Nanomaterial accumulation in boiling brines enhances epithermal bonanzas.

Epithermal bonanza-type ores, characterized by weight-percent contents of e.g., gold and silver in a few mm to cm, are generated by mixtures of magmatic-derived hydrothermal brines and external fluids (e.g., meteoric) that transport a variety of metals to the site of deposition. However, the low solubilities of precious metals in hydrothermal fluids cannot justify the high concentrations necessary to produce such type of hyper-enriched metal ore. Here we show that boiling metal-bearing brines can produce, aggregate, and accumulate metal nanomaterials, ultimately leading to focused gold + silver ± copper over-enrichments. We found direct nano-scale evidence of nanoparticulate gold- and/or silver-bearing ores formed via nonclassical growth (i.e., nanomaterial attachment) during boiling in an intermediate-sulfidation epithermal bonanza. The documented processes may explain the generation of bonanzas in metal-rich brines from a range of mineral deposit types.

A track record of Au-Ag nanomelt generation during fluid-mineral interactions.

Recent studies have reported the significant role of Au-bearing nanoparticles in the formation of hydrothermal gold deposits. Despite the ever-increasing understanding of the genesis and stability of Au-bearing nanoparticles, it is still unknown how they behave when exposed to hydrothermal fluids. Here, we study the nanostructural evolution of Au-Ag nanoparticles hosted within Co-rich diarsenides and sulfarsenides of a natural hydrothermal deposit. We use high-resolution transmission electron microscopy to provide a singular glimpse of the complete melting sequence of Au-Ag nanoparticles exposed to the hydrothermal fluid during coupled dissolution-precipitation reactions of their host minerals. The interaction of Au-Ag nanoparticles with hydrothermal fluids at temperatures (400-500 ºC) common to most hydrothermal gold deposits may promote melting and generation of Au-Ag nanomelts. This process has important implications in noble metal remobilization and accumulation during the formation of these deposits.

Mechanisms for Pd-Au enrichment in porphyry-epithermal ores of the Elatsite deposit, Bulgaria.

Porphyry Cu can contain significant concentrations of platinum-group elements (PGE: Os, Ir, Ru, Rh, Pt, Pd). In this study, we provide a comprehensive in situ analysis of noble metals (PGE, Au, Ag) for (Cu-Fe)-rich sulfides from the Elatsite, one of the world's PGE-richest porphyry Cu deposits. These data, acquired using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), indicate that Pd was concentrated in all the (Cu-Fe)-rich sulfides at ppm-levels, with higher values in pyrite (~6 ppm) formed at the latest epithermal stage (i.e., quartz-galena-sphalerite assemblage) than in bornite and chalcopyrite (<5 ppm) from the hypogene quartz-magnetite-bornite-chalcopyrite ores. Likewise, Au is significantly more concentrated in pyrite (~5 ppm) than in the (Cu-Fe)-rich sulfides (≤0.08 ppm). In contrast, Ag reaches hundreds of ppm in pyrite and bornite (~240 ppm) but is in much lesser amounts in chalcopyrite (<25 ppm). The inspection of the time-resolved spectra collected during LA-IPC-MS analyses indicates that noble metals are present in the sulfides in two forms: (1) structurally bound (i.e., solid solution) in the lattice of sulfides and, (2) as nano- to micron-sized inclusions (Pd-Te and Au). These observations are further confirmed by careful investigations of the PGE-rich (Cu-Fe)-rich sulfides by combining high-spatial resolution of field emission scanning electron microscope (FESEM) and focused ion beam and high-resolution transmission electron microscopy (FIB/HRTEM). A typical Pd-bearing mineral includes the composition PdTe2 close to the ideal merenskyite but with a distinct crystallographic structure, whereas Au is mainly found as native element. Our detailed mineralogical study coupled with previous knowledge on noble-metal inclusions in the studied ores reveals that noble metal enrichment in the Elatsite porphyry ores was mainly precipitated from droplets of Au-Pd-Ag telluride melt (s) entrained in the high-temperature hydrothermal fluid. These telluride melts could separate at the time of fluid unmixing from the silicate magma or already be present in the latter either derived from deep-seated crustal or mantle sources. Significant enrichment in Pd and Au (the latter correlated with As) in low-temperature pyrite is interpreted as remobilization of these noble metals from pre-existing hypogene ores during the epithermal overprinting.

Correction of Secondary Fluorescence Across Phase Boundaries in Electron Probe Microanalysis of Mineral Inclusions.

One of the limiting factors for the analysis of minor elements in multiphase materials by electron probe microanalysis is the effect of secondary fluorescence (SF), which is not accounted for by matrix corrections. Although the apparent concentration due to SF can be calculated numerically or measured experimentally, detailed investigations of this effect for fine-grained materials are scarce. In this work, we use the Monte Carlo simulation program PENEPMA to examine and correct the effect of SF affecting micron-sized mineral inclusions hosted by other minerals. A concentration profile across an olivine [(Mg,Fe)2SiO4] inclusion in chromite (Fe2+Cr2O4) is measured and used to assess the reliability of calculations, where different boundary geometries are examined. Three application examples are presented, which include the determination of Cr in olivine and serpentine [Mg3Si2O5(OH)4] inclusions hosted by chromite and of Fe in quartz (SiO2) inclusions hosted by almandine garnet (Fe3Al2Si3O12). Our results show that neglecting SF leads to concentrations that are overestimated by ~0.1­0.8 wt%, depending on inclusion size. In addition, assuming a straight boundary yields to an underestimation of SF effects by a factor of ~2­4. Because its long-range nature, SF severely compromises trace element analyses even for phases as large as 1 mm in size.