Sample records for cheralite

  1. Incorporation of thorium in the rhabdophane structure: Synthesis and characterization of Pr1-2xCaxThxPO4·nH2O solid solutions

    NASA Astrophysics Data System (ADS)

    Qin, Danwen; Mesbah, Adel; Gausse, Clémence; Szenknect, Stéphanie; Dacheux, Nicolas; Clavier, Nicolas

    2017-08-01

    Thorium incorporation in the rhabdophane structure as Pr1-2xCaxThxPO4·nH2O solid solutions was successfully achieved and resulted in the preparation of a low temperature precursor of the monazite-cheralite type Pr1-2xCaxThxPO4. The rhabdophane compounds are considered as potential neoformed phases in case of release of actinides from the phosphate-based ceramic wasteforms envisaged to host radionuclides in the back-end of the nuclear fuel cycle. A multiparametric study was thus undertaken to specify the wet chemistry conditions (starting stoichiometry, temperature, heating time) leading to single phase Pr1-2xCaxThxPO4·nH2O powdered samples. The excess of calcium appeared to be a prevailing factor with a suggested initial Ca:Th ratio being equal to 10. Similarly, the recommended heating time should exceed 4 days while the optimal temperature of synthesis is 110 °C. Under these conditions, the stability domain of Pr1-2xCaxThxPO4·nH2O ranged from x = 0.00 to x = 0.15. After heating at 1100 °C under air during 6 h, rhabdophane-type samples were fully converted into the highly durable Pr1-2xCaxThxPO4 cheralite ceramic wasteform.

  2. Crystal chemistry of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} double monophosphates

    DOE Office of Scientific and Technical Information (OSTI.GOV)

    Bregiroux, Damien, E-mail: damien.bregiroux@upmc.fr; Popa, Karin; Wallez, Gilles

    2015-10-15

    M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds have been extensively studied for several decades for their potential applications in the field of several domains such as matrices for actinides conditioning, phosphors etc. In this paper, the relationships between composition and crystal structure of these compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. M{sup II}M′{sup IV}(PO{sub 4}){sub 2} structures stem from two different archetypes: the cheralite and the yavapaiite structures, with some exceptions that are also described in this article. The ratio of themore » cations radii appears to be the most relevant parameter. The high ratio between the ionic radii of the divalent and tetravalent cations in yavapaiite derivates results in the ordering of these cations into well-differentiated polyhedra whereas cheralite is the only non-ordered structure encountered for M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds. - Graphical abstract: In this paper, the relationships between composition and crystal structure of M{sup II}M′{sup IV}(PO{sub 4}){sub 2} compounds are established. A review of the various processes used for the synthesis of these compounds is also proposed, as well as their most reported properties. - Highlights: • Crystal structure–composition relationships of MIIM′IV(PO4)2 compounds. • Review of the various processes used for the synthesis of these compounds. • Their most reported properties are described and discussed.« less

  3. Multi-stage evolution of xenotime-(Y) from Písek pegmatites, Czech Republic: an electron probe micro-analysis and Raman spectroscopy study

    NASA Astrophysics Data System (ADS)

    Švecová, E.; Čopjaková, R.; Losos, Z.; Škoda, R.; Nasdala, L.; Cícha, J.

    2016-12-01

    The chemical variability, degree of radiation damage, and alteration of xenotime from the Písek granitic pegmatites (Czech Republic) were investigated by micro-chemical analysis and Raman spectroscopy. Dominant large xenotime-(Y) grains enriched in U, Th and Zr crystallized from a melt almost simultaneously with zircon, monazite and tourmaline. Xenotime is well to poorly crystalline depending on its U and Th contents. It shows complex secondary textures cutting magmatic growth zones as a result of its interaction with F,Ca,alkali-rich fluids during the hydrothermal stage of the pegmatite evolution. The magmatic xenotime underwent intense secondary alteration, from rims inwards, resulting in the formation of inclusion-rich well crystalline xenotime domains of near end-member composition. Two types of recrystallization were distinguished in relation to the type of inclusions: i) xenotime with coffinite-thorite, cheralite and monazite inclusions and ii) xenotime with zirconcheralite and zircon inclusions. Additionally, inner poorly crystalline U,Th-rich xenotime domains were locally altered, hydrated, depleted in P, Y, HREE, U, Si and radiogenic Pb, and enriched in fluid-borne cations (mainly Ca, F, Th, Zr, Fe). Interaction of radiation-damaged xenotime with hydrothermal fluids resulted in the disturbance of the U-Th-Pb system. Alteration of radiation-damaged xenotime was followed by intensive recrystallization indicating the presence of fluids >200 °C. Subsequently other types of xenotime formed as a consequence of fluid-driven alteration of magmatic monazite, and Y,REE,Ti,Nb-oxides or crystallized from hydrothermal fluids along cracks in magmatic monazite and xenotime.

  4. Sulphate incorporation in monazite lattice and dating the cycle of sulphur in metamorphic belts

    NASA Astrophysics Data System (ADS)

    Laurent, Antonin T.; Seydoux-Guillaume, Anne-Magali; Duchene, Stéphanie; Bingen, Bernard; Bosse, Valérie; Datas, Lucien

    2016-11-01

    Microgeochemical data and transmission electron microscope (TEM) imaging of S-rich monazite crystals demonstrate that S has been incorporated in the lattice of monazite as a clino-anhydrite component via the following exchange Ca2+ + S6+ = REE3+ + P5+, and that it is now partly exsolved in nanoclusters (5-10 nm) of CaSO4. The sample, an osumilite-bearing ultra-high-temperature granulite from Rogaland, Norway, is characterized by complexly patchy zoned monazite crystals. Three chemical domains are distinguished as (1) a sulphate-rich core (0.45-0.72 wt% SO2, Th incorporated as cheralite component), (2) secondary sulphate-bearing domains (SO2 >0.05 wt%, partly clouded with solid inclusions), and (3) late S-free, Y-rich domains (0.8-2.5 wt% Y2O3, Th accommodated as the huttonite component). These three domains yield distinct isotopic U-Pb ages of 1034 ± 6, 1005 ± 7, and 935 ± 7 Ma, respectively. Uranium-Th-Pb EPMA dating independently confirms these ages. This study illustrates that it is possible to discriminate different generations of monazite based on their S contents. From the petrological context, we propose that sulphate-rich monazite reflects high-temperature Fe-sulphide breakdown under oxidizing conditions, coeval with biotite dehydration melting. Monazite may therefore reveal the presence of S in anatectic melts from high-grade terrains at a specific point in time and date S mobilization from a reduced to an oxidized state. This property can be used to investigate the mineralization potential of a given geological event within a larger orogenic framework.

  5. Magmatic (silicates/saline/sulfur-rich/CO2) immiscibility and zirconium and rare-earth element enrichment from alkaline magma chamber margins : Evidence from Ponza Island, Pontine Archipelago, Italy

    USGS Publications Warehouse

    Belkin, H.E.; de Vivo, B.; Lima, A.; Torok, K.

    1996-01-01

    Fluid inclusions were measured from a feldspathoid-bearing syenite xenolith entrained in trachyte from Ponza, one of the islands of the Pontine Archipelago, located in the Gulf of Gaeta, Italy. The feldspathoid-bearing syenite consists mainly of potassium feldspar, clinopyroxene, amphibole, biotite, titanite, manganoan magnetite, apatite with minor nosean, Na-rich feldspar, pyrrhotite, and rare cheralite. Baddeleyite and zirkelite occur associated with manganoan magnetite. Detailed electron-microprobe analysis reveals enrichments in REE, Y, Nb, U, Th as well as Cl and F in appropriate phases. Fluid inclusions observed in potassium feldspar are either silicate-melt or aqueous inclusions. The aqueous inclusions can be further classified as. (1) one-phase vapor, (2) two-phase (V + L) inclusions, vapor-rich inclusions with a small amount of CO2 in most cases; homogenization of the inclusions always occurred in the vapor phase between 359 and 424??C, salinities vary from 2.9 to 8.5 wt. % NaCl equivalent; and. (3) three-phase and multiphase inclusions (hypersaline/sulfur-rich aqueous inclusions sometimes with up to 8 or more solid phases). Daughter minerals dissolve on heating before vapor/liquid homogenization. Standardless quantitative scanning electron microscope X-ray fluorescence analysis has tentatively identified the following chloride and sulfate daughter crystals; halite, sylvite, glauberite. arcanite, anhydrite, and thenardite. Melting of the daughter crystals occurs between 459 and 536??C (54 to 65 wt. % NaCI equivalent) whereas total homogenization is between 640 and 755??C. The occurrence of silicate-melt inclusions and high-temperature, solute-rich aqueous inclusions suggests that the druse or miarolitic texture of the xenolith is late-stage magmatic. The xenolith from Ponza represents a portion of the peripheral magma chamber wall that has recorded the magmatic/hydrothermal transition and the passage of high solute fluids enriched in chlorides, sulfur, and incompatible elements.

  6. Magmatic-hydrothermal fluid interaction and mineralization in alkali-syenite nodules from the Breccia Museo pyroclastic deposit, Naples, Italy: Chapter 7 in Volcanism in the Campania Plain — Vesuvius, Campi Flegrei and Ignimbrites

    USGS Publications Warehouse

    Fedele, Luca; Tarzia, Maurizio; Belkin, Harvey E.; De Vivo, Benedetto; Lima, Annamaria; Lowenstern, Jacob

    2007-01-01

    The Breccia Museo, a pyroclastic flow that crops out in the Campi Flegrei volcanic complex (Naples, Italy), contains alkali-syenite (trachyte) nodules with enrichment in Cl and incompatible elements (e.g., U, Zr, Th, and rare-earth elements). Zircon was dated at ≈52 ka, by U-Th isotope systematics using a SHRIMP. Scanning electron microscope and electron microprobe analysis of the constituent phases have documented the mineralogical and textural evolution of the nodules of feldspar and mafic accumulations on the magma chamber margins. Detailed electron microprobe data are given for alkali and plagioclase feldspar, salite to ferrosalite clinopyroxene, pargasite, ferrogargasite, magnesio-hastingsite hornblende amphibole, biotite mica, Cl-rich scapolite, and a member (probable davyne-type) of the cancrinite group. Detailed whole rock, major and minor element data are also presented for selected nodules. A wide variety of common and uncommon accessory minerals were identified such as zircon, baddeleyite, zirconolite, pollucite, sodalite, titanite, monazite, cheralite, apatite, titanomagnetite and its alteration products, scheelite, ferberite, uraninite/thorianite, uranpyrochlore, thorite, pyrite, chalcopyrite, and galena. Scanning electron microscope analysis of opened fluid inclusions identified halite, sylvite, anhydrite, tungstates, carbonates, silicates, sulfides, and phosphates; most are probably daughter minerals. Microthermometric determinations on secondary fluid inclusions hosted by alkali feldspar define a temperature regime dominated by hypersaline aqueous fluids. Fluid-inclusion temperature data and mineral-pair geothermometers for coexisting feldspars and hornblende and plagioclase were used to construct a pressure-temperature scenario for the development and evolution of the nodules. We have compared the environment of porphyry copper formation and the petrogenetic environment constructed for the studied nodules. The suite of ore minerals observed in the nodules supports a potential for mineralization, which is similar to that observed in the alkaline volcanic systems of southern Italy (Pantelleria, Pontine Archipelago, Mt. Somma-Vesuvius).

  7. The Nolans Bore rare-earth element-phosphorus-uranium mineral system: geology, origin and post-depositional modifications

    NASA Astrophysics Data System (ADS)

    Huston, David L.; Maas, Roland; Cross, Andrew; Hussey, Kelvin J.; Mernagh, Terrence P.; Fraser, Geoff; Champion, David C.

    2016-08-01

    Nolans Bore is a rare-earth element (REE)-U-P fluorapatite vein deposit hosted mostly by the ~1805 Ma Boothby Orthogneiss in the Aileron Province, Northern Territory, Australia. The fluorapatite veins are complex, with two stages: (1) massive to granular fluorapatite with inclusions of REE silicates, phosphates and (fluoro)carbonates, and (2) calcite-allanite with accessory REE-bearing phosphate and (fluoro)carbonate minerals that vein and brecciate the earlier stage. The veins are locally accompanied by narrow skarn-like (garnet-diopside-amphibole) wall rock alteration zones. SHRIMP Th-Pb analyses of allanite yielded an age of 1525 ± 18 Ma, interpreted as the minimum age of mineralisation. The maximum age is provided by a ~1550 Ma SHRIMP U-Pb age for a pegmatite that predates the fluorapatite veins. Other isotopic systems yielded ages from ~1443 to ~345 Ma, implying significant post-depositional isotopic disturbance. Calculation of initial ɛNd and 87Sr/86Sr at 1525 Ma and stable isotope data are consistent with an enriched mantle or lower crust source, although post-depositional disturbance is likely. Processes leading to formation of Nolans Bore began with north-dipping subduction along the south margin of the Aileron Province at 1820-1750 Ma, producing a metasomatised, volatile-rich, lithospheric mantle wedge. About 200 million years later, near the end of the Chewings Orogeny, this reservoir and/or the lower crust sourced alkaline low-degree partial melts which passed into the mid- and upper-crust. Fluids derived from these melts, which may have included phosphatic melts, eventually deposited the Nolans Bore fluorapatite veins due to fluid-rock interaction, cooling, depressurisation and/or fluid mixing. Owing to its size and high concentration of Th (2500 ppm), in situ radiogenic heating caused significant recrystallisation and isotopic resetting. The system finally cooled below 300 °C at ~370 Ma, possibly in response to unroofing during the Alice Springs Orogeny. Surface exposure and weathering of fluorapatite produced acidic fluids and intense, near-surface kaolinitised zones that include high-grade, supergene-enriched cheralite-rich ores.

  8. Experimental constraints on the relative stabilities of the two systems monazite-(Ce) - allanite-(Ce) - fluorapatite and xenotime-(Y) - (Y,HREE)-rich epidote - (Y,HREE)-rich fluorapatite, in high Ca and Na-Ca environments under P-T conditions of 200-1000 MPa and 450-750 °C

    NASA Astrophysics Data System (ADS)

    Budzyń, Bartosz; Harlov, Daniel E.; Kozub-Budzyń, Gabriela A.; Majka, Jarosław

    2017-04-01

    The relative stabilities of phases within the two systems monazite-(Ce) - fluorapatite - allanite-(Ce) and xenotime-(Y) - (Y,HREE)-rich fluorapatite - (Y,HREE)-rich epidote have been tested experimentally as a function of pressure and temperature in systems roughly replicating granitic to pelitic composition with high and moderate bulk CaO/Na2O ratios over a wide range of P-T conditions from 200 to 1000 MPa and 450 to 750 °C via four sets of experiments. These included (1) monazite-(Ce), labradorite, sanidine, biotite, muscovite, SiO2, CaF2, and 2 M Ca(OH)2; (2) monazite-(Ce), albite, sanidine, biotite, muscovite, SiO2, CaF2, Na2Si2O5, and H2O; (3) xenotime-(Y), labradorite, sanidine, biotite, muscovite, garnet, SiO2, CaF2, and 2 M Ca(OH)2; and (4) xenotime-(Y), albite, sanidine, biotite, muscovite, garnet, SiO2, CaF2, Na2Si2O5, and H2O. Monazite-(Ce) breakdown was documented in experimental sets (1) and (2). In experimental set (1), the Ca high activity (estimated bulk CaO/Na2O ratio of 13.3) promoted the formation of REE-rich epidote, allanite-(Ce), REE-rich fluorapatite, and fluorcalciobritholite at the expense of monazite-(Ce). In contrast, a bulk CaO/Na2O ratio of 1.0 in runs in set (2) prevented the formation of REE-rich epidote and allanite-(Ce). The reacted monazite-(Ce) was partially replaced by REE-rich fluorapatite-fluorcalciobritholite in all runs, REE-rich steacyite in experiments at 450 °C, 200-1000 MPa, and 550 °C, 200-600 MPa, and minor cheralite in runs at 650-750 °C, 200-1000 MPa. The experimental results support previous natural observations and thermodynamic modeling of phase equilibria, which demonstrate that an increased CaO bulk content expands the stability field of allanite-(Ce) relative to monazite-(Ce) at higher temperatures indicating that the relative stabilities of monazite-(Ce) and allanite-(Ce) depend on the bulk CaO/Na2O ratio. The experiments also provide new insights into the re-equilibration of monazite-(Ce) via fluid-aided coupled dissolution-reprecipitation, which affects the Th-U-Pb system in runs at 450 °C, 200-1000 MPa, and 550 °C, 200-600 MPa. A lack of compositional alteration in the Th, U, and Pb in monazite-(Ce) at 550 °C, 800-1000 MPa, and in experiments at 650-750 °C, 200-1000 MPa indicates the limited influence of fluid-mediated alteration on volume diffusion under high P-T conditions. Experimental sets (3) and (4) resulted in xenotime-(Y) breakdown and partial replacement by (Y,REE)-rich fluorapatite to Y-rich fluorcalciobritholite. Additionally, (Y,HREE)-rich epidote formed at the expense of xenotime-(Y) in three runs with 2 M Ca(OH)2 fluid, at 550 °C, 800 MPa; 650 °C, 800 MPa; and 650 °C, 1000 MPa similar to the experiments involving monazite-(Ce). These results confirm that replacement of xenotime-(Y) by (Y,HREE)-rich epidote is induced by a high Ca bulk content with a high CaO/Na2O ratio. These experiments demonstrate also that the relative stabilities of xenotime-(Y) and (Y,HREE)-rich epidote are strongly controlled by pressure.

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