Sulfide replacement processes revealed by textural and LA-ICP-MS trace element analyses: Example from the early mineralization stages at Cerro de Pasco, Peru

The large Cerro de Pasco Cordilleran base metal deposit in central Peru is the result of three successive mineralizing stages comprising both low- and high-sulfidation mineral associations: (A) several pyrrhotite pipes grading outward to sphalerite and galena replacement bodies, (B) a massive, funnel-shaped pyrite-quartz replacement orebody, and (C) E-W–trending Cu-Ag-(Au-Zn-Pb) enargite-pyrite veins and well-zoned Zn-Pb-(Bi-Ag-Cu) carbonate-replacement orebodies. This superposition of hydrothermal events leads to complex replacement textures and crosscutting relationships. A detailed study of the textures and mineral composition of the up to 15-m-wide replacement front existing between the pyrrhotite pipes and the pyrite-quartz body allows for clarification of the relative chronology of the hydrothermal events. The results show that, in contrast to previous interpretations, the emplacement of the pyrrhotite pipes and their Zn-Pb mineralized rims precedes that of the pyrite-quartz body. The replacement textures affecting pyrrhotite and arsenopyrite and the nature of the newly formed minerals have been used as a qualitative way to track the evolution of fS2, fO2, and pH of the mineralizing fluids. Two steps of pyrrhotite replacement have been recorded. The first one takes place under moderate acidity and relatively reduced to moderately oxidized conditions and is marked by replacement of pyrrhotite by euhedral nonporous pyrite. The second step occurs under more acidic and oxidized conditions and is characterized by replacement of pyrrhotite by porous marcasite and replacement of arsenopyrite by pyrite. Subsequently, marcasite is partly replaced by fine-grained euhedral nonporous pyrite. LA-ICP-MS trace element analyses of the replaced pyrrhotite and arsenopyrite and of the newly formed marcasite and pyrite support dissolution-reprecipitation as the main mechanism for replacement. Positive correlations between some of the elements (e.g., Pb-Sb, Pb-Ag) are indicative of the possible presence of nanoscale solid inclusions as main carriers for those elements; however, coupled substitutions and incorporation of some of the elements at a ppm level into the pyrite and marcasite structures cannot be excluded. The obtained As, Sb, Pb, and Bi values in pyrite are systematically higher than published data of pyrite in epithermal and porphyry systems. Nature and trace element content of the newly formed minerals yield information on the physicochemical conditions during their precipitation, the initial trace element content of replaced minerals, and the subsequently dissolved neighboring phases. The results show that the metal concentration of the fluid is locally influenced by the composition of the dissolved minerals. This study leads to a simpler interpretation of the fluid evolution than previously proposed, with a progressive increase of fS2, fO2, and pH as a result of decreasing wall-rock buffering during the three successive mineralizing stages at Cerro de Pasco