Magmatic-to-hydrothermal crystallization in the W–Sn mineralized Mole Granite (NSW, Australia): Part II: Evolving zircon and thorite trace element chemistry

The Sn–W mineralized Mole Granite in Eastern Australia hosts zircon populations that crystallized at several stages during a protracted magmatic to hydrothermal evolution. Thirty-four elements have been quantified by laser-ablation inductively-coupled-plasma mass-spectrometric microanalysis with the aim of relating the chemistry of zircon to its growth environment. Trace element contents are highly variable for all textural occurrences. Zircon inclusions in earliest quartz phenocryst suggest that zircon was a liquidus phase that crystallized probably deep in the crust. Trace element contents are conspicuously high, showing only a slight positive Ce anomaly but a pronounced negative Eu-anomaly. Successive crystallization stages of magmatic zircon are characterized by progressive depletion in trace element contents, notably the rare earth elements, with an increasingly important positive Ce-anomaly. This evolution reflects saturation of REE accepting minerals such as monazite, thorite, xenotime and possibly apatite and is affected little by the exsolution of a magmatic–hydrothermal fluid. Zircon that is interpreted to have precipitated from aqueous fluids in Sn–W-bearing quartz veins shows REE patterns indistinguishable from those of late magmatic zircon. When combined with experimental evidence on the fluid–melt partitioning of REE, it indicates that the REE distribution coefficients for zircon/melt and zircon/fluid are largely comparable.

The second example of hydrothermal zircon crystallized some 2 My after the host granite. These crystals reveal an intragranular zonation of increasing trace element concentrations from core to rim. Therefore, REE abundances and patterns alone are not conclusive indicators of the geological environment in which zircon crystallized. Nevertheless, variations in trace element contents of zircon that relate to the chemistry of the melt or fluid from which zircon crystallized, as measured in cogenetic melt and fluid inclusions, are promising for future petrogenetic modeling.

Lead and Cs are strongly incompatible in hydrothermal zircon, with estimated zircon–fluid distribution coefficients D ≤ 0.001, while Sn and Li are moderately incompatible, D_Sn  0.6 and D_Li  0.1, and Ce is compatible, D_Ce  14. Moreover, hydrothermal zircon has a more pronounced negative Eu-anomaly and higher Ta/Nb and U/Th ratios than the magmatic zircons of the Mole Granite.