Experimental determination of CePO4 and YPO4 solubilities in H2O–NaF at 800°C and 1 GPa: implications for rare earth element transport in high‐grade metamorphic fluids

Monazite (CePO₄) and xenotime (YPO₄) are important accessory minerals in metasediments. They host significant rare earth elements (REE) and are useful for geochronology and geothermometry, so it is essential to understand their behavior during the metasomatic processes that attend high‐grade metamorphism. It has been proposed that F‐bearing fluids enhance solubility and mobility of REE and Y during high‐grade metamorphism. We assessed this possibility by determining the solubility of synthetic CePO₄ and YPO₄ crystals in H₂O–NaF fluids at 800°C and 1 GPa. Experiments used hydrothermal piston‐cylinder and weight‐loss methods. Compared to the low solubilities of CePO₄ and YPO₄ in pure H₂O (0.04 ± 0.04 and 0.25 ± 0.04 millimolal, respectively), our results indicate an enormous increase in the solubility of both phosphates with increasing NaF concentration in H₂O: CePO₄ solubility reaches 0.97 molal in 20 mol.% NaF, and YPO₄ shows an even stronger solubility enhancement to 0.45 molal in only 10 mol.% NaF. The greatest relative solubility increases occur at the lowest NaF concentration. The solubilities of CePO₄ and YPO₄ show similar quadratic dependence on NaF, consistent with possible dissolution reactions of: CePO₄ + 2NaF =  CeF₂⁺ + Na₂PO₄^? and YPO₄ + 2NaF = YF₂⁺ + Na₂PO₄^?. Solubilities of both REE phosphates are significantly greater in NaF than in NaCl at equivalent salt concentration. A fluid with 10 mol.% NaCl and multiply saturated with fluorite, CePO₄, and YPO₄ would contain 1.7 millimolal Ce and 3.3 millimolal Y, values that are respectively 2.1–2.4 times greater than in NaCl‐H₂O alone. The results indicate that Y, and by extension heavy rare earth elements (HREE), can be fractionated from LREE in fluorine‐bearing saline brines which may accompany granulite‐facies metamorphism. The new data support previous indications that REE/Y mobility at these conditions is enhanced by complexing with F in the aqueous phase.     

Mobilization of ore fluids during Alpine metamorphism: evidence from hydrothermal veins in the Variscan basement of Western Carpathians,Slovakia

Hydrothermal polymetallic veins of the Gemeric unit of the Western Carpathians are oriented coherently with the foliation of their low‐grade Variscan basement host. Early siderite precipitated from homogeneous NaCl‐KCl‐CaCl₂‐H₂O brines with minor CO₂, while immiscible gas–brine mixtures are indicative of the superimposed barite, quartz–tourmaline and quartz–sulphide stages. The high‐salinity aqueous fluid (18–35 wt%) found in all mineralization stages corresponds to formation water modified by interaction with crystalline basement rocks at temperatures between 140 and 300°C. High brominity (around 1000 ppm in average) resulted from evaporation and anhydrite precipitation in a Permo‐Triassic marine basin, and from secondary enrichment by dissolution of organic matter in the marine sediments at diagenetic temperatures. Sulphate depletion reflects thermogenic reduction during infiltration of the formation waters into the Variscan crystalline basement. Crystallization temperatures of the siderite fill (140–300°C) and oxygen isotope ratios of the parental fluids (4–10‰) increase towards the centre of the Gemeric cleavage fan, probably as a consequence of decreasing water/rock ratios in rock‐buffered hydrothermal systems operating during the initial stages of vein evolution. In contrast, buoyant gas–water mixtures, variable salinities and strongly fluctuating P–T parameters in the successive mineralization stages reflect transition from a closed to an open hydrothermal system and mixing of fluids from various sources. Depths of burial were 6–14 km (1.7–4.4 kbar, in a predominantly lithostatic fluid regime) during the siderite and barite sub‐stages of the north‐Gemeric veins, and up to 16 km (1.6–4.5 kbar, in a hydrostatic to lithostatic fluid regime) in the quartz–tourmaline stage of the south‐Gemeric veins. The fluid pressure decreased down to approximately 0.6 kbar during crystallization of sulphides. U‐Pb‐Th, ⁴⁰Ar/³⁹Ar and K/Ar geochronology applied to hydrothermal muscovite–phengite and monazite, as well as cleavage phyllosilicates in the adjacent basement rocks and deformed Permian conglomerates corroborated the opening of hydrothermal veins during Lower Cretaceous thrusting and their rejuvenation during Late Cretaceous sinistral transpressive shearing and extension.