreted to have formed at high magma:sulfide ratios (R factors) through interaction of crustally derived sulfide and a hybrid picritic-ferropicritic magma derived from subduction-metasomatized pyroxenitic mantle during impingement of the Emeishan plume on the Paleo-Tethyan oceanic subduction system.
ABSTRACT The existing classification of pyrochlore group minerals is essentially based on the dominant valence rule. However, coupled heterovalent-homovalent substitutions at the A-, B-, and Y-sites commonly result in charge-imbalanced endmember formulae. The application of the site total charge (STC) method permits the determination of a charge-balanced endmember. Species names are assigned by using the dominant constituent rule. According to the current IMA nomenclature scheme, some previously established pyrochlore species, such as kalipyrochlore, strontiopyrochlore, bariopyrochlore, plumbopyrochlore, ceriopyrochlore, yttropyrochlore, bismutopyrochlore, and uranpyrochlore, are all grouped as zero-valent-dominant pyrochlores, resulting in the loss of petrogenetic information. In this work, the zero-valent-dominant pyrochlores of the pyrochlore group (sensu stricto) are classified into R+-, R2+-, R3+-, and R4+-pyrochlores where the respective cations (R) are the dominant valencies at the A- and Y-sites (for R+-pyrochlores) after vacancies (□) and H2O. The endmember charge arrangements are determined by the STC method to obtain charge-balanced endmember formulae for all possible zero-valent pyrochlore species. It is recommended that suitable adjectival modifiers be used along with the species name to emphasize the abundance of certain cations, which may or may not be reflected in the endmember formula. This approach would facilitate the usage of pyrochlore group minerals for all practical petrological and exploration purposes. It is considered that pyrochlores with significant A-site vacancies do not necessarily reflect formation in a supergene environment, as such pyrochlores can also form in hydrothermal parageneses.
ABSTRACT X-ray diffraction experiments were carried out with protoenstatite, chemical composition Mg2Si2O6, in order to clarify the conditions under which protoenstatite can be retained at room temperature. Our results show that grain size, cooling rate, and shear stress during sample preparation clearly affect the transition from protoenstatite to clinoenstatite. Smaller protoenstatite grains were more likely to be retained, and the relationship between the retained volume ratio of the protoenstatite and grain size was statistically consistent with martensitic nucleation. The most protoenstatite was retained in the experiment using a cooling rate of 3 °C/min; the retained volume ratio decreased in experiments with both faster and slower cooling rates. The martensitic transformation of protoenstatite to clinoenstatite is promoted by shear stress caused by a fast cooling rate. Shear stress caused by grinding and polishing also promotes the transformation, but ion milling, used to prepare samples for transmission electron microscope observation, leaves the protoenstatite unchanged. Therefore, samples including protoenstatite should be prepared without producing shear stress so that the protoenstatite can be observed.
ABSTRACT Silica-rich garronite-Na was found together with epistilbite in Miocene basaltic rock from Shiratobana, Hirado Island, Nagasaki Prefecture in Japan for the first time. Garronite-Na occurs as an anhedral crystal that covers the center of a small cavity in altered basaltic rock, whereas the epistilbite covers the inside of the cavity. Electron probe microanalysis of the garronite-Na gives an empirical formula of (Na1.99K0.27)Σ2.26Ca1.61(Fe0.01Al5.31Si10.64)Σ15.96O32·14.3H2O on the basis of O = 32. Its Na/Ca molar ratio varies from 1.00 to 1.53, and its unit-cell parameters (space group I2) calculated from X-ray powder diffraction data are a = 9.983(11) Å, b = 10.089(14) Å, c = 10.070(10) Å, and β = 90.223(3)° with a calculated density of 2.183 g/cm3. Garronite-Na from Hirado Island formed from an alkaline high-silica solution in the later stages of hydrothermal zeolitization associated with volcanic activity.
The Huzyk Creek area is situated along the boundary between the Reindeer Zone and the Superior Boundary Zone of the Paleoproterozoic Trans-Hudson Orogen, where the Precambrian rocks are overlain by Phanerozoic cover. Two drill holes intersect graphite schist that is enriched in V, as well as U, Zn, Mo, and Cu, and is hosted by a metamorphosed wacke-mudstone sequence interleaved with variably altered mafic rocks. Whole-rock lithogeochemistry and Sm-Nd isotope chemistry suggest that the wacke-mudstone package is related to the turbidite-derived Burntwood Group of the Kisseynew Domain and was likely deposited relatively proximal to the Flin Flon arc-collage. A model is proposed in which redox-sensitive metals were leached from rocks of the Flin Flon arc-collage during weathering under oxidizing conditions. The metals were transported in oxygenated surface run-off draining the arc-collage and discharged into the Kisseynew Basin. Shallow waters of the Kisseynew Basin were likely oxygenated and biologically productive; however, the basin was likely euxinic at mid-depths. The mixing of the metal-enriched, oxygenated water with organic matter and euxinic water resulted in the reduction of the redox-sensitive metals and the formation of insoluble organometallic complexes and particles. A highstand, or period of tectonic quiescence, likely halted turbidite deposition and allowed for the settling organic and metal-rich particles to create relatively thick deposits. Burial and metamorphism resulted in the organic-rich material being transformed into graphite, while Mo, Cu, and Zn were partitioned into sulfides. The mineral hosts of V and U are not known at this time. The model calls for the fractionation of redox-sensitive metals from the water column shortly after discharge into the Kisseynew Basin and implies that graphitic horizons in relatively close proximity to the Flin Flon arc-collage have a greater potential for metal enrichment than graphite deposits farther removed from the arc. This model could apply to basins of similar metamorphic grade, age, and tectonic setting around the globe.
ABSTRACTPotassic alteration is a common feature in hydrothermal ore systems, and both its occurrence and degree can be important features applicable to ore deposit exploration. Here we report results from optical cathodoluminescence (CL) and chemical composition investigations on K-feldspar of different origins in and around the Early Cretaceous lode gold deposits in the Xiaoqinling area, located along the southern margin of the North China Craton.We focus on K-feldspars from an Early Cretaceous biotite monzogranite (G-Kfs), a Paleoproterozoic migmatite (M-Kfs), and a hydrothermal alteration zone of Early Cretaceous gold deposits (H-Kfs). The grain size of G-Kfs ranges from 1 to 4 mm, usually exhibits tartan twinning, and occasionally shows evidence of exsolution. Part of the M-Kfs exhibits tartan twinning, and the grain size shows wide variation (from tens of microns to several centimeters), while the H-Kfs shows no twinning, and the grain size is generally less than 0.5 mm.Optical CL analyses show that the G-Kfs exhibits two emission bands at around 466–472 and 708–713 nm which occur in multiple, alternating dark red and blue zones. The M-Kfs exhibits blue, red, and/or violet-red luminescence resulting from two emission bands at 446–465 and 694–701 nm. The H-Kfs displays a distinct greenish-yellow luminescence resulting from an emission band at 545–550 nm.Electron probe microanalyses show that among the three K-feldspar types, the G-Kfs contains higher Na2O (average: 0.71 wt.%) and Al2O3 (average: 18.79 wt.%) and lower K2O (average: 15.62 wt.%), whereas the H-Kfs shows higher K2O (average: 16.31 wt.%) and lower Na2O (average: 0.45 wt.%) and Al2O3 (average: 18.61 wt.%). The K2O, Na2O, and Al2O3 contents of the M-Kfs are intermediate between those of the G-Kfs and H-Kfs. In transitioning from the G-Kfs, M-Kfs, to H-Kfs, it is noted that the concentrations of Sr, Ba, and Pb decrease progressively, whereas W, V, Zn, Mn, Sc, Ge, and Ga gradually increase. Concentrations of La, Ce, and Eu in the H-Kfs are lower than in the G-Kfs and M-Kfs, and the Cr and Cu concentrations in the G-Kfs are the lowest. Scatter diagrams constructed with Sr, Ba, Pb, and Rb concentrations show that the three types of K-feldspars fall into different fields. These, as well as the CL and spectral properties of K-feldspar, can clearly distinguish the K-feldspars of magmatic, metamorphic, and hydrothermal origin in the study area.
ABSTRACTThe abundance of Ru in chromite has been suggested as an indicator of sulfide liquid saturation in komatiites. The komatiite magma-derived Archean Coobina intrusion is known to be barren in terms of sulfide mineralization. Therefore, the Coobina intrusion can serve as a useful case study to test the applicability of Ru abundance in chromite as a potential indicator for sulfide mineralization, as well as for better understanding the PGE-chromite association in general.The Coobina intrusion is a highly deformed layered intrusion interpreted to be a flared dike. It contains multiple massive chromitite seams that have been recently mined for metallurgical-grade chromite. In this study, 18 samples from chromitite seams throughout this intrusion are investigated for their whole-rock platinum group element (PGE) contents, which are compared to their chromite mineral chemistry (including PGE content), the platinum group mineral (PGM) mineralogy, and Re-Os isotope systematics. Each sample has a similar chromite major and minor element chemistry, but a unique trace element signature, even within the same seam. In general, there are higher concentrations of Ru (>300 ppb) within chromite in the southeast (toward the feeder dike) and lower concentrations (<50 ppb Ru) in the northwest. At a sample scale, Ru in the whole rock and Ru in solid solution in the chromite are inversely correlated, while Ir shows a positive correlation between the whole rock and chromite mineral chemistry, indicating differing partitioning behaviors within the iridium-group PGE (IPGE = Os, Ir, Ru). The inverse correlation between Ru in solid solution within chromite and Ru in whole-rock chromitite suggests that, for seams with high Ru in whole rock, Ru is occurring within separate PGM phases. This is supported by the observation that the samples with high whole-rock Ru also have a high number of visible metal alloy and/or PGM inclusions. Although these inclusions are not necessarily Ru-rich phases, their presence suggests that there is a preference for these samples to form nuggets, which may restrict Ru partitioning into the chromite crystal structure. We suggest that the low Ru values in the Coobina chromite are a result of transient sulfide saturation. The Re-Os isotopic composition of the Coobina chromitite is chondritic [γ187Os(3.189 Ga) = −0.63 ± 0.21] and is consistent with derivation of the Coobina parental magma from the convecting upper mantle source, providing evidence for the mantle origin of the Coobina PGE inventory.If using chromite as a detrital indicator mineral for magmatic sulfide exploration, it must be kept in mind that transient sulfide saturation within chromitite seams may give a false positive signature.
ABSTRACT The Wekusko Lake pegmatite field in central Manitoba, Canada, is known for its multiple pegmatite dike occurrences, most remarkably its Li-rich pegmatites of economic importance. The Li-rich pegmatites from Wekusko Lake are the focus of this study and belong to the Green Bay group of the Wekusko Lake pegmatite field. These dikes were dated at ca. 1.78 Ga and were emplaced early during the D4 brittle–ductile deformational event. The results presented here describe in detail the pegmatite mineralogy, textures, and zonation of the Li-rich dikes of the Green Bay group, with emphasis on white mica chemistry. The aim of this study is to establish the nature and evolution of white micas from the Li-rich pegmatites of the Wekusko Lake pegmatite field in Manitoba. We aim to understand the differentiation mechanisms that allowed the high level of trace element enrichment observed in the white micas of the studied Li-rich pegmatites. Major and trace elements in white micas from a representative and well studied pegmatite dike were analyzed by electron microprobe and LA-ICP-MS. White mica compositions and textural evidence were used to define two different populations that seem to have been affected by magmatic processes (fractional crystallization) and a secondary episode of metasomatism. Fractional crystallization modeling of a granitic melt can explain some of the trace element enrichment, but extreme Cs enrichment cannot be explained via this mechanism. We interpret that many metasomatic white micas crystallized in boundary layers. Their compositions are controlled by the local melt composition, but aqueous fluids likely contributed to the development of the white mica textures. The substitution mechanisms at play depend on the type of trend and on the stage of evolution. Li enrichment without M2+ enrichment in metasomatic white mica grains is observed, and it is postulated that Fe3+ in white mica explains this behavior. The K/Rb ratio decreases in white micas with fractionation, whereas the concentrations of incompatible elements, such as Cs, Rb, Tl, Ta, and Li, increase. At Wekusko Lake, the Nb and Ta contents seem to be controlled in part by the presence of columbite group minerals and in part by crystallization in boundary layers.
ABSTRACTThe Storkwitz carbonatite breccia, located near Delitzsch, Germany, is one of the few European domestic rare earth elements (REE) deposits, but is relatively understudied owing to more than 100 m of Cenozoic sedimentary cover. We present the results of a petrological investigation of the recently acquired ∼700 m-deep SES 1/2012 borehole. The Storkwitz breccia is composed of clasts of country rock and carbonatite ranging from <1 mm to ∼30 cm in size, cemented by ankeritic carbonatite. Extensive fenitization and biotitization mainly affects clasts of coarse-grained granitoids and medium-grained dolomite-calcite-carbonatites. An intersection of Storkwitz breccia at 425 m to 542 m contains local REE enrichment up to ∼1.7 wt.%. total rare earth oxides, which is predominantly contained in a REE-fluorcarbonate bearing mineral assemblage. The assemblage locally forms irregularly shaped vug-like features and rare hexagonal pseudomorphs in clasts of fine-grained ankerite-carbonatite. The REE-fluorcarbonate mineral assemblage formed prior to brecciation in the ankerite-carbonatite, which paragenetically fits with recent experimental and fluid inclusion data demonstrating the importance of late magmatic processes in forming carbonatite-hosted REE mineralization, possibly from an evolved ‘brine-melt' phase. Our findings indicate that minor REE recrystallization and redistribution occurred during late-stage hydrothermal or supergene processes, without leading to significant REE enrichment in the upper part of the breccia compared to the lower part. Cross-cutting faults represent the last deformation event and post-date carbonatite intrusion and fenitization. They may represent important conduits for late-stage hydrothermal or supergene fluids responsible for recrystallization of the breccia matrix to a cryptocrystalline oxide mineral assemblage. Our findings highlight the importance of REE enrichment in late-stage ‘brine-melt' phases through magmatic fractionation and in situ hydrothermal replacement.
ABSTRACT Weathering processes superimposed onto exhumed hydrothermal ore deposits in western North America have developed secondary mineral assemblages that inform the near-surface evolution of these systems within the context of Basin and Range extension. The occurrence of the secondary phosphate mineral turquoise [CuAl6(PO4)4(OH)8·4H2O] in the weathering profile of Laramide porphyry copper deposits is widely documented, although previous studies on the composition and distribution of turquoise are largely restricted to the archaeological literature. In this study, we use the world-class Butte porphyry-epithermal system to study the occurrence, paragenesis, and mineral chemistry of turquoise and related phosphates in the weathering profile of the deposit. Field observations, mineral textures by optical microscopy, electron microprobe analyses, and geochemical modeling show that blue, Al-endmember turquoise formed exclusively at or immediately below the pre-mining water table, within the chalcocite enrichment blanket and in the absence of significant FeIII. At higher structural levels above the pre-mining water table, green FeIII-bearing turquoise [Cu(Al,FeIII)6(PO4)4(OH)8·4H2O] is commonly intergrown with jarosite and/or tinticite at the micron scale. We show that jarosite, tinticite, and FeIII-bearing turquoise formed at the expense of pre-existing, Al-endmember turquoise after extensional faulting caused a relative lowering of the water table in the eastern fault block of the deposit. The low solubility of the FeIII-phosphates tinticite and strengite in the leach cap environment suggests that it is unlikely that these minerals formed directly from oxidized meteoric water. Electron probe microanalysis documented the presence of As and F in blue Al-endmember turquoise and Cl in green FeIII-bearing turquoise. The presence of Cl in FeIII-bearing turquoise may represent an evaporitic signal associated with basin development as the Butte district was exhumed. The paragenesis of Cu- and Fe-phosphate minerals provides another tool with which to interrogate spatial and temporal relationships in the near-surface evolution of porphyry copper systems.
ABSTRACTThe increasing demand for high-tech trace elements supports the need for systematic investigations of their primary occurrences. Mineralogy and trace element characteristics of hydrothermal base-metal veins from the Ruhr Basin (Ruhrgebiet) and the Rhenish Massif (Bergisches Land) in Germany were studied by energy-dispersive X-ray fluorescence mapping, laser ablation-ICP-mass spectrometry, and electron microprobe analyses. Quantitative trace element analysis proves elevated concentrations of Ge and Ga in sphalerite from the Ruhrgebiet. In addition to about 6 Mt of sphalerite-dominated ore, a potential of about 10 t of Ge is indicated to be concentrated in the Auguste Victoria and Graf-Moltke base-metal deposits in the Ruhrgebiet. Assessments on physicochemical fluid properties and metal sources using vitrinite reflectance analysis and host rock investigation indicate a genetic link between the Carboniferous carbonaceous rocks (hosting a number of coal seams) and significant trace metal enrichment in the veins. Gallium enrichment, outlining primary growth zones in ore stage 1 sphalerite, is facilitated by the alteration of Al-bearing minerals in adjacent host rocks due to intense fluid/rock interaction. Reduced Ga and very low In concentrations in ore stage 2 may reflect sealed fluid pathways or changes in the fluid properties. The high level of organic matter in the system probably supported enrichment of Ge in the hydrothermal fluids. The constantly high levels of fixation of Ge in sector zoning patterns of the sphalerite during both ore stages indicate a continuous supply. Elevated contents of Sb together with Cu, As, and Pb in sectors of the sphalerite grains point to a local enrichment of nanometer-scale inclusions of sulfosalt-like phases. Sphalerite of both districts and even of the two ore stages in the Ruhrgebiet shows variations in δ34S isotope compositions due to varying sulfur sources. Both the host rock composition and the presence of organic matter contributed to the trace metal enrichment in the Ruhrgebiet base-metal sulfides as compared to the low contents typical of base-metal ore from the Bergisches Land.
ABSTRACT A new mineral species, dondoellite, ideally Ca2Fe(PO4)2·2H2O, was found in the Grizzly Bear Creek, Dawson mining district, Yukon, Canada. It is polymorphic with messelite, a member of the fairfieldite group. Dondoellite occurs as spherical aggregates (diameters up to 2 cm) of radiating bladed crystals. Associated minerals include hydroxylapatite, siderite, and quartz. No twinning or parting is observed. The mineral is colorless to pale yellow in transmitted light, is transparent with white streak, and has vitreous luster. It is brittle and has a Mohs hardness of 3½–4, with perfect cleavage on {001}. The measured and calculated densities are 3.14(5) and 3.15 g/cm3, respectively. Optically, dondoellite is biaxial (+), with α = 1.649(5), β = 1.654(5), γ = 1.672(5) (white light), 2V (meas.) = 55(2)°, 2V (calc.) = 58°. An electron probe microanalysis yields an empirical formula (based on 10 O apfu) Ca1.99(Fe0.89Mg0.13Mn0.01)Σ1.03(P1.00O4)2·2H2O, which can be simplified to Ca2(Fe2+,Mg,Mn2+)(PO4)2·2H2O. Dondoellite is triclinic, space group P, a = 5.4830(2), b = 5.7431(2), c = 13.0107(5) Å, α = 98.772(2), β = 96.209(2), γ = 108.452(2)°, V = 378.71(2) Å3, and Z = 2. The crystal structure of dondoellite is characterized by isolated FeO4(H2O)2 octahedra that are linked by corner-sharing with PO4 tetrahedra to form so-called kröhnkite-type [Fe(PO4)2(H2O)2]2– chains along [100], similar to that observed in messelite. These chains are connected to one another by large Ca2+ cations and H bonds to form layers parallel to (001). The layers are further linked together by Ca–O and H bonds. However, unlike messelite, the crystal structure of dondoellite contains two symmetrically independent PO4 tetrahedra (P1O4 and P2O4) and two distinct CaO7(H2O) polyhedra (Ca1 and Ca2). The kröhnkite-type chains in dondoellite are constructed with P1O4 tetrahedra on one side and P2O4 tetrahedra on the other. Topologically, the dondoellite structure can be considered a combination of the collinsite and messelite structures alternating along [001], thus representing a new structure type for minerals with kröhnkite-type chains. The discovery of dondoellite raises the question as to whether polymorphs of fairfieldite, Ca2Mn2+(PO4)2·2H2O, or collinsite, Ca2Mg(PO4)2·2H2O, might also be found in nature.
ABSTRACT An occurrence of malhmoodite, Fe2+Zr(PO4)2·4H2O, from the Scott's Rose Quartz mine, Custer County, South Dakota, USA, has been identified. It occurs as divergent groups of yellowish, flat-lying platy crystals on football-size masses of altered löllingite with scorodite, parasymplesite, karibibite, schneiderhöhnite, kahlerite, and zircon. An electron probe microanalysis of malhmoodite yielded an empirical formula (based on 12 O apfu) of Fe1.06(Zr1.10Hf0.03)Σ1.13[(P0.93As0.01)Σ0.94O4]2·4H2O. Single-crystal X-ray structure analysis shows that malhmoodite is the Fe-analogue of zigrasite, MgZr(PO4)2·4H2O. Malhmoodite is triclinic with space group P and unit-cell parameters a = 5.31200(10), b = 9.3419(3), c = 9.7062(3) Å, α = 97.6111(13), β = 91.9796(11), γ = 90.3628(12)°, V = 477.10(2) Å3, Z = 2, in contrast to the previously reported monoclinic symmetry with space group P21/c and unit-cell parameters a = 9.12(2), b = 5.42(1), c = 19.17(2) Å, β = 94.8(1)°, V = 944.26 Å3, Z = 4. The crystal structure of malhmoodite is characterized by sheets composed of ZrO6 octahedra sharing all vertices with PO4 tetrahedra. These sheets are parallel to (001) and are joined together by the FeO2(H2O)4 octahedra. The structure determination of malhmoodite, along with that of zigrasite, warrants a re-investigation of synthetic compounds M2+Zr(PO4)2·4H2O (M = Mn, Ni, Co, Cu, or Zn) that have been assumed previously to be monoclinic.
ABSTRACT Pegmatite bodies with a simple mineral composition are widespread within the Sanandaj-Sirjan Zone (SaSiZ), Zagros Orogen, Iran; however, gem-bearing pegmatite bodies are rare. There is a pegmatitic vein within the Hamadan garnet (± andalusite ± staurolite) schist adjacent to the Alvand Plutonic Complex (APC), south of Hamedan city (western Iran), in which large crystals of gem spodumene occur together with quartz, amazonite, beryl, tourmaline, and apatite. This spodumene-bearing pegmatite consists of four major zones with slightly different mineral compositions from the border to the core. The wall zone of quartz-rich granitoid and the intermediate zone of alkali granite have trondhjemitic compositions near the quartzolitic gem-bearing core zone. All parts of the vein are peraluminous in composition and exhibit S-type affinity. Two types of spodumene which have been distinguished in the core zone are colorless to very pale yellow and pink, transparent with vitreous luster and inclusion-free (eye clean) under 10× magnification. The different color in these minerals can be attributed to the slightly different chemical compositions, particularly lower Fe/Mn ratios in the pink material. The δ7Li values of the spodumene (+5.58 to +6.57‰) are indicative of the incorporation of middle continental crustal components in their genesis. Change in the mineral assemblage from tourmaline-bearing in the intermediate zone to spodumene + tourmaline in the core zone of the spodumene-bearing pegmatite is consistent with increasing lithium content from the wall zone to the core. Petrographic, geochemical, and isotopic data indicate that partial melting of middle-crustal Al-rich metapelitic source was followed by fractional crystallization to generate these rocks. In this concern, the required Li for the crystallization of spodumene was probably supplied by the breakdown of staurolite of the Hamadan schist and/or subsequent fractional crystallization of the parent magma. The results also demonstrate that the regional tectonic regime exerts a primary control on the occurrence and emplacement of the miarolitic pegmatite in the upper crust and the formation of gem spodumene during late-stage magmatic activities.
ABSTRACT Nitroplumbite (IMA2021-045a), [Pb4(OH)4](NO3)4, is a new mineral discovered at the Burro mine, Slick Rock district, San Miguel County, Colorado, USA. It occurs in a secondary efflorescent assemblage on asphaltite and montroseite- and corvusite-bearing sandstone in association with baryte, chalcomenite, and volborthite. The mineral forms as brown equant (pseudocubic) or colorless bladed crystals. The streak is white, luster is vitreous to greasy, Mohs hardness is 2½, tenacity is brittle, and fracture is conchoidal. Nitroplumbite is optically biaxial (–) with α = 1.790(5), β =1.820 (est.), and γ = 1.823 (est.) (white light); 2Vmeas = 35(1)°; optical orientation: Z = b; nonpleochroic. The calculated density is 5.297 g/cm3 for the empirical formula. Electron probe microanalysis provided the empirical formula Pb4.18(OH)4(N0.98O3)4. Nitroplumbite is monoclinic, space group Ia, a = 18.3471(7), b = 17.3057(4), c = 18.6698(8) Å, β = 91.872(3)°, V = 5924.7(4) Å3, and Z = 16. The crystal structure (R1 = 0.0509 for 11161 I > 2σI reflections) is the same as that previously determined for its synthetic analogue. It consists of isolated, internally bonded cubane-like [Pb4(OH)4]4+ clusters and isolated (NO3)– groups that are linked together by long Pb–O bonds and hydrogen bonds.
ABSTRACT Lauraniite, Cu6Cd2(SO4)2(OH)12·5H2O, is a new mineral from the Laurani Mine, Aroma Province, La Paz Department, Bolivia, where it is found as a secondary mineral associated with serpierite and brochantite, on a matrix consisting of tennantite and chalcocite. Lauraniite occurs as bladed crystals up to 110 μm in length. Crystals are pale blue and transparent, with a vitreous luster and a white streak. Fracture is uneven. Cleavage is perfect on {100}. The calculated density is 3.40 g/cm3 based on the empirical formula. Optically, lauraniite is uniaxial (+) with α = 1.637(3), β = 1.638(3), γ = 1.638(3) (white light), 2V = 20(2)°, and orientation Z ≈ a. The empirical formula, based on data obtained from electron microprobe analysis, is Cu6.13(Cd1.62Zn0.24)(SO4)1.96(OH12.03Cl0.05)12.08·5.08H2O. Lauraniite is monoclinic, P21/c, a = 7.3200(15), b = 25.424(5), c = 11.283(2) Å, β = 91.62(3)°, V = 2099.0(7) Å3, and Z = 4. The crystal structure, determined using single-crystal data obtained using synchrotron radiation, refined to R1 = 0.0468% for 5999 observed reflections with Fo > 4σ(Fo). It is characterized by undulating, brucite-like sheets consisting of seven Cuϕ6 (ϕ: O2–, OH–, H2O) octahedra and two Cd(OH)6(H2O) polyhedra. Sheets are decorated on one side by corner-sharing SO4 tetrahedra. Linkages between adjacent sheets are provided by H-bonds.
ABSTRACT Tengchongite, a uranyl molybdate mineral from Tengchong County, Yunnan Province, China, was originally described as orthorhombic, with space group A2122, unit-cell parameters a = 15.616(4) Å, b = 13.043(6) Å, c = 17.716(14) Å, V = 3608 Å3, and an ideal chemistry CaO·6UO2·2MO3·12H2O. Its ideal chemical formula is given as Ca(UO2)6(MoO4)2O5·12H2O in the current IMA-CNMNC List of Mineral Names. Tengchongite is the only mineral with a U:Mo ratio of 3:1, the second-highest ratio of all natural and synthetic uranyl molybdate materials, but its crystal structure remained undetermined until now. This study reports the structure determination of tengchongite from the type sample and a revision of its chemical formula to Ca(UO2)6(MoO4OH)2O2(OH)4·9H2O. Tengchongite is orthorhombic, with space group C2221, Z = 4, a = 13.0866(8) Å, b = 17.6794(12) Å, c = 15.6800(9) Å, and V = 3627.8(4) Å3. Its crystal structure was refined from single-crystal X-ray diffraction data to R1 = 0.0323 for 6055 unique observed reflections. The fundamental building blocks of the tengchongite structure are sheets consisting of six-membered clusters of edge-sharing UO7 pentagonal bipyramids, which are connected by sharing vertices among them, as well as edges and vertices with MoO5 trigonal bipyramids. These sheets, parallel to [010], are linked together by Ca2+ and H2O groups. Tengchongite represents a new type of structural connectivity between U- and Mo-polyhedra for uranyl molybdate minerals.
ABSTRACT The Whabouchi pegmatite, located in the James Bay area of Québec, is a lithium-cesium-tantalum pegmatite of albite-spodumene type. In order to evaluate the mineralogical and geochemical variability of the pegmatite, 168 samples were collected from drill core and analyzed for their whole rock geochemistry and mineralogy. The pegmatite is composed of quartz, albite, K-feldspar, spodumene, and muscovite, with trace amounts of spessartine garnet, apatite, beryl, tourmaline, and oxides. It is mostly homogenous, showing greatest variability with respect to the minerals albite, K-feldspar, and spodumene. The Li2O concentration varies between 0.03 and 4.46 wt.%, for an average of 1.53 wt.% and an estimated variability of 53%. Modal mineralogical data showed an inverse correlation between spodumene and the feldspars (albite + K-feldspar), which could also be observed when comparing the Li2O content with the sum of Na2O and K2O. To improve on this relationship, correlation matrices comparing all geochemical components were constructed and allowed the development of an equation able to estimate the Li2O content of the samples within 0.5 wt.% of the measured value. The applicability of the equation to other albite-spodumene type pegmatites was verified with samples collected from the Georgia Lake area of northwestern Ontario. The calculation provided a good approximation of the Li2O content of the samples, with 92% of the data showing a difference of 0.5 wt.% Li2O or less; however, it has an impact on the statistical mean of the data set, the data being recalculated to return an average closer to 1.5 wt.% Li2O. Considering the difficulty in analyzing lithium content of an in situ sample, this relationship could facilitate estimation in the field using portable X-ray fluorescence with the capability of analyzing all required components.
