Ferrotorryweiserite, Rh5Fe10S16, a New Mineral Species from the Sisim Placer Zone, Eastern Sayans, Russia, and the Torryweiserite–Ferrotorryweiserite Series

Ferrotorryweiserite, Rh5Fe10S16, occurs as small grains (≤20 µm) among droplet-like inclusions (up to 50 μm in diameter) of platinum-group minerals (PGM), in association with oberthürite or Rh-bearing pentlandite, laurite, and a Pt-Pd-Fe alloy (likely isoferroplatinum and Fe-Pd-enriched platinum), hosted by placer grains of Os-Ir alloy (≤0.5 mm) in the River Ko deposit. The latter is a part of the Sisim placer zone, which is likely derived from ultramafic units of the Lysanskiy layered complex, southern Krasnoyarskiy kray, Russia. The mineral is opaque, gray to brownish gray in reflected light, very weakly bireflectant, not pleochroic to weakly pleochroic (grayish to light brown tints), and weakly anisotropic. The calculated density is 5.93 g·cm–3. Mean results (and ranges) of four WDS analyses are: Ir 18.68 (15.55–21.96), Rh 18.34 (16.32–20.32), Pt 0.64 (0.19–1.14), Ru 0.03 (0.00–0.13), Os 0.07 (0.02–0.17), Fe 14.14 (13.63–14.64), Ni 13.63 (12.58–14.66), Cu 4.97 (3.42–6.41), Co 0.09 (0.07–0.11), S 29.06 (28.48–29.44), and total 99.66 wt. %. They correspond to the following formula calculated for a total of 31 atoms per formula unit: (Rh3.16Ir1.72Pt0.06Ru0.01Os0.01)Σ4.95(Fe4.48Ni4.11Cu1.38Co0.03)Σ10.00S16.05. The results of synchrotron micro-Laue diffraction studies indicate that ferrotorryweiserite is trigonal; its probable space group is Rm (#166) based on its Ni-analog, torryweiserite. The unit-cell parameters refined from 177 reflections are a = 7.069 (2) Å, c = 34.286 (11) Å, V = 1484 (1) Å3, and Z = 3. The c:a ratio is 4.8502. The strongest eight peaks in the X-ray diffraction pattern derived from results of micro-Laue diffraction study [d in Å(hkil)(I)] are 2.7950 (205) (100); 5.7143 (0006) (60); 1.7671 (220) (44.4); 3.0486 (201) (39.4); 5.7650 (102) (38.6); 2.5956 (207) (37.8); 3.0058 (116) (36.5); and 1.5029 (412) (35.3). Ferrotorryweiserite and the associated PGM crystallized from microvolumes of residual melt at late stages of crystallization of grains of Os- and Ir-dominant alloys occurred in lode zones of chromitites of the Lysanskiy layered complex. In a particular case, the residual melt is disposed peripherally around a core containing a disequilibrium association of magnesian olivine (Fo72.9–75.6) and albite (Ab81.6–86.4), with the development of skeletal crystals of titaniferous augite: Wo40.8–43.2En26.5–29.3Fs20.3–22.6Aeg6.9–9.5 (2.82–3.12 wt. % TiO2). Ferrotorryweiserite represents the Fe-dominant analog of torryweiserite. We also report occurrences of ferrotorryweiserite in the Marathon deposit, Coldwell Complex, Ontario, Canada, and infer the existence of the torryweiserite–ferrotorryweiserite solid solution in other deposits and complexes.

Genesis of sulfide vein mineralization at the Sakatti Ni-Cu-PGE deposit, Finland

ABSTRACT The Sakatti Ni-Cu-platinum-group element deposit is situated in northern Finland and comprises massive, disseminated, and vein sulfide mineralization. A stockwork is formed by chalcopyrite-rich sulfide veins, which contain exceptionally high platinum-group elements and Au grades. The mineralogy and geochemistry of this stockwork zone ore is documented in this investigation. The results are used to develop the first robust genetic concept and its relationship to massive and disseminated mineralization of the Sakatti deposit. This model is similar to that proposed for many Cu-rich magmatic sulfide ores, most importantly the Cu-rich footwall veins described from the Sudbury Complex in Canada and the Cu-rich ore at Noril'sk-Talnakh in Russia. Detailed petrographic studies using a sample suite from exploration drill core intersecting vein-style mineralization revealed a classic magmatic sulfide assemblage of chalcopyrite ± pyrrhotite, pentlandite, and pyrite. More than 1000 platinum-group mineral grains belonging almost exclusively to the moncheite (PtTe2) – merenskyite (PdTe2) – melonite (NiTe2) solid solution series were identified in the studied samples. Notably, almost two thirds of the platinum-group element-bearing minerals consist of melonite. Some of the platinum-group minerals contain inclusions of Ag-rich gold (AgAu2) and muthmannite (AuAgTe2). Most of the platinum-group minerals occur as inclusions in chalcopyrite, although a few grains are located at base-metal sulfide grain boundaries and in fractures in base-metal sulfides. The whole-rock compositions of the stockwork veins are Cu-rich and are interpreted to represent a fractionated Cu-rich sulfide liquid enriched in Pt, Pd, Au, Ag, As, Bi, Pb, Se, Te, Zn, which separated from a monosulfide solid solution (mss). An intermediate solid solution (iss) solidified from the Cu-rich sulfide liquid, recrystallizing chalcopyrite at <550 °C. Simultaneously, small volumes of intercumulus residual melt contained mainly the precious metals, Bi, and Te due to their incompatibility in iss. Solitary and composite platinum-group minerals as well as Au-minerals crystallized first from the residual melt (<600 °C), followed by a succession of various Bi-, Ag-, and Pb-tellurides (∼540 °C), and finally sphalerite and galena. Melonite crystallized as mostly large, solitary grains exsolved directly from Ni-bearing intermediate solid solution (∼600 °C), shortly after the formation of moncheite and merenskyite from the residual melt. Finally, remobilization of the platinum-group minerals occurred at temperatures of <300 °C, as suggested by the presence of minor amounts of Cl-bearing minerals and ragged grain shapes.

Modeling Changes in Internal Pressure During the Solidification of Hydrous Granitic Intrusives: Implications for the Crystallization of Miarolitic Pegmatites

ABSTRACT Volatile exsolution is widely recognized as an important trigger for eruptions from shallow magma reservoirs, but relatively few studies quantify the effects of exsolution on internal pressure within deeper-seated intrusive bodies. We present a model to predict internal pressure changes during the crystallization of a haplogranite melt containing 3 and 5 mass % H2O and with an emplacement pressure of 200 MPa. Mass and volume relations between phases are used to determine internal pressure assuming a closed, constant-volume system. The results indicate that initial crystallization of alkali feldspar and quartz causes a decrease in pressure prior to the exsolution of an aqueous fluid from the residual melt (i.e., resurgent boiling). Further crystallization toward the core of the body in the presence of a separate volatile phase results in a sharp increase in internal pressure. Our model shows that in closed, isochoric systems, the crystallization of the H2O-saturated melt will generate internal pressures that greatly exceed emplacement pressures typical of miarolitic pegmatites. Extreme overpressure modifies the physical and chemical properties of the residual melt and coexisting aqueous fluid, which in turn influences crystallization kinetics and the development of primary textures. Primary melt and fluid inclusions in pocket minerals thus likely represent samples trapped at various pressures in a rapidly evolving melt–fluid system. In most pegmatites, increasing fluid pressure and the formation of large pockets is regulated by the permeability and tensile strength of the enclosing rock. This explains why many miarolitic pegmatites occur within rigid host rocks such as granite, gabbro, and gneiss.

Microstructure and Fatigue Behaviors of Dissimilar A6061/Galvannealed Steel Joints Fabricated by Friction Stir Spot Welding

The microstructures, tensile shear properties, and tensile shear fatigue properties of dissimilar A6061/Galvannealed steel joints fabricated by friction stir spot welding (FSSW) were investigated. Fe4Al13 phases form as the intermetallic compound (IMC) layer at the joint interface between the A6061 matrix and the galvannealed layer consisting of FeZn7, Fe, and Zn. At the edge of the joint, the stirred layer in which the A6061 matrix and the galvannealed layer are stirred also forms. Moreover, the solidified part of the residual melt discharged from the joint area forms at the outer peripheries of the joint. In this study, FSSW was conducted for two total welding durations: 9 and 10 s. Although the thickness of the remaining A6061 sheet in the welded area decreased with an increase in the welding time, the effects of the total welding time on tensile shear and tensile shear fatigue properties were negligible. A fatigue fracture occurred in the A6061 matrix and at the joint interface at the high cycle fatigue region and the low cycle fatigue region, respectively. In the case of the interfacial fracture, the crack was generated in the solidified part of the residual melt or at the interface between the solidified part and the stirred layer.

Tamuraite, Ir5Fe10S16, a New Species of Platinum-Group Mineral from the Sisim Placer Zone, Eastern Sayans, Russia

Tamuraite, ideally Ir5Fe10S16, occurs as discrete phases (≤20 μm) in composite inclusions hosted by grains of osmium (≤0.5 mm across) rich in Ir, in association with other platinum-group minerals in the River Ko deposit of the Sisim Placer Zone, southern Krasnoyarskiy Kray, Russia. In droplet-like inclusions, tamuraite is typically intergrown with Rh-rich pentlandite and Ir-bearing members of the laurite–erlichmanite series (up to ~20 mol.% “IrS2”). Tamuraite is gray to brownish gray in reflected light. It is opaque, with a metallic luster. Its bireflectance is very weak to absent. It is nonpleochroic to slightly pleochroic (grayish to light brown tints). It appears to be very weakly anisotropic. The calculated density is 6.30 g·cm−3. The results of six WDS analyses are Ir 29.30 (27.75–30.68), Rh 9.57 (8.46–10.71), Pt 1.85 (1.43–2.10), Ru 0.05 (0.02–0.07), Os 0.06 (0.03–0.13), Fe 13.09 (12.38–13.74), Ni 12.18 (11.78–13.12), Cu 6.30 (6.06–6.56), Co 0.06 (0.04–0.07), S 27.23 (26.14–27.89), for a total of 99.69 wt %. This composition corresponds to (Ir2.87Rh1.75Pt0.18Ru0.01Os0.01)Σ4.82(Fe4.41Ni3.90Cu1.87Co0.02)Σ10.20S15.98, calculated based on a total of 31 atoms per formula unit. The general formula is (Ir,Rh)5(Fe,Ni,Cu)10S16. Results of synchrotron micro-Laue diffraction studies indicate that tamuraite is trigonal. Its probable space group is R–3m (#166), and the unit-cell parameters are a = 7.073(1) Å, c = 34.277(8) Å, V = 1485(1) Å3, and Z = 3. The c:a ratio is 4.8462. The strongest eight peaks in the X-ray diffraction pattern [d in Å(hkl)(I)] are: 3.0106(26)(100), 1.7699(40)(71), 1.7583(2016)(65), 2.7994(205)(56), 2.9963(1010)(50), 5.7740(10)(45), 3.0534(20)(43) and 2.4948(208)(38). The crystal structure is derivative of pentlandite and related to that of oberthürite and torryweiserite. Tamuraite crystallized from a residual melt enriched in S, Fe, Ni, Cu, and Rh; these elements were incompatible in the Os–Ir alloy that nucleated in lode zones of chromitites in the Lysanskiy layered complex, Eastern Sayans, Russia. The name honors Nobumichi Tamura, senior scientist at the Advanced Light Source of the Lawrence Berkeley National Laboratory, Berkeley, California.

The Origin and Melt Evolution of Massif-type Anorthosite Parental Magmas: Thermodynamically Controlled Major Element Constraints

<p>The parental magmas of massif-type anorthosites are suggested to originate from either the mantle or lower crust. If the source is the mantle, the magmas are presumed to have undergone crustal assimilation prior to plagioclase crystallization, which has produced melt compositions similar to anorthosite parental magmas (high-Al gabbros/basalts). If the source is the lower crust, the produced anorthosite parental melts are presumed to be monzodioritic (jotunitic) in composition. However, many studies have suggested that the monzodioritic rocks related to massif-type anorthosites rather represent residual melt compositions left after anorthosite fractionation. In this study, we have used the most recent thermodynamic modeling tools, Magma Chamber Simulator (MCS) and Rhyolite-MELTS to conduct partial melting, assimilation-fractional crystallization (AFC), and fractional crystallization (FC) models to address the unresolved questions about the source and compositional evolution of the anorthosite parental magmas.</p><p>AFC models were conducted at high lower crustal pressures (1000 MPa) by using MCS. In the models, we used four different sublithospheric mantle partial melt compositions and 11 different assimilants with representative average lower crustal compositions compiled from literature. In addition, equilibrium partial melting of the same lower crustal compositions was modeled separately by using rhyolite-MELTS. The melt major element compositions produced by both modeling tools were compared to suggested natural anorthosite parental magma compositions. Finally, to further study the evolution of these melts after their generation, FC models were run at different crustal pressures (1000-100 MPa) by using MCS. These differentiated melt compositions were compared to a global array of monzodioritic rocks presumed to represent residual melts left after anorthosite fractionation.</p><p>The preliminary modeling results point towards the mantle being a more suitable candidate for the source of the anorthosite parental magmas and that the parental magma compositions are better represented by high-Al gabbros than monzodioritic rocks: assimilation of mafic lower crustal material by mantle-derived magmas produces melts that are the most fitting analogues. Somewhat similar melts can also be produced by directly melting the lower crust, but this requires the crust to melt completely, which we consider improbable. The models further suggest fractional crystallization of high-Al gabbroic parental magmas produce residual melt evolution trends similar to the array of anorthosite-related monzodioritic rocks.</p>

The geochemistry of thallium and its isotopes in rare-element pegmatites

The Tl isotopic and trace element composition of K-feldspar, mica, pollucite and pyrite from 13 niobium-yttrium-fluorine (NYF)-type and 14 lithium-cesium-tantalum (LCT)-type rare-element pegmatites was investigated. In general, the epsilon-205Tl values for K-feldspar in NYF- and LCT-type pegmatites increases with increasing magmatic fractionation. Both NYF and LCT pegmatites display a wide range in epsilon-205Tl (-4.25 to 9.41), which complicates attempts to characterize source reservoirs. We suggest 205Tl-enrichment during pegmatite crystallization occurs as Tl partitions between the residual melt and a coexisting aqueous fluid or flux-rich silicate liquid. Preferential association of 205Tl with Cl in the immiscible aqueous fluid may influence the isotopic character of the growing pegmatite minerals. Subsolidus alteration of K-feldspar by aqueous fluids, as indicated by the redistribution of Cs in K-feldspar, resulted in epsilon-205Tl values below the crustal average (-2.0 epsilon-205Tl). Such low epsilon-205Tl values in K-feldspar is attributed to preferential removal and transport of 205Tl by Cl-bearing fluids during dissolution and reprecipitation. The combination of thallium isotope and trace element data may be used to examine late-stage processes related to rare-element mineralization in some pegmatites. High epsilon-205Tl and Ga in late-stage muscovite appears to be a favorable indicator of rare-element enrichment LCT pegmatites and may be a useful exploration vector.

Compositional and Textural Variations of Columbite-Group Minerals from Beryl-Columbite Pegmatites in the Maršíkov District, Bohemian Massif, Czech Republic: Magmatic versus Hydrothermal Evolution

We studied compositional variations in columbite group minerals (CGM) from several granitic pegmatites of the beryl-columbite subtype in the Maršíkov district, Silesian Domain of the Bohemian Massif, Czech Republic. The CGM are characterized by distinct zoned patterns in BSE images. Primary magmatic homogeneous to oscillatory zoning is preserved in corroded crystal cores, whereas the majority of the crystal volume is replaced by secondary complexly zoned domains formed via post-magmatic processes. The primary domains show relatively uniform evolutionary trends from core to rim, generally with steeply increasing Ta/(Ta + Nb) and negligible to slightly increasing Mn/(Mn + Fe). In contrast, the compositions of secondary CGM domains indicate a reversed evolution, with: (1) steeply decreasing Ta/(Ta + Nb) and relatively constant Mn/(Mn + Fe) characteristics for CGM in the Bienergraben and Scheibengraben pegmatites, and (2) insignificantly decreasing Ta/(Ta + Nb) and strongly decreasing Mn/(Mn + Fe) characteristics for CGM in the Schinderhübel I and Lysá Hora pegmatites. Patchy zoning and secondary evolution in CGM result from metasomatic replacement processes related to fluids. These fluids are probably late-magmatic and exsolved from the residual melt and in later stages locally mixed with external Mg-enriched fluids derived from the host rocks. The presence of volatiles (mainly H2O, F) facilitated high mobility of the elements and replacement of the early CGM. Textural characteristics and compositional variations in CGM show the complex evolution of the pegmatite system from the magmatic stage to subsolidus-hydrothermal conditions.

The importance of in situ crystallisation and loss of interstitial melt during formation of the Kærven Syenite Complex, Kangerlussuaq, East Greenland

The Kærven Syenite Complex (KSC) is one of the oldest felsic intrusions in the Tertiary East Greenland province. Here we update our previous description of the KSC and supply a greatly expanded and comprehensive geochemical dataset. New data allow us to present a more detailed petrogenetic model for the evolution of the KSC and to investigate the geochemical characteristics of igneous cumulates subjected to loss and, occasionally, replacement of residual liquid. The KSC comprises eleven mappable units that generally young westwards. Rock types range from quartz syenite to quartz alkali feldspar syenite and alkali feldspar granite. Individual intrusive units are relatively narrow and steep-sided and are collectively suggested to represent a ring dyke complex. Basement gneiss and gabbro host rocks have locally contaminated the oldest quartz syenite KSC unit, but most of the main part of the complex escaped significant influence from host rocks. A late suite of E–W to NE–SW striking peralkaline dykes of trachytic to phonolitic compositions intrude the KSC. Compositions of the KSC rocks span a considerable range in SiO2, 59–73 wt%. Concentrations of several elements vary widely for a given SiO2 (especially at SiO2 < 66 wt%), and variation diagrams do not suggest a single model for the evolution of the units of the complex. A cumulative origin is envisaged for several KSC units. Geochemical modelling suggests that KSC magmas were derived from more than one primary magma, and that the complex evolved through a four-stage process: fractional crystallisation in precursory magma chambers was followed by final emplacement of each unit, establishment of a crystal/melt mush, expulsion of part of the residual melt and, finally, crystallisation of the remaining melt. Trace element disequilibria between alkali feldspar and host rocks in two closely associated quartz alkali feldspar syenite units indicate that highly evolved residual melt was replaced by a less evolved melt phase. Modelling of potential parent melt compositions to the Kærven magmas suggests an origin not in the Iceland plume asthenosphere, but rather in a moderately enriched source, possibly in the continental lithosphere. The course of melt evolution by fractional crystallisation is indicated to have taken place in magma chambers at depth, and repeated rise of magma into the upper crustal magma chambers and crystallisation there formed the KSC. Based on our survey of published geochemical data, the inferred parental magmas seem to have few equivalents in the North Atlantic Igneous Province and may have been generated mainly from melting of enriched dry lithospheric mantle of possibly Archaean age.