Mechanisms for Pd—Au enrichment in porphyry-epithermal ores of the Elatsite deposit, Bulgaria

Porphyry Cu can contain significant concentrations of platinum-group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd). In this study, we provide a comprehensive in situ analysis of noble metals (PGE, Au, Ag) for (Cu—Fe)-rich sulfides from the Elatsite, one of the world's PGE-richest porphyry Cu deposits. These data, acquired using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), indicate that Pd was concentrated in all the (Cu—Fe)-rich sulfides at ppm-levels, with higher values in pyrite (~6 ppm) formed at the latest epithermal stage (i.e., quartz–galena–sphalerite assemblage) than in bornite and chalcopyrite (<5 ppm) from the hypogene quartz–magnetite–bornite–chalcopyrite ores. Likewise, Au is significantly more concentrated in pyrite (~5 ppm) than in the (Cu—Fe)-rich sulfides (≤0.08 ppm). In contrast, Ag reaches hundreds of ppm in pyrite and bornite (~240 ppm) but is in much lesser amounts in chalcopyrite (<25 ppm). The inspection of the time-resolved spectra collected during LA-IPC-MS analyses indicates that noble metals are present in the sulfides in two forms: (1) structurally bound (i.e., solid solution) in the lattice of sulfides and, (2) as nano- to micron-sized inclusions (Pd—Te and Au). These observations are further confirmed by careful investigations of the PGE-rich (Cu—Fe)-rich sulfides by combining high-spatial resolution of field emission scanning electron microscope (FESEM) and focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM). A typical Pd-bearing mineral includes the composition PdTe(2) close to the ideal merenskyite but with a distinct crystallographic structure, whereas Au is mainly found as native element. Our detailed mineralogical study coupled with previous knowledge on noble-metal inclusions in the studied ores reveals that noble metal enrichment in the Elatsite porphyry ores was mainly precipitated from droplets of Au-Pd-Ag telluride melt (s) entrained in the high-temperature hydrothermal fluid. These telluride melts could separate at the time of fluid unmixing from the silicate magma or already be present in the latter either derived from deep-seated crustal or mantle sources. Significant enrichment in Pd and Au (the latter correlated with As) in low-temperature pyrite is interpreted as remobilization of these noble metals from pre-existing hypogene ores during the epithermal overprinting.