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The uranium deposit at Niederschlema-Alberoda, Germany, contains a rich variety of Bi minerals deposited between the Permian and the Cretaceous; these have been studied for paragenetic relations, composition, and conditions of formation. Particular attention is given to the rare Bi selenides watkinsonite, nevskite, and cuproan bohdanowiczite. Whereas watkinsonite and nevskite only occur intergrown with clausthalite, bohdanowiczite is more widespread and also is associated with Cu selenides. Watkinsonite from this second confirmed locality worldwide has an average composition (Cu1.47Ag0.49)(Sigma 1.96)(Pb1.01Hg0.01 Fe-0.01)(Sigma 1.03)Bi-3.98(Se7.98S0.05)(Sigma 8.03), ideally (Cu,Ag)(2)PbBi4Se8. These findings suggest that the empirical formula of watkinsonite originally proposed for the type specimen from the Otish Mountains uranium deposit in Quebec [CU2+xPb1+xBi4-xSe,S,Te)(8), x approximate to 0.3] requires revision. The composition of nevskite is (Pb0.06Bi0.95)(Sigma 1.01)Se-0.99, on average. Bohdanowiczite from the Cu- selenide assemblage shows extensive substitution of Cu+ for Ag+, expressed by the crystallochemical formula (Ag1.80- 0.94CU0.16-1.05Pb0.00-0.05)(Sigma 1.97-2.07)BiSigma 1.97-2.03SeSigma 3.96-4.04. This observation seems to argue for the natural existence of CU2Bi2Se4, the Se-dominant analogue of emplectite. The Bi selenides were deposited at temperatures of about 100 degrees C, in the Jurassic. The lack of thermodynamic data for all the Bi selenides limits reliable inferences on the fugacities of selenium and sulfur that prevailed during their formation. Other Bi minerals from this locality comprise members of the bismuthinite-aikinite solid-solution series of Permian age and, more importantly, native Bi and Bi sulfides (matildite, bismuthinite, wittichinite), deposited in the Cretaceous
Annite and Fe-rich siderophyllite constitute the rock-forming micas in the late-Variscan composite granite pluton of Konigshain, Lausitz, Germany. This multiphase pluton is composed of three fractionated, but not chemically specialized monzogranite types, which contain lithophile elements such as Li, Rb, Cs, Sn, and F in average quantities. Abundant miarolitic pegmatites of the NYF family with a broad diversity of rare minerals occur in the apical part of the pluton. These pegmatitic cavities locally contain di- and trioctabedral micas as well as cation-deficient micas. Trioctahedral micas comprise F-rich manganoan lithian siderophyllite to manganoan zinnwaldite, zinnwaldite, and minor lepidolite. The formula [calculated on the basis of 22 anion valencies and 2 (F + OH + Cl)] of the most Mn-rich siderophyllite is (K0.85Rb0.08Na0.04)(0.97)(Al0.99Li0.91Fe0.51Mn0.42Ti0.01Zn0.01)(2.85) (Si3.21Al0.79)(4)O- 10(F1.80OH0.19Cl0.01)(2). This mica constitutes one of the most Mn-rich siderophyllite compositions reported to date. The lithium micas poorer in Mn are distinguished by elevated concentrations of Rb (up to 2.5 wt % Rb2O), CS (UP to 1.2 wt % Cs2O), and F (up to 9.6 wt %). This fluorine content is probably consistent with the maximum possible F occupation of 2 of the (F,OH,Cl)-site. The structural formula of the most Li-rich lepidolite is (K0.83Rb0.07Cs0.03)(0.93) (Li1.62Al1.00Fe0.38)(3.00)(Si3.62Al0.38)(4) O-10(F1.91OH0.09)(2). During hydrothermal alteration, lepidolite and zinnwaldite became partially depleted in K, Li, Rb, Cs, and F and gradually transformed into cation-deficient micas (lithian phengite to illite of phengitic affinity)
In the earliest emplaced granite subintrusion of the multiphase peraluminous Satzung pluton, Erzgebirge, Germany, a mineral aggregate was observed consisting of sekaninaite (X-Fe = 0.74-0.94), Zn-rich hercynite (X-Zn = 0.03- 0.11), tri- and dioctahedral layer silicates of different composition and color, and minor quartz. Geological, textural, and compositional criteria argue that the sekaninaite, hercynite, quartz, and the brown biotite are not primary or secondary granite minerals, but are of metamorphic origin representing a xenolith uptaken from the granite melt near its level of emplacement. The metamorphic origin is supported by the occurrence of this mineral assemblage in metamorphic rocks exposed locally in the Erzgebirge basement. Reaction of the polymineralic metamorphic aggregate with the surrounding melt and subsequent interaction with alkali-, F- and LILE-rich residual fluids account for the widespread decomposition of the sekaninaite and formation of several layer silicates including green biotite, muscovite, berthierine/Fe chlorite, and sericite. The observed enrichment of the relic sekaninaite and its replacement products in elements such as Na, Li, Be, Rb, Cs, and F is result of interaction of the metamorphic fragment with the surrounding melt/fluid, in accordance with the evolved nature of the Satzung magmatic-hydrothermal system
A localized dehydration zone, Sondrum stone quarry, Halmstad, SW Sweden, consists of a central, 1 m wide granitic pegmatoid dyke, on either side of which extends a 2.5-3 m wide dehydration zone (650-700 degrees C; 800 MPa; orthopyroxene-clinopyroxene-biotite-amphibole-garnet) overprinting a local migmatized granitic gneiss (amphibole-biotite- garnet). Whole-rock chemistry indicates that dehydration of the granitic gneiss was predominantly isochemical. Exceptions include [Y + heavy rare earth elements (HREE)], Ba, Sr, and F, which are markedly depleted throughout the dehydration zone. Systematic trends in the silicate and fluorapatite mineral chemistry across the dehydration zone include depletion in Fe, (Y + HREE), Na, K, F, and Cl, and enrichment in Mg, Mn, Ca, and Ti. Fluid inclusion chemistry is similar in all three zones and indicates the presence of a fluid containing CO2, NaCl, and H2O components. Water activities in the dehydration zone average 0.36, or XH2O = 0.25. All lines of evidence suggest that the formation of the dehydration zone was due to advective transport of a CO2-rich fluid with a minor NaCl brine component originating from a tectonic fracture. Fluid infiltration resulted in the localized partial breakdown of biotite and amphiboles to pyroxenes releasing Ti and Ca, which were partitioned into the remaining biotite and amphibole, as well as uniform depletion in (Y + HREE), Ba, Sr, Cl, and F. At some later stage, H2O-rich fluids (H2O activity > 0.8) gave rise to localized partial melting and the probable injection of a granitic melt into the tectonic fracture, which resulted in the biotite and amphibole recording a diffusion profile for F across the dehydration zone into the granitic gneiss as well as a diffusion profile in Fe, Mn, and Mg for all Fe-Mg silicate minerals within 100 cm of the pegmatoid dyke
Reaction rims of titanite on ilmenite are described in samples from four terranes of amphibolite-facies metapelites and amphibolites namely the Tamil Nadu area, southern India; the Val Strona, area of the Ivrea-Verbano Zone, northern Italy, the Bamble Sector, southern Norway, and the northwestern Austroalpine Otztal Complex. The titanite rims, and hence the stability of titanite (CaTiSiO4O) and Al-OH titanite, i.e. vuaganatite (hypothetical end-member CaAlSiO4OH), are discussed in the light of fH(2)O- and fO(2)-buffered equilibria involving clinopyroxene, amphibole, biotite, ilmenite, magnetite, and quartz in the systems CaO-FeO/Fe2O3-TiO2-SiO2-H2O-O-2 (CFTSH) and CaO-FeO/Fe2O3-Al2O3- SiO2-H2O-O-2 (CFASH) present in each of the examples. Textural evidence suggests that titanite reaction rims on ilmenite in rocks from Tamil Nadu, Val Strona, and the Bamble Sector originated most likely due to hydration reactions such as clinopyroxene + ilmenite +quartz+ H2O = amphibole +titanite and oxidation reactions such as amphibole + ilmenite + O-2 = titanite + magnetite + quartz + H2O during amphibolite-facies metamorphism, or, as in the case of the Otztal Complex, during a subsequent greenschist-facies overprint. Overstepping of these reactions requires fH(2)O and fO(2) to be high for titanite formation, which is also in accordance with equilibria involving Al-OH titanite. This study shows that, in addition to P, T, bulk-rock composition and composition of the coexisting fluid, fO(2) and fH(2)O also play an important role in the formation of Al-bearing titanite during amphibolite- and greenschist-facies metamorphism.
In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H2SO4 solutions at temperatures of 300, 600, and 900 degrees C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H2SO4 experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H2SO4 experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600 degrees C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10-20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H2SO4 experiment at 900 degrees C and 1,000 MPa indicates a pervasive nano- porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution-reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions
"Hastite", the orthorhombic dimorph of CoSe2, formerly considered as a valid mineral species occurring in the Trogtal quarries, Harz Mountains, Germany, is discredited as being identical with ferroselite, orthorhombic FeSe2. The discreditation has been unanimously approved by the IMA Commission on New Minerals, Nomenclature and Classification (CNMNC) (IMA No. 07-E). We also provide observations on the composition, homogeneity, and origin of trogtalite (cubic CoSe2) from its type locality.
Accessory minerals of the Caledonian Rumburk granite are investigated to gain insight into its magmatic and post-magmatic evolution history. Recent geothermometers calibrated for trace elements in rutile (Zr), zircon (Ti), and quartz (Ti) were used to determine mineral-formation temperatures, which are compared with T data obtained from melt and fluid-inclusion Studies on quartz. Improved electron-microprobe analytical conditions allowed distinguishing several generations of rutile. Submicron-sized rutile needles included in quartz crystallized at around 739 +/- 13 degrees C and, thus, are evidently magmatic. Simultaneous crystallization of the high-T rutile and quartz is the favoured concept compared with an exsolution model for the needles. Th-U-total Pb dating of xenotime-(Y) by electron microprobe yielded a bimodal age distribution of 494 +/- 8 Ma (2 sigma; n = 44) and 311 +/- 8 Ma (2 sigma; n = 48), which is missing in monazite-(Ce). The older age correlates with the early Ordovician granite emplacement age Suggested by earlier isotopic Studies. The younger Carboniferous age also may be geologically reasonable, because the granite experienced a minor tectonothermal overprint during the Variscan orogenesis. However, whether this event has caused the resetting of the isotopic system in the xenotime is uncertain. This also holds for the age of the partial breakdown of monazite and xenotime into reaction coronas composed of fluorapatite, allanite-(Ce), epidote +/- clinozoisite. This alteration assemblage was likely produced already during autometasomatic reworking of the solidifying magma in Ordovician time, but it cannot be excluded that it relates to a Carboniferous fluid imprint connected with late-Variscan processes.
Quartz crystals from topaz-zinnwaldite-albite granites from Zinnwald (Erzgebirge, Germany) contain, in addition to primary and secondary fluid inclusions (FIs), abundant crystalline silicate-melt inclusions (MIs) with diameters up to 200 mum. These MIs represent various stages of evolution of a highly evolved melt system that finally gave rise to granite-related Sn-W mineralization. The combination of special experimental techniques with confocal laser Raman- microprobe spectroscopy and EMPA permits precise measurement of elevated contents of H2O, F, and B in re-homogenized MIs. The contents of H2O and F were observed to increase from 3 to 30 and 1.9 to 6.4 wt%, respectively, during magma differentiation. However, there is a second MI group, very rich in H2O, with values up to 55 wt% H2O and an F concentration of approximately 3 wt%. Ongoing enrichment of volatiles H2O, F, B, and Cl and of Cs and Rb can be explained in terms of magma differentiation triggered by fractional crystallization and thus, is suggested to reflect elemental abundances in natural magmas, and not boundary-layer melts. Partitioning between melt and cogenetic fluids has further modified the magmatic concentrations of some elements, particularly Sn. The coexistence of two types of MIs with primary FIs indicates fluid saturation early in the history of magma crystallization, connected with a continuous sequestration of Sn, F, and B. The results of this study provide additional evidence for the extraordinary importance of the interplay of H2O, F, and B in the enrichment of Sn during magma differentiation by decreasing the viscosity of and increasing the diffusivity in the melts as well as by the formation of various stable fluoride complexes in the melt and coexisting fluid