Formation Environments of Metasomatites and Ores of the Epithermal Gold–silver Deposits

Geology of Ore Deposits - Preore metasomatites of epithermal gold–silver deposits are formed by various types of hydrothermal solutions—from highly acidic and oxidized (argillization,...     

Formation conditions of high-grade gold–silver ore of epithermal Tikhoe deposit,Russian Northeast

The Tikhoe epithermal deposit is located in the Okhotsk–Chukotka volcanic belt (OChVB) 250 km northeast of Magadan. Like other deposits belonging to the Ivan’insky volcanic–plutonic depression (VTD), the Tikhoe deposit is characterized by high-grade Au–Ag ore with an average Au grade of 23.13 gpt Au and Au/Ag ratio varying from 1: 1 to 1: 10. The detailed explored Tikhoe-1 orebody is accompanied by a thick (20 m) aureole of argillic alteration. Pyrite is predominant among ore minerals; galena, arsenopyrite, sphalerite, Ag sulfosalts, fahlore, electrum, and küstelite are less abundant. The ore is characterized by abundant Sebearing minerals. Cu–As geochemical specialization is noted for silver minerals. Elevated Se and Fe molar fractions of the main ore minerals are caused by their formation in the near-surface argillic alteration zone. The veins and veinlets of the Tikhoe-1 ore zone formed stepwise at a temperature of 230 to 105°C from Nachloride solution enriched in Mg and Ca cations with increasing salinity. The parameters of the ore-forming fluid correspond to those of epithermal low-sulfidation deposits and assume the formation of high-grade ore under a screening unit of volcanic rocks. In general, the composition of the ore-forming fluid fits the mineralogy and geochemistry of ore at this deposit. The similarity of the ore composition and parameters of the ore-forming fluid between the Tikhoe and Julietta deposits is noteworthy. Meanwhile, differences are mainly related to the lower temperature and fluid salinity at the Julietta deposit with respect to the Tikhoe deposit. The fluid at the Julietta deposit is depleted in most components compared with that at the Tikhoe deposit except for Sb, Cd, and Ag. The results testify to a different erosion level at the deposits as derivatives of the same ore-forming system. The large scale of the latter allows us to predict the discovery of new high-grade objects, including hidden mineralization, which is not exposed at the ore field flanks and beyond them.     

The mechanisms of paragenesis and separation of silver, lead and zinc in hydrothermal solutions

On the basis of an experimental study and thermodynamic calculation, the mechanisms of paragenesis and separation of silver, lead and zinc in the hydrothermal system have been studied. At acidic to nearly neutral pH, their chloride complexes are stable, and among them the chloride complexes of zinc are most stable. And the sulfide complexes are the dominant species at nearly neutral to alkaline pH,while the sulfide complexes of silver are most stable. With decreasing temperature, [ Cl^-] ,fO2, and increasing pH, the solubilities of silver, lead and zinc will decrease, leading to their deposition and separation. For sulfide complexes, the concentrations of reduced sulfur and pH are two important factors affecting their stabilities. Complexes of different forms and stabilities respond to the variation of conditions to different extents, which gave rise to the paragenesis and separation of silver, lead and zinc in the whole ore-forming process of dissolution, transport and deposition.     

Impact of amide–amide hydrogen bonding on the stability of two nicotinamide complexes of silver(I)

The nicotinamide (pyridine-3-carboxamide, nia) complexes of silver(I), [Ag(nia)₂(NO₃)]·H₂O (1), [Ag(nia)₂(NO₃)] (2), and {K[Ag(nia)₂](NO₃)₂} _n (3), were prepared and characterised by IR spectroscopy and TG/DTA thermal methods. The solid state structures of 2 and 3 were determined by single-crystal X-ray diffraction analysis. In both complexes two nicotinamide ligands are coordinated to silver(I) through the nitrogen atom of the pyridine ring in a near-linear fashion. In 2, additional coordination by two oxygen atoms of one nitrate group leads to the distorted tetrahedral coordination environment of silver(I). In 3, nitrate ions bridge potassium cations giving rise to a 2D coordination network which is further stabilised by cross-bridging of each two potassium atoms in [1 0 0] direction by complex cations, [Ag(nia)₂]⁺. Despite different aggregation of 2 and 3 in the solid state, both complexes demonstrate quite similar thermal stability. The amide self-complementary hydrogen bonds appear to be the main driving force for establishing the crystal structures of both 2 and 3.     

Regional geochemical indicators of large-sized silver polymetallic deposits in Daxing＇ anling Metallogenic Belt

如何利用地球化学填图数据来预测大型矿是当前面临的一个重要课题。文中利用大兴安岭地区1∶20万区域化探扫面数据和1∶100万中蒙边界地球化学填图数据进行综合研究。发现1∶100万地球化学编图圈定的地球化学省与矿集区存在十分密切的关系,1∶20万地球化学编图圈定的区域地球化学异常与大型矿存在对应关系。以大兴安岭3个大型银铅锌矿为例建立了预测大型矿的地球化学指标。大型银多金属矿具有Pb、Zn、Ag等3个以上元素异常在空间上相套合;异常具有3层以上套合结构,即地球化学省（〉500km2）包裹区域异常（〉100km2）,区域异常包裹局部浓集中心（n×10km2）;标准化综合异常下限大于4.5,异常衬度大于2.0。     

Classification,metallogenesis and exploration of silver deposits in Daxing’anling of Inner Mongolia and its adjacent areas

By the end of 2020, 83 silver deposits (or ore occurrences), including four super-large-scale deposits, nine large-scale deposits, 33 medium-scale deposits and 37 small-scale deposits or ore occurrences, have been proved. The amount of silver metal exceeds 86000 t with average grade of 100 g/t, which makes Daxing’ anling region one of the the most important silver ore belt in China. However, the metallogenic characteristics and metallogenesis need to be clarified. The silver deposits in the study area are classified into three main types, which are magmatic hydrothermal vein type, continental volcano-subvolcanic type and skarn type, respectively. The supergiant deposits include the Shuangjianzishan deposit (silver metal amount of 15214 t with average grade of 138 g/t), the Baiyinchagandongshan deposit (silver metal amount of 9446 t with average grade of 187 g/t), the Huaobaote deposit (silver metal amount of 6852 t with average grade of 170 g/t), and the Fuxingtun deposit (silver metal amount of 5240 t with average grade of 196 g/t). The silver deposits are mainly distributed in the central and south of the Daxing’anling area, and mainly formed in the Yanshanian period. The silver polymetallic deposits in the Daxinganling area are significantly controlled by regional faults and the junction zone of volcanic rock basins and their margins. The north-east trending deep faults are the most important ore-controlling structures in this area. The distribution of silver polymetallic deposits along the main faults is obvious, and the intersection area of multiple groups of faults often form important mine catchments. The Permian is the most important ore-bearing formation in this area, but some important silver polymetallic deposits occur in Mesozoic volcanic basins or pre-Mesozoic strata. The magmatic rocks related to mineralization are mainly intermediate acidic or acidic intrusions, intermediate acidic lavas, pyroclastic rocks, and small intrusions of ultra-shallow or shallow facies of the Yanshanian Period. The mineralization element combination is mainly determined by the elemental geochemical background of surrounding rocks or source layers. In addition, the type of deposit, the distance from the mineralization center, and the degree of differentiation of ore-forming rock mass are also important influence factors. The article analyzes the prospecting prospects of each silver deposit type in the study area, discusses the relationship between mineralization center and deep prospecting, and proposes that porphyry silver deposits should be paid attention to. In the prospecting and exploration of silver deposits, comprehensive evaluation and multi-target prospecting need to be strengthened because silver can coexist or be associated with a variety of metals.©2022 China Geology Editorial Office.     

Kysylga gold–silver deposit in the terrigenous sequences of the Verkhoyansk–Kolyma mesozoides

The paper reports the mineralogical and geochemical features of the Kysylga gold deposit located in the hornfelsed Norian sedimentary rocks and classified with low-sulfide gold–quartz type of deposits typical of the Verkhoyansk–Kolyma metallogenic province. Detailed typomorphic study of the major minerals (quartz, arsenopyrite, and gold) of the ore veins shows that the deposit is assigned to the gold–silver type. Mineralogical and geochemical data substantiate this conclusion.     

Texture and chemistry of pyrite at Chah Zard epithermal gold–silver deposit,Iran

Gold mineralization at Chah Zard, Iran, is mostly concentrated in breccia and veins, and is closely associated with pyrite. Optical and scanning electron microscopy-backscattered electron observations indicate four different pyrite types, each characterized by different textures: porous and fractured py1, simple-zoned, oscillatory-rimmed, framboidal and fibrous py2, colloform py3, and inclusion-rich py4. Laser ablation ICP–MS analysis and elemental mapping reveal the presence of invisible gold in all pyrite types. The highest concentrations (161–166 ppm Au) are found in py2 and py4, which correlate with the highest As concentrations (73,000–76,000 ppm). In As-poor grains, Au concentrations decrease by about two orders of magnitude. Copper, Pb, Zn, Te, Sb, and Ag occur with invisible gold, suggesting that at least part of the gold occurs in nanoparticles of sulfosalts of these metals and metalloids. Gold distribution patterns suggest that only negligible Au was originally trapped in py1 from the initial ore fluids. However, most, if not all, Au was transported and deposited during subsequent overprinting hydrothermal fluid flow in overgrowth rims around the margins of the py2 and within microfractures of py4 grains. Oscillatory zonation patterns for Co, Ni, Sb, Cu, Pb, and Ag in pyrite reflect fluctuations in the hydrothermal fluid chemistry. The LA-ICP–MS data reveal that Cu, Pb and Ag show systematic variations between different pyrite types. Thus, Cu/Pb and Pb/Ag ratios in pyrite may provide a potentially powerful exploration vector to epithermal gold mineralization at Chah Zard district and elsewhere.     

Specific composition of native silver from the Rogovik Au–Ag deposit,Northeastern Russia

The first data on native silver from the Rogovik Au–Ag deposit in northeastern Russia are presented. The deposit is situated in central part of the Okhotsk–Chukchi Volcanic Belt (OCVB) in the territory of the Omsukchan Trough, unique in its silver resources. Native silver in the studied ore makes up finely dispersed inclusions no larger than 50 μm in size, which are hosted in quartz; fills microfractures and interstices in association with küstelite, electrum, acanthite, silver sulfosalts and selenides, argyrodite, and pyrite. It has been shown that the chemical composition of native silver, along with its typomorphic features, is a stable indication of the various stages of deposit formation and types of mineralization: gold–silver (Au–Ag), silver–base metal (Ag–Pb), and gold–silver–base metal (Au–Ag–Pb). The specificity of native silver is expressed in the amount of trace elements and their concentrations. In Au–Ag ore, the following trace elements have been established in native silver (wt %): up to 2.72 S, up to 1.86 Au, up to 1.70 Hg, up to 1.75 Sb, and up to 1.01 Se. Native silver in Ag–Pb ore is characterized by the absence of Au, high Hg concentrations (up to 12.62 wt %), and an increase in Sb, Se, and S contents; the appearance of Te, Cu, Zn, and Fe is notable. All previously established trace elements—Hg, Au, Sb, Se, Te, Cu, Zn, Fe, and S—are contained in native silver of Au–Ag–Pb ore. In addition, Pb appears, and silver and gold amalgams are widespread, as well as up to 24.61 wt % Hg and 11.02 wt % Au. Comparison of trace element concentrations in native silver at the Rogovik deposit with the literature data, based on their solubility in solid silver, shows that the content of chalcogenides (S, Se, Te) exceeds saturated concentrations. Possible mechanisms by which elevated concentrations of these elements are achieved in native silver are discussed. It is suggested that the appearance of silver amalgams, which is unusual for Au–Ag mineralization not only in the Omsukchan Trough, but also in OCVB as a whole, is caused by superposition of the younger Dogda–Erikit Hg-bearing belt on the older Ag-bearing Omsukchan Trough. In practice, the results can be used to determine the general line of prospecting and geological exploration at objects of this type.     

Geological setting and timing of the Chah Zard breccia-hosted epithermal gold–silver deposit in the Tethyan belt of Iran

The breccia-hosted epithermal gold–silver deposit of Chah Zard is located within a high-K, calc-alkaline andesitic to rhyolitic volcanic complex in the central part of the Urumieh-Dokhtar Magmatic Arc (UDMA), west central Iran. The total measured resource for Chah Zard is ∼2.5 million tonnes of ore at 12.7 g/t Ag and 1.7 g/t Au (28.6 t Ag, 3.8 t Au), making it one of the largest epithermal gold deposits in Iran. Magmatic and hydrothermal activity was associated with local extensional tectonics in a strike-slip regime formed in transtensional structures of the Dehshir-Baft strike-slip fault system. The host rocks of the volcanic complex consist of Eocene sedimentary and volcanic rocks covered by Miocene sedimentary rocks. LA-ICP–MS U–Pb zircon geochronology yields a mean age of 6.2 ± 0.2 Ma for magmatic activity at Chah Zard. This age represents the maximum age of mineralization and may indicate a previously unrecognized mineralization event in the UDMA. Breccias and veins formed during and after the waning stages of explosive brecciation events due to shallow emplacement of rhyolite porphyry. Detailed systematic mapping leads to the recognition of three distinct breccia bodies: volcaniclastic breccia with a dominantly clastic matrix; gray polymict breccia with a greater proportion of hydrothermal cement; and mixed monomict to polymict breccia with clay matrix. The polymictic breccias generated bulk-mineable ore, whereas the volcaniclastic breccia is relatively impermeable and largely barren. Precious metals occur with sulfide and sulfosalt minerals as disseminations, as well as in the veins and breccia cements. There is a progression from pyrite-dominated (stage 1) to pyrite-base metal sulfide and sulfosalt-dominated (stages 2 and 3) to base metal sulfide-dominated (stage 4) breccias and veins. Hydrothermal alteration and deposition of gangue minerals progressed from illite-quartz to quartz-adularia, carbonate, and finally gypsum-dominated assemblages. Free gold occurs in stages 2 and 4, principally intergrown with pyrite, quartz, chalcopyrite, galena, sphalerite, and Ag-rich tennantite–tetrahedrite, and also as inclusions in pyrite. High Rb/Sr ratios in ore-grade zones are closely related to sericite and adularia alteration. Positive correlations of Au and Ag with Cu, As, Pb, Zn, Sb, and Cd in epithermal veins and breccias suggest that all these elements are related to the same mineralization event.     

Silver and silver microparticles of the Cretaceous-Paleogene boundary sediment of Fish Clay Højerup (Stevns Klint,Denmark)

We report the occurrence of micrometer-sized silver particles in the red (“impact” or “ejecta”) layer of the Fish Clay. These appear to be embedded into the biogenic/abiogenic calcite matrix. Energy dispersive X-ray analysis indicates that these microparticles are composed of pure silver (>99% of the total weight). Scanning electron microscopy images reveal irregular and predominantly rounded shapes with rugged surfaces. Numerous silver microparticles are spherical, and some exhibit dendritic textures. These microparticles were probably originated during the Chicxulub asteroid impact event, or immediately afterwards, and dispersed globally.     

Transport of gold and silver in oxygen‐saturated fluids and the formation of high‐fineness gold in saprolitic supergene environments

This paper presents the results of thermodynamic calculations on the solubility of gold and silver in low‐temperature, moderately saline, oxygen‐saturated fluids. Based on the solubilities of gold and silver it is argued that the quantity of gold transported by the fluids depends on the concentration of silver in the primary ores. In ores where the silver/gold ratio is high (1 to > 10), the fluids become saturated in silver and can not dissolve geologically significant concentrations of gold. In ores where the silver/gold ratio is low (< 1), the fluids remain undersaturated with respect to silver and are able to dissolve geologically realistic concentrations of gold and silver. The oxidized fluids start depositing gold and silver as they move downwards and are reduced by the Fe⁺²‐bearing minerals of the primary ores. The occurrence of gold in lateritic profiles can be explained by a prolonged process of interaction between the fluid and primary ores, during which gold and silver precipitate and redissolve selectively at the gradually advancing oxidation‐reduction interface.     

Geochronology and isotopic–geochemical characteristics of magmatic complexes of gold–silver ore–magmatic structures in the Chukotka sector of the Russian Arctic coast

The first results of SHRIMP dating of magmatic complexes and associated gold–silver deposits and ore occurrences (Kupol, Dvoinoe, Moroshka, and others) in the Chukotka sector of the Russian Arctic coast are discussed. The petrological and isotopic–geochronological data are used for reconstructing their formation conditions.     

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

Dualistic distribution coefficients of trace elements in the system mineral–hydrothermal solution. IV. Platinum and silver in pyrite

The FeS₂–Ag–Pt–As system was studied using hydrothermal thermogradient synthesis (with internal sampling) of pyrite crystals at a temperature of 500°C and pressure of 1 kbar in ammonium chloridebased solutions. The modes of occurrence of precious metals (PM) were determined using atomic absorption spectrometry (AAS) in its version of statistical selections of analytical data on single crystals (SSADSC), electron microprobe analysis (EMPA), scanning electron microscopy with energy-dispersive spectrometry (SEM-EDS), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The concentration of Pt in its structural mode in pyrite is as high as 10–11 ppm and is practically not correlated with the As concentration. The dualistic distribution coefficient of Pt between pyrite and hydrothermal solution is 21 ± 7 for the structural mode and 210 ± 80 for the surface-related mode of this element. No inclusions of either any Pt-bearing minerals or Pt itself was detected. Platinum is an element highly compatible with hydrothermal pyrite and is different in this sense from gold, and pyrite is underestimated as a potential concentrator of platinumgroup elements (PGE). The distribution of Ag in pyrite is highly heterogeneous. The likely reason for this is that the Ag solid solution cannot be quenched, and hence, the Ag concentrations broadly vary and are very unsystematically distributed in natural pyrite crystals. Assuming this hypothesis, the limit for Ag accommodation in FeS₂ can be estimated using SSADSC at 0.09 ± 0.06 wt % under the experimental parameters, and the distribution coefficient of the structural Ag mode is thereby evaluated at 1400 ± 700. When crystallizing together with FeS₂ proustite (Ag₃AsS₃) near its melting point, forms mixtures with dervillite (Ag₂AsS₂), in which Ag deficit is counterbalanced by excess divalent As. The limit of As incorporation into pyrite under these conditions is ≤0.1 wt %. SEM-EDS and XPS data indicate that the surface phases are of three types. In the course of crystal growth, practically two-dimensional nonautonomous phases (NP) are aggregated into submicroscopic and micrometer-sized crystalline bodies (mesocrystals) that largely inherit their unusual minor-element composition from NP and are enriched in Ag, Pt, As, and other minor elements. NP and mesocrystals are enriched in Al, which was transferred into them from the Al-bearing Ti alloy of the reaction containers. Silver occur in the volume of the crystals and on their surface as monovalent silver sulfide. Arsenic was detected mostly in the form of di- and trivalent arsenic sulfides. Pentavalent arsenic oxide was identified only on the surface of the crystals and can be easily eliminated by ion milling.     

Combining multiple correspondence analysis with factorial kriging analysis for geochemical mapping of the gold–silver deposit at Marrancos (Portugal)

This study concerns the application of multiple correspondence analysis and factorial kriging analysis to soil data, and aims to identify spatial patterns and superficial soil anomalies of the Au and Ag deposit at Marrancos, Vila Verde. The mineral deposit can be described as a quartz auriferous shear-zone, consisting of a quartz breccia of tectonic origin hosted by metamorphic rocks (hornfels). Gold is associated with arsenopyrite and pyrite, and Ag with galena and galenobismuthite. A total of 286 soil samples were analysed for Fe, Cu, Zn, Pb, Co, Ni, Mn, Ag and Bi by atomic absorption spectrometry, As, Se, Te and Sb by atomic absorption spectrometry–hydride generation system and Au by inductively coupled plasma–atomic emission spectroscopy after extraction of the metal by an organic solvent (methyl-isobutylketone). The methodology used included (a) multiple correspondence analysis applied to soil data to obtain some factors that summarize geochemical information, (b) a structural analysis (variography) in order to account for spatial variability of these factors, and (c) factorial kriging analysis used to split these factors into their spatial components. This methodology allowed an efficient multi-element characterization of the spatial patterns as well as the identification and interpretation of significant anomalies, not always associated to Au-bearing geological structures.     

Visible and “invisible” forms of gold and silver in the crystallization products of melts in the Fe–S–Ag–Au system: experimental data

The forms of Au and Ag occurrence in the crystallization products of melts in the Fe–S–Ag–Au system depending on the proportions of Fe/S and Ag/Au have been studied at (Fe + S)/(Ag + Au) = 0.1. It is shown that the S-rich systems with S/Fe = 2 contain Au–Ag sulfides and Au–Ag alloys. The systems depleted in S with S/Fe = 1 contain only Au–Ag alloys. The results of XPS provide evidence for the sulfide and metallic components of Au and Ag among the crystallization products of melts in the system studied at S/Fe = 2 and a metallic component with S/Fe = 1. According to the data of electron microprobe analysis, the content of “invisible” forms of noble metals in pyrite and pyrrhotite is < 0.024 wt % for Au and <0.030 wt % for Ag; the contents of “invisible” Au and Ag in troilites are 0.040 ± 0.013 wt % Au and 0.079 ± 0.016 wt % Ag.