The coupled geochemistry of Au and As in pyrite from hydrothermal ore deposits

The ubiquity of Au-bearing arsenian pyrite in hydrothermal ore deposits suggests that the coupled geochemical behaviour of Au and As in this sulfide occurs under a wide range of physico-chemical conditions. Despite significant advances in the last 20years, fundamental factors controlling Au and As ratios in pyrite from ore deposits remain poorly known. Here we explore these constraints using new and previously published EMPA, LA-ICP-MS, SIMS, and μ-PIXE analyses of As and Au in pyrite from Carlin-type Au, epithermal Au, porphyry Cu, Cu–Au, and orogenic Au deposits, volcanogenic massive sulfide (VHMS), Witwatersrand Au, iron oxide copper gold (IOCG), and coal deposits. Pyrite included in the data compilation formed under temperatures from ∼30 to ∼600°C and in a wide variety of geological environments. The pyrite Au-As data form a wedge-shaped zone in compositional space, and the fact that most data points plot below the solid solubility limit defined by Reich et al. (2005) indicate that Au1+ is the dominant form of Au in arsenian pyrite and that Au-bearing ore fluids that deposit this sulfide are mostly undersaturated with respect to native Au. The analytical data also show that the solid solubility limit of Au in arsenian pyrite defined by an Au/As ratio of 0.02 is independent of the geochemical environment of pyrite formation and rather depends on the crystal-chemical properties of pyrite and post-depositional alteration. Compilation of Au–As concentrations and formation temperatures for pyrite indicates that Au and As solubility in pyrite is retrograde; Au and As contents decrease as a function of increasing temperature from ∼200 to ∼500°C. Based on these results, two major Au–As trends for Au-bearing arsenian pyrite from ore deposits are defined. One trend is formed by pyrites from Carlin-type and orogenic Au deposits where compositions are largely controlled by fluid-rock interactions and/or can be highly perturbed by changes in temperature and alteration by hydrothermal fluids. The second trend consists of pyrites from porphyry Cu and epithermal Au deposits, which are characterised by compositions that preserve the Au/As signature of mineralizing magmatic-hydrothermal fluids, confirming the role of this sulfide in controlling metal ratios in ore systems.