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Magnetite is common in various magmatic and hydrothermal ore deposit types, and its trace element geochemistry has become increasingly used in ore genesis studies and mineral exploration. While fractional crystallization has been shown to influence the chemistry of igneous magnetite, the extent to which this process regulates the trace element composition of hydrothermal magnetite remains poorly understood. In this study, we analyzed trace elements in hydrothermal magnetite from the Baijian Fe-(Co) skarn deposit in eastern China and used Rayleigh and equilibrium fractionation modeling to demonstrate the importance of magnetite precipitation in controlling fluid and magnetite chemistry during Fe skarn mineralization. The Baijian Fe-(Co) skarn deposit has three stages of magnetite. From early Mag-1 to later Mag-2 and Mag-3, the concentrations of compatible elements (Ni and V) decrease, whereas those of incompatible elements (Zn, Mn, and Co) increase. There are obvious trends of increasing incompatible/compatible element ratios (e.g., Co/Ni, Zn/V, and Zn/Ni) and decreasing compatible/incompatible element ratios (e.g., V/Mn, Ni/Mn, and V/Co) from Mag-1 to Mag-3, with strong correlations between each of these ratios. Such systematic trace element variations in successive stages of magnetite can be best explained by increasing degrees of fractional crystallization with time. The wide range of incompatible/compatible element ratios (spanning 2-4 orders of magnitude) in Mag-2 and Mag-3 suggests that magnetite crystallization follows a process akin to Rayleigh fractionation. Results from this study highlight the significant role that magnetite crystallization during skarn formation has on the trace element chemistry of this mineral. Moreover, as the crystallization of magnetite progresses, the Co/Fe ratio of residual hydrothermal fluids is elevated, which favors the precipitation of Co in late-stage sulfides. This process helps to explain why some Fe skarn deposits, as well as magnetite-rich iron oxide-apatite and iron oxide-copper-gold deposits, are potentially important economic sources for Co, currently necessary as one component in Li-ion batteries. [ABSTRACT FROM AUTHOR]

Apatite is a ubiquitous phase in granite plutons and in most adjacent country rocks, thus contamination of a granite magma with wall-rock material results in two genetic types of apatite in the magma: cognate and foreign. These two textural and chemical varieties of apatite undergo textural and compositional changes to reach physical and chemical equilibrium (perfect assimilation) in the melt. Our experiments replicate the conditions in such contaminated granites. The starting materials consist of a peraluminous synthetic SiO2-Al2O3-Na2O-K2O (SANK 1.3) granite gel with A/NK of 1.3, synthetic F-apatite, synthetic Cl-apatite, and natural Durango apatite. Initial experiments in cold-seal hydrothermal pressure vessels at magmatically realistic temperatures of 750 °C and pressures of 200 MPa produced negligible reactions, even after run times of 2000 h. Instead, we used an argon-pressurized internally heated pressure vessel with a rapid-quench setup at temperatures of 1200 °C, pressure of 200 MPa, and run durations of 192 h. An advantage of this high temperature is that it exceeds the liquidus for quartz and feldspar; therefore, apatite is the only solid phase in the run products. The starting composition of each run was 90 wt% SANK 1.3 granite gel and 10 wt% crushed apatite (consisting of one, two, or three varieties), with and without 4 wt% added H2O. Run products were examined by SEM for texture and by EMPA and LA-ICP-MS for composition. The starting synthetic granite composition contains no Ca, F, Cl, or REEs thus, in every run, apatite was initially undersaturated in the melt. In all experiments, most large apatite grains consisted of anhedral shards with rounded corners, most small apatite grains were round, and a small proportion of apatite grains developed one or more crystal faces. In experiments with two or three apatite compositions, the run-product apatite grains had compositions intermediate between those of the starting-material grains, and they were homogeneous with respect to Cl, and probably F, but not with respect to REEs. The processes to reach textural equilibrium consist of dissolution until the melt is saturated in apatite, followed by Ostwald ripening to eliminate small grains and to develop crystal faces on larger ones. The processes to reach chemical equilibrium consist of dissolution of apatite, diffusion of cations (Ca, P, REE) and anions (F, Cl, OH) through the silicate melt, and solid-state diffusion in the undissolved apatite grains. The halogens approached chemical equilibrium in all experiments, but in the experiments containing Durango apatite, the REEs have not. Models involving radial diffusion into spherical apatite grains at the temperatures of the experiments show complete re-equilibration of the halogens, but changes in the REE concentrations affecting only the outer few micrometers. We conclude that the rate of chemical equilibrium for the halogens is greater than the rate of physical equilibrium for texture, which in turn is greater the rate of chemical equilibrium for REEs. We illustrate these processes with a natural example of contaminated granite from the South Mountain Batholith in Nova Scotia. Given that all granites are contaminated rocks, we propose that future petrogenetic studies focus on developing techniques for a minerals-based quantitative estimation of contamination (QEC). [ABSTRACT FROM AUTHOR]

Recent advances in the dating of monazite using the electron microprobe indicate that ThSi[O.sub.4]- and/ or CaTh[(P[O.sub.4]).sub.2]-enriched intergrowths in monazite can give ages younger than the original monazite. The morphology of the intergrowths suggests that the original monazite grain has been partly altered by a fluid in which Th, Si, and Ca are mobile. This hypothesis has been tested in the piston-cylinder apparatus at 1000 MPa and 900[degrees]C utilizing a natural, unzoned, Th- and Pb-bearing monazite-(Ce) and [Na.sub.2][Si.sub.2][O.sub.5]+[H.sub.2]O. During the experiment, a subset of the monazite grains acquired ThSi[O.sub.4]-enriched areas with sharp compositional boundaries devoid of Pb and show evidence of being a pseudomorphic partial replacement of the monazite rather than an overgrowth of the monazite. These experiments support the hypothesis that similar Th-enriched or Th-depleted patches with sharp compositional boundaries observed in natural monazite could be the result of fluid-induced alteration via coupled dissolution-reprecipitation. If so, such altered regions would yield information concerning the nature of the fluid responsible for their formation as well as allow for the dating of single or multiple metasomatic events assuming that all pre-existing radiogenic Pb is removed during alteration. Keywords: Monazite, huttonite, alkali-bearing fluids, dissolution-reprecipitation, geochronology, experimental petrology, high-grade metamorphism, Th-U-Pb dating DOI: 10.2138/am.2010.3525

Solution calorimetric measurements have been made on 17 synthetic fluorapatite-chlorapatite crystalline solutions at 50[degrees]C in 20.0 wt% HCl under isoperibolic conditions. Analysis of the calorimetric data indicates that heats of mixing across the series may reach values as high as 8.3 kJ/mol. Normally such a high degree of thermodynamic nonideality would be associated with immiscibility, yet no such miscibility gap is indicated by either synthetic or natural fluor-chlorapatite specimens. Based on full chemical analyses, all Cl-rich samples ([X.sub.Cl] > 0.65) of this study have halogen deficiencies that imply the presence of 4-11 mol% vacancies in the anion sites, which are interpreted to be associated with oxyapatite substitution. Separate analysis of data for the vacancy-free samples produces a linear fit for enthalpy of solution vs. composition, which yields an alternative interpretation of thermodynamic ideality. Together these models define the limits of enthalpy behavior for the fluor-chlorapatite system. Keywords: Enthalpies of mixing, fluorapatite, chlorapatite, thermodynamics DOI: 10.2138/am.2010.3485

Thorite and uraninite inclusions are documented in metasomatized regions in three xenotime crystals and one monazite crystal collected from three granitic pegmatites hosted within an anorthosite intrusion located on the island of Hidra, southwestern Norway. Formation of these inclusions is demonstrated to be the result of dissolution-reprecipitation processes that occurred in an effectively closed chemical system. The reaction was initiated by interaction between the early crystallizing orthophosphate minerals and the evolving pegmatite fluid. This fluid was dominated by [H.sub.2]O, but also contained F and minor amounts of C1, and significant quantities of dissolved [Na.sup.+] and [K.sup.+]. This is an example of auto-metasomatism and highlights a natural case where Th-U-Si-enriched orthophosphate minerals have been partially altered such that the Th, U, and Si have been converted to secondary inclusions within the now Th-U-Si-depleted orthophosphate via reaction with fluids rich in alkali elements. Keywords: Monazite, xenotime, thorite, uraninite, dissolution-reprecipitation, pegmatite, alkali-rich fluids

The formation of sillimanite, under metastable conditions, relative to corundum and quartz has been defined experimentally, approximately 700 to 800 MPa inside the kyanite stability field thereby allowing for the approximate location of the metastable Sil = Cnd + Qtz equilibrium to be outlined in P-T space from 600 to 800 [degrees]C. Experiments involved using a NaCl assembly with a graphite furnace in a two-piston-cylinder apparatus. The thermocouple tip was in direct contact with the flat-lying, folded Pt capsule thereby minimizing thermal gradients to Keywords: Sillimanite, kyanite, corundum, quartz, rate of reaction, experimental petrology, Rietveld refinement, aluminosilicates

Monazite is both partially replaced and overgrown by a ThSi[O.sub.4] phase along grain rims in a series of experiments from 300 to 900 [degrees]C and 200 to 1000 MPa. All experiments consisted of 10 mg of 100-500 [micro]m size, euhedral to subhedral crystals of a natural Th-free monazite-(Ce), 5 mg of Th[(N[O.sub.3]).sub.4]*5[H.sub.2]O, 2.5 mg of Si[O.sub.2], and 5 mg of [H.sub.2]O loaded into 3 mm wide, 1 or 1.3 cm long platinum capsules that were arc welded shut. Experimental conditions were: 300 [degrees]C at 200 and 500 MPa; 300, 400, 500, 600, and 700 [degrees]C at 500 MPa (cold seal hydrothermal autoclave); and 900[degrees]C at 1000 MPa (Catz assembly; pistoncylinder press). Back-scattered electron (BSE) imaging, electron back-scattered diffraction (EBSD) analysis, and transmission electron microscopy (TEM) indicates that in the experiments from 500 to 900[degrees]C, the ThSi[O.sub.4] phase took the form of monoclinic huttonite implying that huttonite, associated with monazite, could exist metastably over a much greater P-T range than previously thought. TEM analysis of a foil cut perpendicular to the monazite-huttonite interface from the 600 [degrees]C, 500 MPa experiment using a focused ion beam (FIB) indicates that the huttonite as well as the interface between the huttonite and monazite is characterized by fluid inclusions. High-resolution TEM analysis indicates that the huttonite-monazite interface is coherent. In the case of replacement of monazite by huttonite, fluid-aided dissolution-reprecipitation is proposed as the most likely mechanism responsible. Keywords: Monazite, huttonite, dissolution-reprecipitation, metastability, metasomatism, EBSD, TEM, pseudomorphism