Relative oxidation states of magmas inferred from Ce(IV)/Ce(III) in zircon: application to porphyry copper deposits of northern Chile

Major- and trace-element compositions of zircons and whole rocks from 14 barren and seven ore-bearing calc-alkaline intrusions from the Chuquicamata-El Abra porphyry copper belt of northern Chile have been measured in situ by excimer laser ablation (ELA) ICP-MS. These data permit the Ce(IV)/Ce(III) ratio within zircon to be calculated using a lattice-strain model for mineral-melt partitioning of Ce(IV) and Ce(III). Zircon Ce(IV)/Ce(III) and Eu_N/Eu_N* ratios, and by inference magmatic oxidation states, generally increase from older, mafic to younger, felsic units. Within this sequence, porphyry copper mineralization is directly associated only with intrusions with zircon Ce(IV)/Ce(III)>300 and Eu_N/Eu_N*>0.4. Such trends can be understood in terms of interdependent relations between oxygen fugacity, sulfur speciation and solubility, and chalcophile element partitioning in silicate magmas. Because zircon occurs in most calc-alkaline intrusions and is resistant to subsolidus alteration, zircon Ce(IV)/Ce(III) ratios provide a useful tool for evaluating the economic potential of such rocks for magmatic-hydrothermal Cu-Au mineralization. The approach is general and may provide a means to infer relative oxidation state in a wide range of intermediate to felsic igneous rocks.