ALBERT

Notes: Contact metamorphic marbles, affected by metasomatic fluids at the contact to the Bergell and Adamello Intrusives, contain various accessory minerals (zirconolite, allanite, titanite, rutile, geikielite, hoegbomite), which provide new evidence for the hydrothermal mobility of Ti and Zr. In both examples, Ti and Zr migrated along with U, Th, Y and REE in a metasomatic fluid rich in potassium. The composition of the main minerals (fluorine-rich phlogopite, pargasite and titanian clinohumite) and the abundance of fluor-apatite demonstrate that fluorine and phosphorus were important components of the fluid. The textural relationships indicate that the formation of the accessory phases is linked to the crystallization of the hydrous minerals.

Notes: Abstract 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.

Notes: Abstract The assemblage titanian clinohumite+forsterite +spinel+calcite is widespread in marbles from the eastern Bergell contact aureole (Switzerland/Italy). The Bergell titanian clinohumites vary considerably in composition (TiO2: 0.19 to 2.05 wt%, F: 2.2 to 3.4 wt%). Electron microprobe analyses show that the titanian clinohumites contain less than detectable amounts of Co, Cu, Ni, Zn, Al, Cr and Cl. No trace of ferric iron could be detected by Moessbauer spectroscopy. Moreover, the Moessbauer spectra indicate that Fe2+ occurs only in one of the five octahedral positions in the crystal structure of the studied titanian clinohumite. Under the conditions of the contact metamorphism (600–650° C, 3 kb total pressure) the compositional variation along the exchange vector TiO2M−1 (OH,F)−2 takes place at constantx OH which is fixed by the pore fluid. Titanian clinohumite sometimes contains geikielite inclusions which strongly fractionate Fe and Mn relative to titanian clinohumite. The geikielites from the Bergell marbles are poor in Cr2O3, Fe2O3 and MnO, and thus different from those found in carbonatites, kimberlites and serpentinized ultramafic rocks.

Notes: Abstract Zirconolite, allanite and hoegbomite are present as accessory phases in a metasomatically altered spinel-calcite-marble from the contact with the Bergell intrusives (Switzerland/Italy). Textural relationships indicate a step-wise alteration of spinel to 1) hoegbomite or corundum + magnetite, 2) margarite and 3) chlorite. Replacement of spinel by hoegbomite can be described by the substitution 1.94(Mg2+, Fe2+, Zn2+, Mn2+, Ca2+)⇋Ti4+ +0.12(OH−) where Al3+ and Fe3+ are held constant. The average composition of the Bergell hoegbomites is given by the formula Fe 0.97 2+ Mg0.69Zn0.04Ti0.17Al3.94Fe 0.06 3+ O7.98(OH)0.02 and seems to be imposed by the composition of pre-existing spinel. During the first two steps of spinel alteration, calcite was replaced by anorthite+phlogopite, and the rare earth element(REE)-bearing minerals zirconolite, allanite and sphene were formed. Allanites have characteristic chondrite-normalized REE patterns with enrichment in the light REE. The zirconolite patterns show a marked increase in concentration from La to Ce, followed by an almost constant section. Sphene lacks detectable La, and its REE patterns vary from grain to grain. Contemporaneous formation of phlogopite, REE-bearing minerals and hoegbomite during replacement of the spinel-calcite-marble indicates that the metamorphic fluid introduced potassium along with REE and other high valence cations (Ti4+, Zr4+, U4+, Th4A3804265, Nb5A3804265, Y3A3804265) possibly as polynuclear complexes. The abundance of fluorine-bearing phlogopite and fluor-apatite as well as their close association with REE-bearing minerals and hoegbomite suggests F− and PO 4 3− as likely ligands for complexing of the above mentioned elements.