Contributions to Mineralogy and Petrology
Zirconolite, aeschynite-(Ce), titanite and apatite have been found as minor or accessory minerals in a Ti-rich (TiO2=2.1–4.5 wt.%) hydrothermal vein occurring in dolomite marbles at the contact with a tonalite intrusion of the Tertiary Adamello batholith (northern Italy). The vein consists of four distinct mineral zones, comprising from margin to center: (1) forsterite+calcite, (2) pargasite+calcite+titanite+sulfides, (3) phlogopite +calcite+titanite+sulfides, and (4) titanian clinohumite +spinel+calcite+sulfides. Zirconolite occurs in two vein zones only: in the phlogopite zone it is invariably anhedral, often corroded, and exhibits complex chemical zonation patterns. In the titanian clinohumite zone zirconolite is idiomorphic and characterized by a pronounced discontinous chemical zoning, but shows no evidence of corrosion. The considerable compositional variation observed for zirconolite (in wt.%: ∑(REE2O3)=0.74–16.8, UO2=0.59–24.0, ThO2=0.67–17.1) is due to the zoning, and may be attributed to four major substitutions described by the exchange vectors: 1. (Th, U) (Mg, Fe2+) Ca-1 Ti-1 2. REE Al Ca-1 Ti-1 3. REE Fe2+ (Nb, Ta) Ca-1 Ti-1 4. Hf Zr-1 Exchange vector (2) is effective at total REE2O3 contents up to approximately 5 wt.%, whereas vector (3) is operating at higher concentrations. Both titanite and aeschynite-(Ce) exhibit, like zirconolite, complex chemical zonation patterns which document that the trace element content of the metasomatic fluid was variable during the vein-forming process. As indicated by thermodynamic analysis of the phase assemblages, the vein zones containing the REE-bearing minerals formed at 500–600°C (Ptotal≈2 kbar) from a reducing fluid rich in H2S, HCl°, HF° and phosphorus, but relatively poor in CO2(XCO 2 ≈0.2). Geochemical and isotopic data are consistent with the interpretation of the fluid as being derived from the nearby tonalite intrusion. The abundance of idiomorphic fluor-apatite as well as textural relations between apatite, the other REE-bearing minerals and the fluorine-bearing hydrous silicates suggest F- and PO 4 3- to be the most likely ligands for complexing REE, Ti, Zr and other high-field-strength elements in the veinforming fluid. The corrosive features observed for zirconolite demonstrate that hydrothermal fluids are able to dissolve zirconolite, which is one of the main components of SYNROC-C, the most promising disposal option for high-level nuclear waste. Therefore, immobilization of radioactive waste in zirconolite can be guaranteed only if an effective sealing material prevents any hydrothermal fluid from access to the final disposal site.
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