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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
The Niederschlema-Alberoda uranium deposit, in the Erzgebirge region of Germany, contains an uncommon assemblage of metallic minerals, in particular selenides, sulfides, arsenides, tellurides, and native elements, in addition to uraninite and coffinite. The complex mineralogy resulted from the superposition of several mineralizing events over the time interval from the Permian to the Cretaceous; these events introduced and redeposited a great variety of metallic elements within the hydrothermal uranium deposit (Pb, Ag, Cu, Hg, Tl, Bi, Co, Ni, As, Sb, Se, S, Te). One of the exotic minerals is jolliffeite, an arsenoselenide with end-member composition NiAsSe, so far only known from Lake Athabasca, Saskatchewan, Canada. A single, small, anhedral grain of jolliffeite from Niederschlema-Alberoda is included and partly replaced by sulfurian eskebornite. Associated minerals comprise hematite, Ni-Co-Se-bearing lollingite, clausthalite, tiemannite, mercurian hakite-giraudite solid solutions, sulfurian berzelianite, sulfurian umangite, hessite, Ni-Co-As-bearing pyrite, and Se-rich chalcopyrite. The sulfurian jolliffeite has the empirical formula (Ni0.85Cu0.09Co0.05Fe0.02Ag0.01)Sigma(1.02)As(0.98)(Se0.77S0.23)(Sigma1. 00) and differs from type jolliffeite mainly by substantial substitution of Cu (2.6-3.3 wt.%) for Ni and S (3.2-4.1 wt.%) for Se. Substantial S-for-Se substitution in jolliffeite implies extensive and probably complete miscibility between NiAsSe and its S-dominant analogue, gersdorffite-Pa3 (NiAsS). We suggest that a localized accumulation of Ni and As in the Se-(S)-bearing hydrothermal fluid gave rise to the crystallization of jolliffeite at some rare locations at a late stage of formation of the Jurassic selenide assemblage
Hessite, Ag2Te, and native tellurium (?) constitute two, previously unknown tellurium species within the complex mineral assemblage at Niederschlema-Alberoda, Erzgebirge, Germany. Hessite is always intimately associated with clausthalite and has a composition close to ideal stoichiometry. The mean empirical formula is (Ag1.98Sb0.01)(1.99)(Te0.96Se0.05)(1.01). Paragenetic relations and thermodynamic data suggest that hessite crystallized in equilibrium with clausthalite, berzelianite, and tiemannite under conditions of almost identical, high fugacitities of Se-2 and Te-2, which very locally were approached in the main selenide stage of Jurassic age. Native tellurium (?) formed as replacement product of hessite. Niederschlema-Alberoda provides the first record of hessite from an uranium deposit worldwide. Hessite and native Te are the first tellurium minerals reported from the Erzgebirge metallogenic province
A system based on variation of the octahedrally coordinated cations is proposed for graphical presentation and subdivision of tri- and dioctahedral K micas, which makes use of elemental differences (in a.p.f.u.): (Mg - Li) [= mgli] and (Fe-tot + Mn + Ti - Al-VI) [= feal]. All common true tri- and dioctahedral K micas are shown in a single polygon outlined by seven main compositional points forming its vertices. Sequentially clockwise, starting from Mg-3 (phlogopite), these points are: Mg2.5Al0.5, Al(2.167)square(0.833), Al1.75Li1.25, Li2Al (polylithionite), Fe22+Li, and Fe-3(2+) (annite). Trilithionite (Li1.5Al1.5), Li1.5Fe2+Al0.5, Fe22+Mg, and Mg2Fe2+ are also located on the perimeter of the polygon. IMA-siderophyllite (Fe22+Al) and muscovite (Al(2)square) plot inside. The classification conforms with the IMA-approved mica nomenclature and differentiates among the following mica species according to their position in a diagram consisting of nigh and feal axes plotted orthogonally; trioctahedral: phlogopite, biotite, siderophyllite, annite, zinnwaldite, lepidolite and tainiolite: dioctahedral: muscovite, phengite and celadonite. Potassium micas with [Si] <2.5 a.p.f.u. including IMA-siderophyllite, KFe22+AlAl2Si2O10(OH)(2), and IMA-eastonite, KMg2AlAl2Si2O10(OH)(2) seem not to form in nature. The proposed subdivision has several advantages. All common true, trioctahedral and dioctahedral K micas, whether Li-bearing or Li-free, are shown within one diagram, which is easy to use and gives every mica composition an unambiguously defined name. Mica analyses with Fe2+, Fe3+, Fe2+ + Fe3+, or Fe-tot can be considered, which is particularly Valuable for microprobe analyses. It facilitates easy reconstruction of evolutionary pathways of mica compositions during crystallization, a feature having key importance in petrologically oriented research. Equally important, the subdivision has great potential for understanding many of the crystal-chemistry features of the K micas. In turn this may allow one to recognize and discriminate the extent to which crystal chemistry or bulk composition controls the occurrence of some seemingly possible or hypothetical K mica
We remelted and analyzed crystallized silicate melt inclusions in quartz from a porphyritic albitezinnwaldite microgranite dike to determine the composition of highly evolved, shallowly intruded, Li- and F-rich granitic magma and to investigate the role of crystal fractionation and aqueous fluid exsolution in causing the extreme extent of magma differentiation. This dike is intimately associated with tin- and tungsten-mineralized granites of Zinnwald, Erzgebirge, Germany. Prior research on Zinnwald granite geochemistry was limited by the effects of strong and pervasive greisenization and alkali-feldspar metasomatism of the rocks. These melt inclusions, however, provide important new constraints on magmatic and mineralizing processes in Zinnwald magmas. The mildly peraluminous granitic melt inclusions are strongly depleted in CAFEMIC constituents (e.g., CaO, FeO, MgO, TiO2), highly enriched in lithophile trace elements, and highly but variably enriched in F and Cl. The melt inclusions contain up to several thousand ppm Cl and nearly 3 wt% F, on average; several inclusions contain more than 5 wt% F. The melt inclusions are geochemically similar to the corresponding whole-rock sample, except that the former contain much more F and less CaO, FeO, Zr, Nb, Sr, and Ba. The Sr and Ba abundances are very low implying the melt inclusions represent magma that was more evolved than that represented by the bulk rock. Relationships involving melt constituents reflect increasing lithophile-element and halogen abundances in residual melt with progressive magma differentiation. Modeling demonstrates that differentiation was dominated by crystal fractionation involving quartz and feldspar and significant quantities of topaz and F-rich zinnwaldite. The computed abundances of the latter phases greatly exceed their abundances in the rocks, suggesting that the residual melt was separated physically from phenocrysts during magma movement and evolution. Interactions of aqueous fluids with silicate melt were also critical to magma evolution. To better understand the role of halogen-charged, aqueous fluids in magmatic differentiation and in subsequent mineralization and metasomatism of the Zinnwald granites, Cl-partitioning experiments were conducted with a F-enriched silicate melt and aqueous fluids at 2,000 bar (200 MPa). The results of the experimentally determined partition coefficients for Cl and F, the compositions of fluid inclusions in quartz and other phenocrysts, and associated geochemical modeling point to an important role of magmatic-hydrothermal fluids in influencing magma geochemistry and evolution. The exsolution of halogen-charged fluids from the Li- and F- enriched Zinnwald granitic magma modified the Cl, alkali, and F contents of the residual melt, and may have also sequestered Li, Sri, and W from the melt. Many of these fluids contained strongly elevated F concentrations that were equivalent to or greater than their Cl abundances. The exsolution of F-, Cl-, Li-, +/- W- and Sn-bearing hydrothermal fluids from Zinnwald granite magmas was important in effecting the greisenizing and alkali-feldspathizing metasomatism of the granites and the concomitant mineralization
To address one of the central questions of plate tectonics-How do large transform systems work and what are their typical features?-seismic investigations across the Dead Sea Transform (DST), the boundary between the African and Arabian plates in the Middle East, were conducted for the first time. A major component of these investigations was a combined reflection/ refraction survey across the territories of Palestine, Israel and Jordan. The main results of this study are: (1) The seismic basement is offset by 3-5 km under the DST, (2) The DST cuts through the entire crust, broadening in the lower crust, (3) Strong lower crustal reflectors are imaged only on one side of the DST, (4) The seismic velocity sections show a steady increase in the depth of the crust-mantle transition (Moho) from 26 km at the Mediterranean to 39 km under the Jordan highlands, with only a small but visible, asymmetric topography of the Moho under the DST. These observations can be linked to the left-lateral movement of 105 km of the two plates in the last 17 Myr, accompanied by strong deformation within a narrow zone cutting through the entire crust. Comparing the DST and the San Andreas Fault (SAF) system, a strong asymmetry in subhorizontal lower crustal reflectors and a deep reaching deformation zone both occur around the DST and the SAF. The fact that such lower crustal reflectors and deep deformation zones are observed in such different transform systems suggests that these structures are possibly fundamental features of large transform plate boundaries
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
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
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)
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
In a sample from the Niederschlema-Alberoda U-Se-polymetallic deposit, western Erzgebirge, Germany, the entire PbSe-PbS solid-solution series was observed associated with uraninite, coffinite, hematite, acanthite, sphalerite, chalcopyrite, pyrite, and lollingite. Early deposited, Se-rich members of the Pb(Se, S) series occur as fracture fillings inside spherical uraninite or on its surface or form anhedral to subhedral grains precipitated in the immediate neighbourhood of the U minerals. Later crystallized, S-rich members of the series are affiliated with the sulfide minerals. The solid-solution series covers the range PbS1.00-Pb(S0.04Se0.96)(&USigma; 1.00) virtually free of gaps, consistent with a temperature of formation of &GE; 100° C. The PbSe-PbS solid solutions were likely deposited from hydrothermal fluids that became successively depleted in Se and enriched in S. The fugacities of selenium and sulfur covered the range -17 < logfSe(2) < -26 and -17 < logfS(2) < -22, respectively, implying fSe(2)/fS(2) &LE; 1. The spherical texture of the uraninite, as well as its U-Th-total Pb age (192 ± 21 Ma), imply deposition of the Pb(Se, S) series during the Jurassic, contemporaneous with the formation of the bulk of the other selenium minerals. The electron-microprobe data from this study confirm earlier inferences on complete miscibility between clausthalite and galena deduced from X-ray patterns of PbSe-PbS solid solutions from different uranium-vanadium deposits of the Colorado Plateau (COLEMAN 1959). In Niederschlema-Alberoda, the entire clausthalite-galena series occurs in a single section
Thermobarometrical and mineral-chemical investigations by electron microprobe and LA-ICP-MS on a sillimanite- bearing pegmatoid from the Reinbolt Hills provide important constraints on the P-T-X-age relations of part of East Antarctica during Pan-African tectonism. U-Th-total Pb ages of monazite imply that the pegmatoid of originally Grenvillan age (zircon U-Pb age of ca. 900 Ma) underwent a major, late Pan-African (Cambrian) regional, granulite-facies metamorphism between 500 and 550 Ma. Most of the monazite formed during this event, as result of apatite metasomatism owing to infiltration of high-grade metamorphic fluids. Apatite-biotite and other mineral thermobarometers define the peak metamorphic temperatures and pressures with 850-950 degrees C and 0.8-1.0 GPa. The F-Cl-OH relations in apatite, and biotite, the chemistry of fluid inclusions and the presence of K-feldspar microveins suggest that the metasomatising fluid was a CO2-bearing, diluted KCl brine. The pegmatoid is the first record of monazite-(Ce) formed from fluorapatite that is rich in U (up to 2.6 Wt% UO2) and possesses Th/U ratios <1 (0.09 on average). These chemical signatures are direct reflection of the U and Th concentration patterns in the parental fluorapatite
The mildly peraluminous granite of Seiffen, in the eastern Erzgebirge of Germany, is exposed by drillcores and associated with an abandoned Sri mine. The granite is of Stefanian age, with overlapping Th-U-total Pb monazite (302 +/- 4 Ma) and K-Ar siderophyllite ages (301 +/- 5 Ma). It is among the youngest granites in the Erzgebirge, emplaced in an extensional setting. The medium-grained, equigranular granite classifies as high-F, low-P Li-mica granite of A-type affinity. It is spatially associated with a high-Si rhyolitic microgranite, documenting the shallow intrusion level of this igneous association. Zircon, monazite-(Ce), and xenotime-(Y) constitute important radioactive accessory minerals in the granite, hosting the major proportions (> 80-90%) of the bulk-rock budgets of the REE, Y, and Th. A significant percentage of U (40-50%) may reside within unidentified phases or precipitated along grain boundaries. The most uncommon accessory phase is late-magmatic ytterbian xenotime-(Y) containing up to 11.2 wt% Yb2O3, in addition to 7.3 wt% Er2O3 and 7.9 wt% Dy2O3. The Seiffen granite (epsilon(Nd(300)) = -4.6) is geochemically evolved and rich in Sri (23-63 ppm) and W (11-14 ppm). It contains elevated to high concentrations of incompatible lithophile elements such as F, Li, Ga, Rb, Y, Nb, Cs, REE, Th, and U, thus having much in common chemically with subvolcanic ongonites. The most prominent compositional feature is the strong enrichment (in ppm) in Be (51-55) and Ta (23-28). The granite exhibits flat chondrite-normalized REE patterns (La-N/Lu-N = 1.35-1.48) and a moderate negative Eu anomaly (Eu/Eu* = 0.12-0.13). Indications for alteration-induced, postmagmatic disturbances of initial elemental abundances are weak and mainly relate to the ore-forming elements Sri and U.
Fractional crystallization of peraluminous F- and H(2)O-rich granite magmas progressively enriches the remaining melt with volatiles. We show that, at saturation, the melt may separate into two immiscible conjugate melt fractions, one of the fractions shows increasing peraluminosity and the other increasing peralkalinity. These melt fractions also fractionate the incompatible elements to significantly different degrees. Coexisting melt fractions have differing chemical and physical properties and, due to their high density and viscosity contrasts, they will tend to separate readily from each other. Once separated, each melt fraction evolves independently in response to changing T/P/X conditions and further immiscibility events may occur, each generating its own conjugate pair of melt fractions. The strongly peralkaline melt fractions in particular are very reactive and commonly react until equilibrium is attained. Consequently, the peralkaline melt fraction is commonly preserved only in the isolated melt and mineral inclusions. We demonstrate that the differences between melt fractions that can be seen most clearly in differing melt inclusion compositions are also visible in the composition of the resulting ore-forming and accessory minerals, and are visible on scales from a few micrometers to hundreds of meters.
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.
A comprehensive survey of the accessory-mineral assemblages in Variscan granites of the German Erzgebirge and Pan-African granites from Jordan revealed the occurrence of intermediate solid solutions of the tetragonal thorite- xenotime-zircon-coffinite mineral group with partially novel compositions. These solid solutions preferentially formed in evolved and metasomatically altered, P-poor leucogranites of either I- or A-type affinity. Thorite from the Erzgebirge contained up to 18-8 Wt-% Y2O3, 16.1 wt.% ZrO2, and 23.3 Wt-% UO2. Xenotime and zircon have incorporated Th in abundances up to 36.3 wt.% and 41.8 wt.% ThO2, respectively. Extended compositional gradation with only minor gaps is confined to hydrated members of this mineral group, and is observed to exist between thorite and xenotime, thorite and coffinite, and Y-HREE-bearing thorite and zircon. Complex, hydrous solid solutions containing elevated abundances of three or more of the endmembers are subordinate. Previously reported intermediate solid solutions between anhydrous zircon and xenotime, and anhydrous zircon and thorite, are not observed and are in conflict with experimental work demonstrating very limited miscibility between anhydrous species of endmember composition. The majority of hydrous intermediate solid solutions in the Th-Y-Zr-U system are likely thermodynamically unstable. Instead, they are probably metastable responses to unusual physico-chemical conditions involving various parameters and conditions, the relative importance of which is incompletely known. Leaching and dissolution of preexisting accessory phases during interaction with F-bearing hydrous fluids enriched in Th, Y(HREE), Zr, and/or U, and common deposition of the various elements at disequilibrium (supersaturation) seems to play a key role, but other processes may be of similar importance. Experimental work involving hydrous conditions and complex systems composed of more than two endmembers are needed to shed light into the stability relations of the chemically uncommon compositions treated in this study.
The strongly peraluminous and P-rich, protolithionite and zinnwaldite leucogranites from Podlesi, western Krusne Hory Mts., Czech Republic, contain accessory zircon with extraordinary enrichment of several elements, which constitute trace elements in common zircon. Elements showing a not yet reported anomalous enrichment include P (up to 20.2 wt.% P2O5; equivalent to 0.60 apfu, formula calculated on the basis of 4 oxygen atoms), Bi (up to 9.0 wt.% Bi2O3; 0.086 apfu), Nb (up to 6.7 wt.% Nb2O5, 0.12 apfu), Sc (up to 3.45 wt.% Sc2O3; 0.10 apfu), U (up to 14.8 wt.% UO2; 0.12 apfu) and F (up to 3.81 wt.% F; 0.42 apfu). Strong enrichment of P preferentially involved the berlinite-type substitution (2 Si4+ double left right arrow P5+ + Al3+) implying that significant Al may enter the Si position in zircon. Incorporation of other exotic elements is primarily governed by the xenotime (Si4++Zr4+ double left right arrow P5++Y3+), pretulite (Sc3++P5+ double left right arrow Zr4++Si4+), brabantite-type (Ca2++(U, Th)(4+)+2P(5+) double left right arrow 2Zr(4+)+2Si(4+)), and ximengite-type (Bi3++P5+double left right arrow Zr4++Si4+) substitution reactions. One part of the anomalous zircons formed late-magmatically, from a strongly peraluminous, P-F-U-rich hydrous residual melt that gave rise to the zinnwaldite granite. Interaction with aggressive residual fluids and metamictization have further aided in element enrichment or depletion, particularly in altered parts of zircon contained in the protolithionite granite. Most of the zircon from F-rich greisens have a composition close to endmember ZrSiO4 and are chemically distinct from zircon in its granite parent. This discrepancy implies that at Podlesi, granitic zircon became unstable and completely dissolved during greisenization. Part of the mobilized elements was reprecipitated in newly grown, hydrothermal zircon.