Constraints on Hf and Zr mobility in high-sulfidation epithermal systems: formation of kosnarite, KZr2(PO4)3, in the Chaquicocha gold deposit, Yanacocha district, Peru

Abstract

We report the first occurrence of Hf-rich kosnarite [K(Hf,Zr)2(PO4)3], space group R-3c, Z = 6, in the giant Chaquicocha high-sulfidation epithermal gold deposit in the Yanacocha mining district, Peru. Kosnarite crystals are small (<100 μm) and occur in 2–3-mm-thick veins that cut intensively silicified rocks. The paragenesis includes a first stage of As-free pyrite and quartz (plus gratonite and rutile), followed by trace metal-rich pyrite [(Fe,As,Pb,Au)S2] and secondary Fe sulfates. Kosnarite is associated with quartz and is clearly late within the paragenetic sequence. Electron microprobe analyses (EMPA) of kosnarite show relatively high concentrations of HfO2 and Rb2O (7.61 and 1.05 wt.%, respectively). The re-calculated chemical formulas of kosnarite vary from KΣ1.00(Zr1.93Na0.01Hf0.01Mn0.01)Σ1.96(P3.04O4)Σ3 to (K0.92Rb0.05Na0.03)Σ1.00(Zr1.81Hf0.19)Σ2.00 [(P2.98Si0.02As0.01)Σ3.01O4]Σ3, where Hf and Rb are most likely incorporated according to a coupled substitution of Hf4+ + Rb+ ⇔ Zr4+ + K+. Back-scattered electron (BSE) images and elemental mapping of kosnarite reveal that Hf and Rb are enriched in 2–10-μm-wide oscillatory and/or sector zones. High-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) observations of such zones reveal a pattern of alternating, 5–50-nm-thick, Hf-rich and Zr-rich nanozones. These high-resolution observations indicate that the incorporation of Hf does not appear to cause significant distortion in the kosnarite structure. Semiquantitative TEM-energy-dispersive X-ray spectrometry (EDS) analyses of the nano-layers show up to 22 wt.% of HfO2, which corresponds to 31 mol% of the hypothetical, KHf2(PO4)3, end-member. The presence of kosnarite in the advanced argillic alteration zone at Yanacocha is indicative of Hf and Zr mobility under highly acidic conditions and points towards an unforeseen role of phosphates as sinks of Zr and Hf in high-sulfidation epithermal environments. Finally, potentially new geochronological applications of highly insoluble vein kosnarite, including Rb-Sr dating, may provide further age constraints in pervasively altered areas where other isotopic systems might have been reset.