Fractionation of Rare Earth Elements in Greisen and Hydrothermal Veins Related to A-Type Magmatism

This study focuses on concentrations and fractionation of rare earth elements (REE) in a variety of minerals and bulk materials of hydrothermal greisen and vein mineralization in Paleoproterozoic monzodiorite to granodiorite related to the intrusion of Mesoproterozoic alkali- and fluorine-rich granite. The greisen consists of coarse-grained quartz, muscovite, and fluorite, whereas the veins mainly contain quartz, calcite, epidote, chlorite, and fluorite in order of abundance. A temporal and thus genetic link between the granite and the greisen/veins is established via high spatial resolution in situ Rb-Sr dating, supported by several other isotopic signatures (δ34S, 87Sr/86Sr, δ18O, and δ13C). Fluid-inclusion microthermometry reveals that multiple pulses of moderately to highly saline aqueous to carbonic solutions caused greisenization and vein formation at temperatures above 200–250°C and up to 430°C at the early hydrothermal stage in the veins. Low calculated ∑REE concentration for bulk vein (15 ppm) compared to greisen (75 ppm), country rocks (173–224 ppm), and the intruding granite (320 ppm) points to overall low REE levels in the hydrothermal fluids emanating from the granite. This is explained by efficient REE retention in the granite via incorporation in accessory phosphates, zircon, and fluorite and unfavorable conditions for REE partitioning in fluids at the magmatic and early hydrothermal stages. A noteworthy feature is substantial heavy REE (HREE) enrichment of calcite in the vein system, in contrast to the relatively flat patterns of greisen calcite. The REE fractionation of the vein calcite is explained mainly by fractional crystallization, where the initially precipitated epidote in the veins preferentially incorporates most of the light REE (LREE) pool, leaving a residual fluid enriched in the HREE from which calcite precipitated. Fluorite occurs throughout the system and displays decreasing REE concentrations from granite towards greisen and veins and different fractionation patterns among all these three materials. Taken together, these features confirm efficient REE retention in the early stages of the system and minor control of the REE uptake by mineral-specific partitioning. REE-fractionation patterns and fluid-inclusion data suggest that chloride complexation dominated REE transport during greisenization, whereas carbonate complexation contributed to the HREE enrichment in vein calcite.

Thermodynamic description of Tc(iv) solubility and carbonate complexation in alkaline NaHCO3–Na2CO3–NaCl systems

A comprehensive thermodynamic model is derived for the system Tc4+–Na+–Cl−–OH−–HCO3−–CO32−–H2O(l) based upon solubility experiments in alkaline carbonate solutions, advanced spectroscopic techniques and DFT calculations.

Influence of Carbonate on Uranium Solubility in the WIPP

ABSTRACTIn the performance assessment (PA) for the Waste Isolation Pilot Plant (WIPP), the solubility of uranium (VI) was conservatively set at 10-3 M for all expected WIPP conditions, including the potential and likely effects of carbonate complexation [1]. Under WIPP-relevant conditions, long-term experiments were performed to establish the uranium (VI) solubility limits in WIPP-simulated brine over a broad range of pCH+ values [7.5-12.5] and to evaluate the contribution of carbonate complexation and hydrolysis to uranium (VI) speciation. Data obtained in carbonate-free ERDA-6 brine, a simulated WIPP brine, were reported earlier [2]. In the absence of carbonate, uranium solubility approached 10-7 M at the expected pCH+ in the WIPP (~ 9.5). In the presence of a significant amount of carbonate (millimole levels), recent experimental results showed that uranium (VI) concentrations will not exceed 10-4M. This measured solubility limit is an order of magnitude lower than the uranium solubility value currently used in the WIPP PA [3]. A small effect of borate complexation was found in the pCH+ range [7.5-10]. At pCH+ ≥ 10, hydrolysis overwhelmed carbonate effects, and no amphoteric effect was observed.

Uranium (VI) Solubility in Carbonate-Free ERDA-6 Brine

When present, uranium is usually an element of importance in a nuclear waste repository. In the Waste Isolation Pilot Plant (WIPP), uranium is present in significant quantities, with about 647 metric tons to be placed in the repository [1]. Therefore, the chemistry of uranium, and especially its solubility, needs to be determined under WIPP-relevant conditions.Long-term experiments were performed to measure the solubility of uranium (VI) in carbonate-free ERDA-6 brine, a simulated WIPP brine, at pCH+ values between 8 and 12.5. These data, obtained from the over-saturation approach, were the first WIPP repository-relevant data for the VI actinide oxidation state. The solubility trends observed pointed towards low uranium solubility in WIPP brine and a lack of amphotericity. At the expected pCH+ in the WIPP (˜ 9.5), measured uranium solubility approached 10-7 M. The objective of these experiments was to establish a baseline solubility to further investigate the effects of carbonate complexation on uranium solubility in WIPP brines, during the ongoing research program in actinide solubility under WIPP-relevant conditions.