Evolution of invisible Au in arsenian pyrite in carlin-type Au deposits

A significant characteristic distinguishing Carlin-type Au deposits from other Au deposits is the abundance of invisible Au in arsenian pyrite. Gold occurs primarily as ionic Au (super 1+) in arsenian pyrite and is unstable during subsequent thermal events. In this study, we used the focused ion beam combined with scanning electron microscope (FIB-SEM) techniques, and a transmission electron microscope (TEM) to examine invisible Au and how it evolved through later geologic events that eventually led to the formation of Au nanoparticles. FIB-SEM techniques were used to prepare site-specific TEM foils from four Carlin-type gold deposits, including Getchell and Cortez Hills, Nevada, USA, and Shuiyindong and Jinfeng, Guizhou Province, China. These samples were analyzed to quantify ore pyrite chemistry and evaluate textures at the nanometer scale. In 17 examined TEM foils, we observed widespread Au-rich domains in high-grade Au arsenian pyrites from the Getchell and Cortez Hills Au deposits and the Jinfeng deposit but only 10 Au-bearing nanoparticles, approximately 10 to 20 nm in diameter. The Au-rich domains exhibit Au (Sb), (Tl), (Hg), and (Cu) peaks in the energy dispersive X-ray (EDX) spectrum without the presence of recognizable nanoparticles. This confirms that Au is invisible even at a nanometer scale and is most likely present in the crystal structure of arsenian pyrite. Stacking faults and nanometer-sized fluid inclusions were commonly observed in Au-bearing arsenian pyrite from the four deposits, implying rapid crystallization. Moreover, unlike the coarsely crystalline arsenian pyrite from Guizhou Carlin-type Au deposits, arsenian pyrite from Carlin-type deposits in Nevada consists of fine-grained polycrystalline aggregates, further implying rapid crystallization. Additionally, curved dislocations were commonly pinned by solid inclusions, reflecting a former annealing process. Combining nanoscale textures with geologic information previously reported for Carlin-type deposits, invisible ionic Au was initially incorporated into the crystal structure of arsenian pyrite during rapid precipitation. Subsequent post-ore magmatic events in both districts initiated the annealing of the ionic Au-bearing arsenian pyrite, leading to the redistribution of trace elements and formation of Au-bearing nanoparticles in the arsenian pyrite. The presence of predominantly ionically bonded Au in arsenian pyrite confirms that ore fluids were not saturated in Au when Au-bearing arsenian pyrite formed, as previously reported for Carlin-type deposits. Ionic Au that was scavenged from an undersaturated ore fluid and incorporated into the arsenian pyrite crystal structure formed the giant Carlin-type Au deposits.