Pyrite as a record of hydrothermal fluid evolution in a porphyry copper system: A SIMS/EMPA trace element study

Abstract

Porphyry copper deposits are currently the world’s largest source of copper and molybdenum, and are also among the largest reservoirs of gold in the upper crust. Despite the fact that pyrite is a ubiquitous mineral phase in these deposits and secondary Cu enrichment processes are commonly controlled by the abundance of this sulfide, the major and trace element chemistry of pyrite from porphyry systems remains unconstrained. In this study, we report the first comprehensive trace element database of pyrite from the Dexing deposit, China’s largest porphyry Cu deposit. By combining high-spatial resolution and X-ray mapping capabilities of electron microprobe analysis (EMPA) with low detection limits and depth-profiling capabilities of secondary-ion mass spectrometry (SIMS) in a suite of samples from the Dexing deposit, we show that the concentrations of precious metals (e.g., Au, Ag), metalloids (e.g., As, Sb, Se, Te) and heavy metals (e.g., Cu, Co, Ni, Zn, Hg) in pyrite from porphyry systems are more significant than previously thought. Among the elements analyzed, Cu, As, Au and Ni are the most abundant with concentrations that vary from sub-ppm levels to a few wt.% (i.e., 6 wt.% Cu, 3 wt.% As, 0.25 wt.% Au, and 0.2 wt.% Ni). Detailed wavelength-dispersive spectrometry (WDS) X-ray maps and SIMS depth vs. isotope concentration profiles reveal that pyrite from the Dexing deposit is characterized by complex chemical zoning where the studied elements occur in different mineralogical forms. While As occurs as a structurally bound element in pyrite, Cu and Au can occur as both solid solution and micro- to nano-sized particles of chalcopyrite and native Au (or Au tellurides), respectively, indicating that pyrite can control metal speciation and partitioning during porphyry Cu mineralization. The well-developed oscillatory zoning detected in pyrite, where Cu-rich, As-depleted growth zones alternate with Cu-depleted, As-rich layers, indicates that Cu is geochemically decoupled from As, suggesting that this selective partitioning of metals into pyrite is most likely the result of changes in hydrothermal fluid composition.