Mineralogy of Noble Metals and “Invisible” Speciations of These Elements in Natural Systems

A special issue of Minerals (ISSN 2075-163X). This special issue belongs to the section "Mineral Deposits".

Deadline for manuscript submissions: closed (31 October 2019) | Viewed by 54871

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1. Sobolev Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, 630090 Novosibirsk, Russia
2. Department of Geology and Geophysics, Novosibirsk State University, 630090 Novosibirsk, Russia
Interests: ore-forming processes; experiment; thermodynamic modeling; minerals-indicators; fluid−mineral−rock interactions; gold mineralization; gold deposits; mechanisms of ore formation; reconstruction of T,P,X-conditions
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Dear Colleagues,

In nature, gold most commonly occurs as an alloy with silver and, more rarely, with platinum, palladium, and other elements, and ranges in size from nanoparticles to big nuggets. The origin of nuggets has been still debated. More and more novel mineral species, including the minerals of noble metals, are discovered every year. New phases containing Au, Ag, Pt, Pd, Rh, Ru are also known to be discovered, but the mineral has not been named yet. Still unsolved is the problem of the “invisible” speciations of gold, silver and other noble metals in sulfides and other minerals-concentrators of these elements. The chemistry and scales of the processes of dissolution, transport and deposition of noble metals have not been fully studied. Improved understanding of the genesis of deposits of noble metals in endogenic and supergene environments is necessary. The knowledge of the nature of gold occurrence and sites in gold-bearing minerals is significant for developing better process to extract gold from ores. The processes of consolidation, aggregation and purification of native elements under the conditions of formation of oxidation zones and placer deposits are poorly studied. It is known that gold content in the weathering crust considerably exceed that in endogenous sources. The mechanisms of this effect are still ambiguous and are attributed to different processes, including physicochemical and biological ones. Revealing of the role of the biogenic factor in the geochemistry of gold and other noble metals is an important task. Noble metals are a very popular in nanotechnology.

Dr. Galina Palyanova
Guest Editor

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Keywords

  • Mineralogy of gold and other noble metals
  • New minerals of noble metals
  • The geochemistry of noble metals
  • Chemistry and scales of processes of dissolution, transport and deposition of noble metals
  • “Invisible” speciations of gold, silver, platinum, palladium in sulfides and other minerals
  • Processes of consolidation, aggregation and mechanisms of formation of noble metal nuggets
  • Differentiation of noble metals in ore forming processes
  • Models for the formation of noble metals deposits
  • Biogenic noble metals
  • Noble metals and nanotechnology

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Published Papers (12 papers)

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Editorial

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4 pages, 190 KiB  
Editorial
Editorial for Special Issue: “Mineralogy of Noble Metals and “Invisible” Speciations of These Elements in Natural Systems”
by Galina Palyanova
Minerals 2020, 10(3), 210; https://doi.org/10.3390/min10030210 - 26 Feb 2020
Cited by 2 | Viewed by 1482
Abstract
This Special Issue of Minerals covers a broad range of topics related to the mineralogy of noble metals (Au, Ag, Pt, Pd, Rh, Ru) and the forms of occurrence, formation and distribution of these elements in natural ore-forming systems [...] Full article

Research

Jump to: Editorial

21 pages, 5911 KiB  
Article
Characteristics of Supergene Gold of Karst Cavities of the Khokhoy Gold Ore Field (Aldan Shield, East Russia)
by Galina S. Anisimova, Larisa A. Kondratieva and Veronika N. Kardashevskaia
Minerals 2020, 10(2), 139; https://doi.org/10.3390/min10020139 - 6 Feb 2020
Cited by 10 | Viewed by 6226
Abstract
Typomorphic features of supergene gold in karst cavities were studied in the recently discovered Au–Te–Sb–Tl deposit within the Khokhoy gold ore field of the Aldan-Stanovoy auriferous province (Aldan shield, East Russia). Two morphological types of supergene gold, massive and porous, are recognized there. [...] Read more.
Typomorphic features of supergene gold in karst cavities were studied in the recently discovered Au–Te–Sb–Tl deposit within the Khokhoy gold ore field of the Aldan-Stanovoy auriferous province (Aldan shield, East Russia). Two morphological types of supergene gold, massive and porous, are recognized there. The first type is represented by gold crystals and irregular mass, with the fineness ranging from 835 to 1000‰. They are closely associated with goethite, siderite, unnamed Fe, Te, and Tl carbonates, Tl tellurites/tellurates and antimonates, as well as avicennite with a Te impurity. The second type is represented by mustard gold of two types with different internal structure: microporous and dendritic. The supergene gold is characterized by persistently high fineness. Along with Ag, it invariably contains Hg (up to 5.78 wt%) and Bi, and, rarely, Pb, Cu, and Fe. The supergene gold is chemically homogeneous, and its particles are all marked by high fineness, without any rims or margins. The obtained characteristics made it possible to prove the existence of two genetic types of supergene gold. Mustard microporous gold is the result of the decomposition of the associated minerals—goethite, Tl oxides, tellurium, Fe, Mn and Tl carbonates and antimonates, containing microinclusions of gold. Massive gold and dendrites are newly formed. The decomposition, remobilization, and reprecipitation of residual gold nanoparticles and their aggregation led to the formation of dendrites, and with further crystal growth and filling of pores, to gold of massive morphology. In terms of morphology, internal structure, fineness, and trace element composition, supergene gold of the Khokhoy gold ore field is comparable to gold from the Kuranakh deposit (Russia) and the Carlin-type gold deposits. It also is similar to spungy and mustard gold from Au–Te and Au–Sb deposits, weathering crusts, and placers. Its main characteristic feature is a close paragenesis with Tl minerals. Full article
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14 pages, 8815 KiB  
Article
Mustard Gold in the Oleninskoe Gold Deposit, Kolmozero–Voronya Greenstone Belt, Kola Peninsula, Russia
by Arkadii A. Kalinin, Yevgeny E. Savchenko and Ekaterina A. Selivanova
Minerals 2019, 9(12), 786; https://doi.org/10.3390/min9120786 - 13 Dec 2019
Cited by 8 | Viewed by 3742
Abstract
The Oleninskoe intrusion-related gold–silver deposit is the first deposit in the Precambrian of the Fennoscandian Shield, where mustard gold has been identified. The mustard gold replaces küstelite with impurities of Sb and, probably, gold-bearing dyscrasite and aurostibite. The mosaic structure of the mustard [...] Read more.
The Oleninskoe intrusion-related gold–silver deposit is the first deposit in the Precambrian of the Fennoscandian Shield, where mustard gold has been identified. The mustard gold replaces küstelite with impurities of Sb and, probably, gold-bearing dyscrasite and aurostibite. The mosaic structure of the mustard gold grains is due to different orientations and sizes of pores in the matrix of noble metals. Zonation in the mustard gold grains is connected with mobilization and partial removal of silver from küstelite, corresponding enrichment of the residual matter in gold, and also with the change in the composition of the substance filling the pores. Micropores in the mustard gold are filled with iron, antimony or thallium oxides, silver chlorides, bromides, and sulfides. The formation of mustard gold with chlorides and bromides shows that halogens played an important role in the remobilization of noble metals at the stage of hypergene transformation of the Oleninskoe deposit. Full article
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24 pages, 3375 KiB  
Article
Formation of Au-Bearing Antigorite Serpentinites and Magnetite Ores at the Massif of Ophiolite Ultramafic Rocks: Thermodynamic Modeling
by Valery Murzin, Konstantin Chudnenko, Galina Palyanova and Dmitry Varlamov
Minerals 2019, 9(12), 758; https://doi.org/10.3390/min9120758 - 5 Dec 2019
Cited by 3 | Viewed by 4613
Abstract
We constructed thermodynamic models of the formation of two types of gold-ore mineralization at the Kagan ultramafic massif in the Southern Urals (Russia). The first type of gold-mineralization is widely spread at the massif in the tectonic zones of schistose serpentinites containing typically [...] Read more.
We constructed thermodynamic models of the formation of two types of gold-ore mineralization at the Kagan ultramafic massif in the Southern Urals (Russia). The first type of gold-mineralization is widely spread at the massif in the tectonic zones of schistose serpentinites containing typically ≤ 0.1 ppm Au. The second type of gold-ore mineralization is represented by veined massive, streaky and impregnated magnetite ores in contact with serpentinites. It contains to 5 vol.% sulfides and 0.2–1.2 ppm Au. Our thermodynamic calculations explain the formation of two types of gold-ore mineralization in the bedrocks of ultramafic massifs. Metamorphic water, which is the result of the dehydration of early serpentinites (middle Riphean) during high-temperature regional metamorphism (700 °C, 10 kbar) (late Precambrian), is considered as the source of ore-bearing fluid in the models. The metasomatic interaction of metamorphic fluid with serpentinites is responsible for the gold-poor mineralization of the 1st type at T = 450–250 °C and P = 2.5–0.5 kbar. The hydrothermal gold-rich mineralization of the 2nd type was formed during mixing of metamorphic and meteoric fluids at T = 500–400 °C and P = 2–3 kbar and discharge of mixed fluid in the open space of cracks in serpentinites. The model calculations showed that the dominant forms of gold transport in fluids with pH = 3–5 are AuCl2 complexes (≥450 °C) and, as the temperature decreases, AuHS0, or AuOH0. Mineral associations obtained in model calculations are in general similar to the observed natural types of gold mineralization. Full article
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19 pages, 4358 KiB  
Article
Composition and Ligand Microstructure of Arsenopyrite from Gold Ore Deposits of the Yenisei Ridge (Eastern Siberia, Russia)
by Anatoly M. Sazonov, Sergey A. Silyanov, Oleg A. Bayukov, Yuriy V. Knyazev, Yelena A. Zvyagina and Platon A. Tishin
Minerals 2019, 9(12), 737; https://doi.org/10.3390/min9120737 - 28 Nov 2019
Cited by 8 | Viewed by 4103
Abstract
The Mössbauer spectroscopy method was used to study the ligand microstructure of natural arsenopyrite (31 specimens) from the ores of the major gold deposits of the Yenisei Ridge (Eastern Siberia, Russia). Arsenopyrite and native gold are paragenetic minerals in the ore; meanwhile, arsenopyrite [...] Read more.
The Mössbauer spectroscopy method was used to study the ligand microstructure of natural arsenopyrite (31 specimens) from the ores of the major gold deposits of the Yenisei Ridge (Eastern Siberia, Russia). Arsenopyrite and native gold are paragenetic minerals in the ore; meanwhile, arsenopyrite is frequently a gold carrier. We detected iron positions with variable distribution of sulfur and arsenic anions at the vertexes of the coordination octahedron {6S}, {5S1As}, {4S2As}, {3S3As}, {2S4As}, {1S5As}, {6As} in the mineral structure. Iron atoms with reduced local symmetry in tetrahedral cavities, as well as iron in the high-spin condition with a high local symmetry of the first coordination sphere, were identified. The configuration {3S3As} typical for the stoichiometric arsenopyrite is the most occupied. The occupation degree of other configurations is not subordinated to the statistic distribution and varies within a wide range. The presence of configurations {6S}, {3S3As}, {6As} and their variable occupation degree indicate that natural arsenopyrites are solid pyrite {6S}, arsenopyrite {3S3As}, and loellingite {6As} solutions, with the thermodynamic preference to the formation of configurations in the arsenopyrite–pyrite–loellingite order. It is assumed that in the variations as part of the coordination octahedron, the iron output to the tetrahedral positions and the presence of high-spin Fe cations depend on the physical and chemical conditions of the mineral formation. It was identified that the increased gold concentrations are typical for arsenopyrites with an elevated content of sulfur or arsenic and correlate with the increase of the occupation degree of configurations {5S1As}, {4S2As}, {1S5As}, reduction of the share of {3S3As}, and the amount of iron in tetrahedral cavities. Full article
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33 pages, 6967 KiB  
Article
Distribution of “Invisible” Noble Metals between Pyrite and Arsenopyrite Exemplified by Minerals Coexisting in Orogenic Au Deposits of North-Eastern Russia
by Vladimir Tauson, Sergey Lipko, Raisa Kravtsova, Nikolay Smagunov, Olga Belozerova and Irina Voronova
Minerals 2019, 9(11), 660; https://doi.org/10.3390/min9110660 - 27 Oct 2019
Cited by 9 | Viewed by 4050
Abstract
The study focused on the forms of occurrence and distribution of hidden (“invisible”) noble metals (NMs = Au, Ag, Pt, Pd, Ru) in the coexisting pyrites and arsenopyrites of four samples of mineral associations from three Au deposits in the north-east of Russia. [...] Read more.
The study focused on the forms of occurrence and distribution of hidden (“invisible”) noble metals (NMs = Au, Ag, Pt, Pd, Ru) in the coexisting pyrites and arsenopyrites of four samples of mineral associations from three Au deposits in the north-east of Russia. The unique nature of our approach was the combination of methods of local analysis and statistics of the compositions of individual single crystals of different sizes. This allowed us to take into account the contribution of the surface component to the total NM content and to distinguish the structurally bound form of the elements. The following estimates of the distribution coefficients of the structural (str) and surficial (sur) forms of elements were obtained: D ¯ P y / A s p s t r   = 2.7 (Au), 2.5 (Pd), 1.6 (Pt), 1.7 (Ru) and D ¯ P y / A s p s u r   = 1.6 (Au), 1.1 (Pd), 1.5 (Pt and Ru). The data on Ag in most cases indicated its fractionation into pyrite ( D ¯ P y / A s p s t r   = 17). Surface enrichment was considered as a universal factor in “invisible” NM distribution. A number of elements (i.e., Pt, Ru, Ag) tended to increase their content with a decrease in the crystallite size in pyrite and arsenopyrite. This may be due to both the phase size effect and the intracrystalline adsorption of these elements at the interblock boundaries of a dislocation nature. The excess of metal (or the presence of S vacancies) in pyrite increased Ag and Pt content in its structure and, to a lesser extent, the content of Ru, Pd and Au. Arsenopyrite exhibited a clear tendency to increase the content of Pt, Ru and Pd in samples with excess As over S. Sulphur deficiency was a favourable factor for the incorporation of Ag and platinoids into the structures of the mineral associations studied. Perhaps this was due to the lower sulphur fugacity. Pyrite with excess Fe was associated with higher contents of some NMs. The presence of other impurity elements was not an independent factor in NM concentration. Full article
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18 pages, 10620 KiB  
Article
Experimental Modeling of Noble and Chalcophile Elements Fractionation during Solidification of Cu-Fe-Ni-S Melt
by Elena Sinyakova, Victor Kosyakov, Galina Palyanova and Nikolay Karmanov
Minerals 2019, 9(9), 531; https://doi.org/10.3390/min9090531 - 31 Aug 2019
Cited by 12 | Viewed by 2882
Abstract
We carried out a directed crystallization of a melt of the following composition (in mol. %): Fe 31.79, Cu 15.94, Ni 1.70, S 50.20, Sn 0.05, As 0.04, Pt, Pd, Rh, Ru, Ag, Au, Se, Te, Bi, and Sb by 0.03. The obtained [...] Read more.
We carried out a directed crystallization of a melt of the following composition (in mol. %): Fe 31.79, Cu 15.94, Ni 1.70, S 50.20, Sn 0.05, As 0.04, Pt, Pd, Rh, Ru, Ag, Au, Se, Te, Bi, and Sb by 0.03. The obtained cylindrical sample consisted of monosulfide solid solution (mss), nonstoichometric isocubanite (icb*), and three modifications of intermediate solid solution (iss1, iss2, iss3) crystallized from the melt. The simultaneous formation of two types of liquids separated during cooling of the parent sulfide melt was revealed. In the first, concentrations of noble metals associated with Bi, Sb, and Te were found. The second is related to Cu and was found to contain a large amount of S in addition to Bi and Sb. We established the main types of inclusions formed during fractional crystallization of Pt-bearing sulfide melt. It was shown that noble metals are concentrated in inclusions in the form of RuS2, PdTe2, (Pt,Pd)Te2, PtRhAsS, and Ag2Se, doped with Ag, Cu, and Pd, in mss and in the form of PtAs2; Au-doped with Ag, Cu, and Pd; Ag2Te; and Pd(Bi,Sb)xTe1−x in icb* and iss. As solid solutions in the base metal sulfides, Rh is present in mss, Sn in iss. Full article
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18 pages, 19812 KiB  
Article
Mustard Gold of the Gaching Ore Deposit (Maletoyvayam Ore Field, Kamchatka, Russia)
by Nadezhda D. Tolstykh, Galina A. Palyanova, Ol’ga V. Bobrova and Evgeny G. Sidorov
Minerals 2019, 9(8), 489; https://doi.org/10.3390/min9080489 - 15 Aug 2019
Cited by 19 | Viewed by 5145
Abstract
The Gaching high-sulfidation (HS) epithermal Au–Ag deposits, part of the Maletoyvayam ore field, which is located in the volcanic belts of the Kamchatka Peninsula (Russia). The main ore components are native gold, tellurides, selenides, and sulphoselenotellurides of Au and oxidation products of Au-tellurides. [...] Read more.
The Gaching high-sulfidation (HS) epithermal Au–Ag deposits, part of the Maletoyvayam ore field, which is located in the volcanic belts of the Kamchatka Peninsula (Russia). The main ore components are native gold, tellurides, selenides, and sulphoselenotellurides of Au and oxidation products of Au-tellurides. This study examines the different types of native gold in this ore deposit and the mechanisms and sequential transformation of calaverite (AuTe2) into mustard gold. The primary high fineness gold (964‰–978‰) intergrown with maletoyvayamite Au3Te6Se4 and other unnamed phases (AuSe, Au(Te,Se)) differ from the secondary (mustard) gold in terms of fineness (1000‰) and texture. Primary gold is homogeneous, whereas mustard is spongy. Two types of mustard gold were identified: (a) Mixtures of Fe-Sb(Te,Se,S) oxides and fine gold particles, which formed during the hypogenic transformation stage of calaverite due to the impact of hydrothermal fluids, and (b) spotted and colloform gold consisting of aggregates of gold particles in a goethite/hydrogoethite matrix. This formed during the hypergenic transformation stage. Selenides and sulphoselenotellurides of gold did not undergo oxidation. Pseudomorphic replacement of calaverite by Au-Sb(Te,Se,S,As) oxides was also observed. Full article
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15 pages, 5515 KiB  
Article
Quartz Rb-Sr Isochron Ages of Two Type Orebodies from the Nibao Carlin-Type Gold Deposit, Guizhou, China
by Lulin Zheng, Ruidong Yang, Junbo Gao, Jun Chen, Jianzhong Liu and Depeng Li
Minerals 2019, 9(7), 399; https://doi.org/10.3390/min9070399 - 28 Jun 2019
Cited by 18 | Viewed by 3697
Abstract
The Nibao gold deposit, which includes both fault-controlled and strata-bound gold orebodies, constitutes an important part of the Yunnan–Guizhou–Guangxi “Golden Triangle” region. Defining the mineralization age of these gold orebodies may provide additional evidence for constraining the formation ages of low-temperature orebodies and [...] Read more.
The Nibao gold deposit, which includes both fault-controlled and strata-bound gold orebodies, constitutes an important part of the Yunnan–Guizhou–Guangxi “Golden Triangle” region. Defining the mineralization age of these gold orebodies may provide additional evidence for constraining the formation ages of low-temperature orebodies and their metallogenic distribution in South China. Petrographic studies of gold-bearing pyrites and ore-related quartz veins indicate that these pyrites coexist with quartz or filled in vein-like quartz, which suggests a possible genetic relationship between the two from Nibao gold deposit. Minerals chemistry shows that Rb and Sr are usually hosted in fluid inclusions in quartz ranging from 0.0786 to 2.0760 ppm and 0.1703 to 2.1820 ppm, respectively. The Rb–Sr isotopic composition of gold-bearing quartz-hosted fluid inclusions from the Nibao gold deposit were found to have Rb–Sr isochron ages of 142 ± 3 and 141 ± 2 Ma for both fault-controlled and strata-bound orebodies, respectively, adding more evidence to previous studies and thus revealing a regional gold mineralization age of 148–134 Ma. These results also confirm the Middle-Late Yanshanian mineralizing events of Carlin-type gold deposits in Yunnan, Guizhou, and Guangxi Provinces of Southwest China. In addition, previous studies indicated that antimony deposits in the region which were formed at ca. 148–126 Ma have a close affinity with gold deposits. This illustrates that the regional low-temperature hydrothermal gold mineralization is related in space and time to the Yanshanian (ca. 146–115 Ma) magmatic activity. Specifically, the large-scale gold and antimony mineralization are considered to be inherently related to mantle-derived mafic and ultramafic magmatic rocks associated with an extensional tectonic environment. Based on the initial 87Sr/86Sr ratios of 0.70844 ± 0.00022 (2σ) and 0.70862 ± 0.00020 (2σ) for gold-bearing quartz veins from fault-controlled and strata-bound gold orebodies, respectively, at the Nibao gold deposit, as well as the C, H, O, and S isotopic characteristics of gold deposits located in the Golden Triangle region, we suggest that the mantle-derived material can be involved in the formation of the Nibao gold deposit and that the ore-forming fluid can be derived from a mixed crust–mantle source. Full article
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17 pages, 6626 KiB  
Article
Source of the Chaoyangzhai Gold Deposit, Southeast Guizhou: Constraints from LA-ICP-MS Zircon U–Pb Dating, Whole-rock Geochemistry and In Situ Sulfur Isotopes
by Hinyuen Tsang, Jingya Cao and Xiaoyong Yang
Minerals 2019, 9(4), 235; https://doi.org/10.3390/min9040235 - 16 Apr 2019
Cited by 4 | Viewed by 3585
Abstract
The Chaoyangzhai gold deposit is one of the newly discovered medium to large scale turbidite-hosted gold deposits in Southeast Guizhou, South China. In this study, laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) zircon U–Pb dating on the tuffaceous- and sandy-slates of Qingshuijiang Formation, Xiajiang [...] Read more.
The Chaoyangzhai gold deposit is one of the newly discovered medium to large scale turbidite-hosted gold deposits in Southeast Guizhou, South China. In this study, laser ablation-inductively coupled plasma-mass spectrometer (LA-ICP-MS) zircon U–Pb dating on the tuffaceous- and sandy-slates of Qingshuijiang Formation, Xiajiang Group, and gold-bearing quartz vein yielded similar age distributions, indicating that zircon grains in gold-bearing quartz vein originated from the surrounding tuffaceous- and sandy-slates. In addition, the youngest weighted mean ages of the zircon grains from the tuffaceous- and sandy-slates were 775 ± 13 Ma and 777 ± 16 Ma, respectively, displaying that the tuffaceous- and sandy-slates of the Qingshuijiang Formation were likely deposited in Neoproterozoic. Based on their major and trace element compositions, the tuffaceous- and sandy-slates were sourced from a felsic igneous provenance. The sandy slates have higher contents of Au (mostly ranging from 0.019 to 0.252 ppm), than those of the tuffaceous slates (mostly lower than 0.005 ppm). The δ34SV-CDT values of pyrite and arsenopyrite of the gold-bearing samples range from +8.12‰ to +9.99‰ and from +9.78 to +10.78‰, respectively, indicating that the sulfur source was from the metamorphic rocks. Together with the evidence of similar geochemical patterns between the tuffaceous- and sandy-slates and gold-bearing quartz, it is proposed that the gold might be mainly sourced from sandy slates. The metamorphic devolatilization, which was caused by the Caledonian orogeny (Xuefeng Orogenic Event), resulted in the formation of the ore-forming fluid. Gold was likely deposited in the fractures due to changes of the physico-chemical conditions, leading to the formation of the Chaoyangzhai gold deposit, and the large-scale gold mineralization in Southeast Guizhou. Full article
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14 pages, 2344 KiB  
Article
X-ray Photoelectron Spectroscopy (XPS) Study of the Products Formed on Sulfide Minerals Upon the Interaction with Aqueous Platinum (IV) Chloride Complexes
by Alexander Romanchenko, Maxim Likhatski and Yuri Mikhlin
Minerals 2018, 8(12), 578; https://doi.org/10.3390/min8120578 - 8 Dec 2018
Cited by 37 | Viewed by 10314
Abstract
The interaction of aqueous solutions bearing platinum-group elements (PGEs) with sulfides is important for understanding the formation and weathering of PGE ore deposits, mineral processing, and synthesis of nanomaterials. Here, the surface species formed upon the contact of the main sulfide minerals (pyrite, [...] Read more.
The interaction of aqueous solutions bearing platinum-group elements (PGEs) with sulfides is important for understanding the formation and weathering of PGE ore deposits, mineral processing, and synthesis of nanomaterials. Here, the surface species formed upon the contact of the main sulfide minerals (pyrite, pyrrhotite, galena, chalcopyrite and valleriite) with the solutions of H2PtCl6 (pH 1.5, 20 °C) have been studied using X-ray photoelectron spectroscopy (XPS). Uptake of Pt increased gradually with increasing interaction time, and depended, as well as the composition of immobilized products, on the mineral nature and the state of its surface, e.g., the chemical pre-treatment. The highest rate of Pt deposition was observed on galena and valleriite and the lowest on pyrite and pyrrhotite. The preliminary moderate oxidation of pyrrhotite promoted Pt deposition, which, however, was hindered under harsh reaction conditions. The pre-oxidation of pyrite in all cases resulted in a decrease of the Pt deposition. Initially, Pt(IV) chloride complexes adsorb onto the mineral surface, and then the reduction of Pt(IV) to Pt(II) and substitution of chloride ions with sulfide groups occur forming sulfides of Pt(II) and then, Pt(IV). The reduction of Pt species to the metallic state was observed at valleriite after 24 h, probably due the negative charge of the sulfide nanolayers of this sulfide-hydroxide composite mineral. Full article
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14 pages, 2217 KiB  
Article
Colloidal and Deposited Products of the Interaction of Tetrachloroauric Acid with Hydrogen Selenide and Hydrogen Sulfide in Aqueous Solutions
by Sergey Vorobyev, Maxim Likhatski, Alexander Romanchenko, Nikolai Maksimov, Sergey Zharkov, Alexander Krylov and Yuri Mikhlin
Minerals 2018, 8(11), 492; https://doi.org/10.3390/min8110492 - 31 Oct 2018
Cited by 11 | Viewed by 3740
Abstract
The reactions of aqueous gold complexes with H2Se and H2S are important for transportation and deposition of gold in nature and for synthesis of AuSe-based nanomaterials but are scantily understood. Here, we explored species formed at different proportions of [...] Read more.
The reactions of aqueous gold complexes with H2Se and H2S are important for transportation and deposition of gold in nature and for synthesis of AuSe-based nanomaterials but are scantily understood. Here, we explored species formed at different proportions of HAuCl4, H2Se and H2S at room temperature using in situ UV-vis spectroscopy, dynamic light scattering (DLS), zeta-potential measurement and ex situ Transmission electron microscopy (TEM), electron diffraction, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Metal gold colloids arose at the molar ratios H2Se(H2S)/HAuCl4 less than 2. At higher ratios, pre-nucleation “dense liquid” species having the hydrodynamic diameter of 20–40 nm, zeta potential −40 mV to −50 mV, and the indirect band gap less than 1 eV derived from the UV-vis spectra grow into submicrometer droplets over several hours, followed by fractional nucleation in the interior and coagulation of disordered gold chalcogenide. XPS found only one Au+ site (Au 4f7/2 at 85.4 eV) in deposited AuSe, surface layers of which partially decomposed yielding Au0 nanoparticles capped with elemental selenium. The liquid species became less dense, the gap approached 2 eV, and gold chalcogenide destabilized towards the decomposition with increasing H2S content. Therefore, the reactions proceed via the non-classical mechanism involving “dense droplets” of supersaturated solution and produce AuSe1−xSx/Au nanocomposites. Full article
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