We studied the feasibility of automated mineralogy to discriminate between tennantite and enargite, the main sulfosalts found in the Rio Blanco deposit, Codelco-Chile, in order to predict the content of minor elements (As, Sb, Ag, Pb, Zn) that impact on the process and concentrate prices. The identification of these minerals is feasible using traditional microscopy, however not possible by automated mineralogy. This drawback prevents comparing the databases generated in the past by means of conventional microscopy with the information obtained at present by QEMSCAN. To differentiate enargite from tennantite the mineral composition of both sulfosalts was studied by electron microprobe. The presence of associated minor element contents of about 8% zinc in tennantites and not exceeding 0.07% in enargites were used to modify the SIP database of QEMSCAN to enable the quantification of these phases in samples of head, residue and concentrate coming from As-bearing domains of the deposits. Detection limits allowed to determine the mineral species in the head, concentrate and residues. The integration of methodologies such as automated mineralogy and microprobe can be used successfully to quantify the presence of some ore forming solid solution.