Economic By-products in Copper Porphyries: Silver in the Ascutita Cu-Porphyry, Romania

The Ascutita porphyry Cu-Mo prospect is located in the SW Poiana Rusca Mountains, Romania. Current assessment estimates a resource of 110 Mt @ 0.15 % Cu-equivalent. In relatively low-grade deposits such as this, by-products such as Ag (2–3 ppm) are important in determining the economic feasibility of the overall orebody. Assayed Cu and Ag have a clear downhole correlation. In the absence of other silver-bearing minerals, or correlations of Ag with other sulphides (e.g., Pb indicating Ag-bearing galena) this suggests Cu-sulphides are instead the dominant hosts of Ag. Petrography of 21 samples from various drillholes show chalcopyrite is the dominant Cu-sulphide present, spatially associated to two stages of pyrite. LA-ICP-MS analysis determined that both chalcopyrite and Stage 3 pyrite (younger) co-host the Ag. Chalcopyrite hosts Ag mostly in solid solution, whilst pyrite hosts Ag within a variety of complex, sulphosalt micro-inclusions undetectable on an SEM, but apparent on time-resolved LA-ICP-MS spectra. These micro-inclusions lock in Cu and Ag, with a bulk median Ag content of 0.79 ppm. The pyrite also contains mean concentrations of 52 ppm Bi and 46 ppm Se: both typically penalty-incurring elements at smelters. The chalcopyrite has a greater Ag concentration than the pyrite (median = 30.3 ppm with potential for 181 ppm), presumably in solid solution. The lattice-bound Ag partitioned into the chalcopyrite through monovalent, simple substitution of Ag+ for Cu+. Occurrence of Ag in the main Cu-bearing phase at Ascutita raises the possibility of combined recovery, and this study demonstrates the value of trace element analysis in geometallurgical assessments of orebodies.