—Gold and silver are capable of forming stable natural compounds with different elements. For gold 36 minerals are known: 10 in the class “Native metals, intermetallic compounds” and 26 in the class “Sulfides (selenides, tellurides, arsenides, antimonides, bismuthides).” For silver, 194 minerals are registered in the MMA, presented in 8 classes. Compared to gold in the class “Native metals, intermetallic compounds” there are far fewer silver minerals. They are widely represented in the classes “Sulfides” and “Sulfosalts” (124). Among silver minerals “halides” are also known (fluorides, chlorides, bromides, iodides), seven; simple and complex oxides, two; there is one mineral each in the classes “sulfates,” “phosphates,” “arsenates,” and “vanadates.” Both metals are in the compositions of 12 minerals: native gold, native silver, weishanite, uytenbogaardtite, petrovskaite, fishesserite, penzhinite, petzite, mutmannite, sylvanite, krennerite, and bezsmertnovite. Every year, the MMA commission registers four to six gold and silver minerals, so there are prospects for the discovery of new minerals of these precious metals in the near future.
The indicator elements (fixers) that form natural compounds with gold and indicate the possible presence of gold minerals in sulfide ores include 13 elements: 7 metals (Ag, Cu, Pd, Hg, Sn, Tl, Fe), 3 chalcogens (Te, S, Se), and 3 metalloids (As, Sb, Bi). For silver, this range is wider and also includes such elements as Mn, Zn, Ge, Cd, V, O, H, F, Cl, Br, I, In, and N.
This review presents and summarizes the results of studies on the composition of native gold with copper, mercury, and palladium impurities in different types of gold deposits. The article describes the gold and silver minerals established by the author together with colleagues in a study of productive mineral assemblages in some gold deposits in Russia: the Ulakhan, Yunoe, Krutoe, Dzhulietta, Dorozhnoe (Magadan region), Konechnoe (Taimyr Peninsula), Kupol, Valunistoe (Chukotka), Maletoyvayam (Kamchatka), etc.
Data are presented on gold and silver minerals found in sulfide ores and of economic importance. Some of their technological properties are characterized, including solubility and behavior under the influence of various reagents. The presence of refractory minerals (calaverite, sylvanite, krennerite, petzite, aurostibite, maldonite, fishesserite, uytenbogaardtite, petrovskaite, penzhinite, weishanite, yuanjianite, hunchunite, anyuite, krynovite, nadjagite, and bogdanovite, bilibinskite, criddleite, etc.), as well as the chemical composition gold and silver, are important technological factors and should be taken into account when developing a technology for extracting precious metals from ores. The presence of increased concentrations of indicator elements (fixers) of gold and silver minerals in sulfide ores is an important indicator and argument for detailed mineralogical and geochemical studies of the source raw material. Identification of mineral (micro-, nano-) forms of gold and silver in sulfide ores is necessary for developing and improving rational dressing schemes.

Gold and Silver Minerals in Sulfide Ore

The state of Au and As in pyrite studied by X-ray absorption spectroscopy of natural minerals and synthetic phases

Scientific studies that use pyrite trace element signatures to facilitate interpretations of the geological history of hydrothermal gold deposits are becoming more common. Given this rise in popularity in pyrite trace element chemistry studies, a review of trace element incorporation in pyrite from various gold deposit classes is highly timely. We provide a global compilation of over 20 000 chemical data points resulting from over 5520 spot measurements of pyrites from five separate ore deposit classes, each of which is known to have high gold concentrations. The ore deposit classes considered here include orogenic gold deposits, Carlin-type gold deposits, high- and low-sulphidation gold deposits, and Au-bearing porphyry systems, whereas the pyrite minor- and trace elements that we consider include Au, As, Bi, Co, Cu, Ni, Pb, Sb, Se, Te, Tl, and Zn. Meta-analyses of these data suggest that, on a global scale, both existing pyrite trace element chemistry discrimination tools and newly-established Principal Component Analysis (PCA) approach have a relatively low efficacy in correctly predicting the metallogenic setting in which the pyrite formed. At a deposit scale however, pyrite trace element chemistry continues to be a useful tool for understanding Au mineralizing processes, especially when coupled with additional analytical techniques or lines of geological evidence. Further meta-analysis of the data tentatively suggests the solubility limits for the various trace elements in pyrite mineral structure and reveals that the correlations between temperature and trace element incorporation (i.e., pyrite geothermometry) are complex. The study highlights that pyrite, by virtue of its mineralogy and propensity for element substitutions, remains an important repository of chemical information related to the evolution of hydrothermal gold mineralizing systems. Inasmuch as this repository is now readily accessed utilizing modern analytical techniques (e.g., routine LA-ICP-MS mapping of trace element distributions at ppb concentrations; mapping element distributions at the nanoscale using atom probe tomography), its full value will only be realized through continued study into the kinetics and mechanisms of trace element incorporation into pyrite structure at conditions relevant to ore-forming processes.Supplementary material at https://doi.org/10.6084/m9.figshare.c.5882221

Trace elements in pyrite from five different gold ore deposit classes: A review and meta-analysis

“Invisible” gold in hydrothermal ores is frequently scattered in the most abundant minerals of the Fe–As–S system. It is assumed that “invisible” gold does not incorporate into the mineral structure (nanoscale inclusions of the metal or its compounds) or is chemically bound (isomorphous substitution). The aim of this study is to determine the concentration range of “invisible” gold, species of its occurrence in arsenopyrite, and conditions facilitating the formation of gold-bearing arsenopyrite using synthetic crystals and natural samples from the Vorontsovka Carlin-type deposit in the Northern Urals. Arsenopyrite crystals have been synthesized using the ampoule method in a eutectic melt of alkali metal chlorides and Al at a stationary thermal gradient and 400–500°C at the cold ampoule end. The chemical composition of arsenopyrite has been measured by electron probe microanalysis. The chemical composition of synthesized arsenopyrite is, at %: 32.6–34.4 Fe, 30–36.5 As, and 29.4–36.0 As. The gold concentration ranges from below the detection limit ( 1 at %) arsenopyrite and is close to stoichiometry, whereas in the S-rich variety, the Au content is as low as 0.25 wt %. This dependence is not only within individual grains, but also at the deposit in general: later As-rich arsenopyrite formed at lower temperature and sulfur fugacity (T = 250–370°C, log f  S2 = –12 to –17) is enriched in Au compared to early arsenopyrite (T = 270–400°C, log f  S2 = –7 to –9). Comparison of our data with the literature shows that an increasing Au content with increasing As concentration and decreasing Fe content in arsenopyrite is a common feature of Carlin-type deposits. We believe that in contrast to the negative correlation between Au and Fe, the correlation between Au and As is not obvious and may be caused by external factors, different composition of hydrothermal fluids, and sulfur fugacity.

“Invisible” Gold in Synthetic and Natural Arsenopyrite Crystals, Vorontsovka Deposit, Northern Urals

Thallium is a highly toxic metal and is predominantly hosted by sulfides associated with low-temperature hydrothermal mineralization. Weathering and oxidation of sulfides generate acid drainage with a high concentration of thallium, posing a threat to surrounding environments. Thallium may also be incorporated into secondary sulfate minerals, which act as temporary storage for thallium. We present a state-of-the-art review on the formation mechanism of the secondary sulfate minerals from thallium mineralized areas and the varied roles these sulfate minerals play in Tl mobility. Up to 89 independent thallium minerals and four unnamed thallium minerals have been documented. These thallium minerals are dominated by Tl sulfosalts and limited to several sites. Occurrence, crystal chemistry, and Tl content of the secondary sulfate minerals indicate that Tl predominantly occurs as Tl(I) in K-bearing sulfate. Lanmuchangite acts as a transient source and sink of Tl for its water-soluble feature, whereas dorallcharite, Tl-voltaite, and Tl-jarosite act as the long term source and sink of Tl in the surface environments. Acid and/or ferric iron derived from the dissolution of sulfate minerals may increase the pyrite oxidation process and Tl release from Tl-bearing sulfides in the long term.

Secondary Sulfate Minerals from Thallium Mineralized Areas: Their Formation and Environmental Significance

This paper is focused on the new data for geology, mineralogy, and geochemistry of stockworks consisting of steep and gentle quartz veins and veinlets forming a complex multilevel structure at the Rodion deposit These stockworks range from 25 to 150 m in thickness Average gold grade is 18 g/t Ore minerals pyrite, arsenopyrite, chalcopyrite, sphalerite, galena, and native gold are predominantly concentrated on the vein and veinlet walls Thermal metamorphism caused by the intrusion of the Ulakhan granodiorite pluton is the important singularity of the deposit The deposit ore is enriched in chalcophile microelements Au, Ag, As, Sb, Cu, Pb, Zn, and Bi as compared to the average composition of the upper crust and hosting Permian sequences The enrichment factors range from a few to hundreds of times Bi, W, Pb, Ag, and Na2O are positively correlated between each other and with Au The highest correlation coefficient 059 is between Au and Bi Au is negatively correlated with Ba, Li, Co, Ni, Mn, Ti, and Be The stockwork ores were formed involving homogeneous low-saline (94–43 wt % NaCl equiv) substantially aqueous bicarbonate-chloride fluid at 275–330°C and 300–1840 bar fluid pressure Fluid has a high concentration of CO2 (up to 349 g/kg of water) and is reductive (СО2/СН4 = 17–373) Na and Ca are the major cations in the fluid, whereas K and Mg are minor In addition, many microelements were detected in the fluid: As, Li, Rb, Cs, Mo, Ag, Sb, Cu, Zn, Cd, Pb, U, Ga, Ge, Ti, Mn, Fe, Co, Ni, V, Cr, Y, Zr, Sn, Ba, W, Au, Hg, and REE The results obtained are consistent with the metamorphic–magmatic formation model of orogenic gold–quartz deposits within the Yana–Kolyma belt

New data for geology and geochemistry of the Rodion gold–quartz deposit, northeastern Russia

Vorontsovka Carlin-style gold deposit in the North Urals: Mineralogy, fluid inclusion and isotope data for genetic model

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New data for geology and geochemistry of the Rodion gold–quartz deposit, northeastern Russia

Vorontsovka Carlin-style gold deposit in the North Urals: Mineralogy, fluid inclusion and isotope data for genetic model