The coupled geochemistry of Au and As in pyrite from ore deposits and geothermal fields: monitoring fluid evolution and external forcing factors in hydrothermal systems

Gold and arsenic incorporation into pyrite (FeS₂) is strongly coupled in different types of ore deposits, including Carlin-type Au, porphyry Cu, epithermal Au, orogenic Au, volcanogenic massive sulphide (VMS) and iron-oxide Cu-Au (IOCG), among others. Despite significant advances in the last decades, the fundamental factors controlling Au and As partition in pyrite from hydrothermal systems formed under different tectonic settings and crustal levels remain poorly known. Furthermore, the complexity of pyrite microtextures and growth features suggest multi-stage growth that may be useful to monitor changes in fluid composition related to episodic pumping of fluids.

Here we report a comprehensive database of EMPA, SIMS, LA-ICP-MS and micro-PIXE Au-As analyses that cover temperature conditions of pyrite formation from ~30ºC to ~600ºC. The global pyrite Au-As data form a wedge-shaped zone in compositional space, and show that the solid solubility limit of Au in arsenian pyrite is independent of the geochemical environment of pyrite formation and rather depends on its crystal-chemical properties and post-depositional alteration. Compilation of Au-As concentrations and formation temperatures for pyrite indicates that Au and As solubility is retrograde in this mineral, as Au and As contents decrease with increasing temperature from ~200-500ºC.

Based on these results, we define one Au-As trend formed by pyrites from Carlin-type and orogenic Au deposits where compositions are largely controlled by fluid-rock-interactions and can be highly perturbed by changes of temperature or subsequent alteration. The second trend consists of pyrites from porphyry Cu, epithermal Au deposits and geothermal systems, which are characterized by compositions that preserve the Au/As signature of mineralizing magmatic-hydrothermal fluids. The well-developed oscillatory zoning in pyrite detected in these systems, where Cu-rich, Au-As-depleted growth zones alternate with Cu-poor, Au-As-rich layers, indicates that Cu is geochemically decoupled from As and Au. These data suggest that selective partitioning of metals into pyrite may be related to abrupt phase separation events and periodic changes in fluid composition, triggered by external forcing factors such as earthquakes.