Experimental and Thermodynamical Modeling of Ore-Forming Processes in Magmatic and Hydrothermal Systems

A special issue of Minerals (ISSN 2075-163X).

Deadline for manuscript submissions: closed (30 June 2018) | Viewed by 53341

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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,

Experimental investigations and thermodynamical modeling have been successfully used to solve many problems, in which ore-forming processes play an important role. Experimental study of simple systems with precisely controlled parameters provides data necessary for obtaining reliable thermodynamic characteristics of minerals, aqueous species (ions and complex ions and molecules), gas mixtures and solid solutions. The main obstacles to the experiments are multi-component, multi-phase and multi-aggregate features of natural systems and the inevitability of their simplification. Thermodynamic modeling can be an alternative to complex model experiments. To construct quantitative genetic models of ore formation processes, computer thermodynamic modeling on the basis of modern program complexes is used. The reconstruction of the sources of ore components and fluids, physico-chemical parameters, mechanisms of accumulation and separation of elements during the formation of ore deposits is an important task of fundamental problems of ore-forming processes. We invite researchers to contribute to the Special Issue on the experimental investigations and thermodynamical modeling of ore-forming processes in magmatic and hydrothermal systems.

Dr. Galina Palyanova
Guest Editor

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Keywords

  • The source and chemistry of ore fluids
  • Geofluid-rock interaction
  • Solubilities of ore minerals
  • Transport of the metals
  • Models of ore formation
  • Mechanisms of ore formation
  • Mineral equilibria
  • Nonequilibrium processes
  • Reconstruction of T,P,X-conditions

Published Papers (11 papers)

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Editorial

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5 pages, 183 KiB  
Editorial
Editorial for the Special Issue: Experimental and Thermodynamic Modeling of Ore-Forming Processes in Magmatic and Hydrothermal Systems
by Galina Palyanova
Minerals 2018, 8(12), 590; https://doi.org/10.3390/min8120590 - 13 Dec 2018
Cited by 1 | Viewed by 2122
Abstract
A number of excellent books and articles on the ore-forming processes, magmatic and hydrothermal systems, physicochemical conditions of the ore-forming fluids, and thermodynamic modeling in the geosciences have been published over the past 50 years [...] Full article

Research

Jump to: Editorial

21 pages, 11703 KiB  
Article
Physicochemical Conditions of Formation for Bismuth Mineralization Hosted in a Magmatic-Hydrothermal Breccia Complex: An Example from the Argentine Andes
by Francisco J. Testa, Lejun Zhang and David R. Cooke
Minerals 2018, 8(11), 486; https://doi.org/10.3390/min8110486 - 26 Oct 2018
Cited by 3 | Viewed by 5497
Abstract
The San Francisco de los Andes breccia-hosted deposit (Frontal Cordillera, Argentina) is characterized by complex Bi–Cu–Pb–Zn–Mo–As–Fe–Ag–Au mineralization. After magmatic-hydrothermal brecciation, tourmaline and quartz partially cemented open spaces, followed by quiescent periods where Bi–Cu–Pb–Zn ore formed. Bismuth ore precipitation is characterized by Bi-sulfides, sulfosalts, [...] Read more.
The San Francisco de los Andes breccia-hosted deposit (Frontal Cordillera, Argentina) is characterized by complex Bi–Cu–Pb–Zn–Mo–As–Fe–Ag–Au mineralization. After magmatic-hydrothermal brecciation, tourmaline and quartz partially cemented open spaces, followed by quiescent periods where Bi–Cu–Pb–Zn ore formed. Bismuth ore precipitation is characterized by Bi-sulfides, sulfosalts, and tellurosulfide inclusions, which temporally co-exist with Ag-telluride inclusions and chalcopyrite. Three distinct Bi mineralizing stages have been defined based on the following mineral assemblages: (1) Bismuthinite (tetradymite–hessite inclusions); (2) Bismuthinite (tetradymite–hessite inclusions) + cosalite (tetradymite inclusions) + chalcopyrite; and (3) Cosalite (tetradymite inclusions) + chalcopyrite. Overall, Ag-poor bismuthinite hosts both Bi-tellurosulfide and Ag-telluride inclusions, whereas Ag-rich cosalite only hosts tetradymite inclusions. Full article
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22 pages, 7979 KiB  
Article
Nature and Evolution of Paleoproterozoic Sn and Rare Metal Albitites from Central Brazil: Constraints Based on Textural, Geochemical, Ar-Ar, and Oxygen Isotopes
by Ana Rita F. Sirqueira, Márcia A. Moura, Nilson F. Botelho and T. Kurt Kyser
Minerals 2018, 8(9), 396; https://doi.org/10.3390/min8090396 - 8 Sep 2018
Cited by 5 | Viewed by 6521
Abstract
Economic and subeconomic concentrations of Sn, In, rare earth elements (REE), Ta, and Nb are known in Central Brazil, in the Goias Tin Province. The Sn-P enriched albitites studied in this paper occur in sharp contact with peraluminous granites of the Aurumina Suite [...] Read more.
Economic and subeconomic concentrations of Sn, In, rare earth elements (REE), Ta, and Nb are known in Central Brazil, in the Goias Tin Province. The Sn-P enriched albitites studied in this paper occur in sharp contact with peraluminous granites of the Aurumina Suite (2.0–2.17 Ga) and schists of the Archean to Paleoproterozoic Ticunzal Formation, as dikes or lenses from late-stage magma of the peraluminous magmatism, probably in granite cupolas. Geological, petrological, and isotopic studies were conducted. The albitites consist of albite, quartz, cassiterite, apatite, K-feldspar, and muscovite, and have magmatic texture, such as alignment of albite laths, and snowball texture in quartz, apatite, and cassiterite. They are enriched in Na2O, P2O5, Sn, Ta, and Nb (Ta > Nb), and depleted in CaO, K2O, TiO2, MgO, Sr, Ba, Th, and REE. 40Ar/39Ar in muscovite gave a plateau age of 1996.55 ± 13 Ma, interpreted as approaching the crystallization age. Oxygen isotope data in albite-cassiterite pairs resulted in an equilibrium temperature of 653–1016 °C and isotopic fluid composition of 8.66–9.72‰. They were formed by crystallization of a highly evolved and sodic granitic magma. This study has implications for Central Brazil’s economic potential and offers better understanding of tin behavior in rare, evolved peraluminous granitic magmas. Full article
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15 pages, 6515 KiB  
Article
Sulfide Formation as a Result of Sulfate Subduction into Silicate Mantle (Experimental Modeling under High P,T-Parameters)
by Yuliya Bataleva, Yuri Palyanov and Yuri Borzdov
Minerals 2018, 8(9), 373; https://doi.org/10.3390/min8090373 - 29 Aug 2018
Cited by 11 | Viewed by 4041
Abstract
Ca,Mg-sulfates are subduction-related sources of oxidized S-rich fluid under lithospheric mantle P,T-parameters. Experimental study, aimed at the modeling of scenarios of S-rich fluid generation as a result of desulfation and subsequent sulfide formation, was performed using a multi-anvil high-pressure apparatus. Experiments were carried [...] Read more.
Ca,Mg-sulfates are subduction-related sources of oxidized S-rich fluid under lithospheric mantle P,T-parameters. Experimental study, aimed at the modeling of scenarios of S-rich fluid generation as a result of desulfation and subsequent sulfide formation, was performed using a multi-anvil high-pressure apparatus. Experiments were carried out in the Fe,Ni-olivine–anhydrite–C and Fe,Ni-olivine–Mg-sulfate–C systems (P = 6.3 GPa, T of 1050 and 1450 °C, t = 23–60 h). At 1050 °C, the interaction in the olivine–anhydrite–C system leads to the formation of olivine + diopside + pyrrhotite assemblage and at 1450 °C leads to the generation of immiscible silicate-oxide and sulfide melts. Desulfation of this system results in the formation of S-rich reduced fluid via the reaction olivine + anhydrite + C → diopside + S + CO2. This fluid is found to be a medium for the recrystallization of olivine, extraction of Fe and Ni, and subsequent crystallization of Fe,Ni-sulfides (i.e., olivine sulfidation). At 1450 °C in the Ca-free system, the generation of carbonate-silicate and Fe,Ni-sulfide melts occurs. Formation of the carbonate component of the melt occurs via the reaction Mg-sulfate + C → magnesite + S. It is experimentally shown that the olivine-sulfate interaction can result in mantle sulfide formation and generation of potential mantle metasomatic agents—S- and CO2-dominated fluids, silicate-oxide melt, or carbonate-silicate melt. Full article
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18 pages, 3372 KiB  
Article
Hydrothermal Metasomatism and Gold Mineralization of Porphyritic Granite in the Dongping Deposit, North Hebei, China: Evidence from Zircon Dating
by Hao Wei, Jiuhua Xu, Guorui Zhang, Xihui Cheng, Haixia Chu, Chunjing Bian and Zeyang Zhang
Minerals 2018, 8(9), 363; https://doi.org/10.3390/min8090363 - 21 Aug 2018
Cited by 9 | Viewed by 4029
Abstract
A porphyritic granite intrusion was recently discovered in the Zhuanzhilian section of the Dongping gold deposit. There is as many as one tonnage of Au in the fractured shear zone within the porphyritic granite intrusion, but no relevant reports concerning the origin and [...] Read more.
A porphyritic granite intrusion was recently discovered in the Zhuanzhilian section of the Dongping gold deposit. There is as many as one tonnage of Au in the fractured shear zone within the porphyritic granite intrusion, but no relevant reports concerning the origin and age of the intrusion has been published as yet. In this paper, zircon U-Pb dating is used to study the geochronology of porphyritic granite, in order to find out the evidence of age and the relationship with gold mineralization. There are two groups of zircon 207Pb/235U-206Pb/238U concordant ages of porphyritic granites: The concordant age of 373.0 ± 3.5 Ma, with the weighted mean age of 373.0 ± 6.4 Ma; and the concordant age of 142.02 ± 1.2 Ma with the weighted mean age of 142.06 ± 0.84 Ma. We believe that the first group might represent the age of residual zircon of alkaline complex, while the second group might be related with main gold mineralization. The obtained results of the petrography and electron probe analysis indicate that the porphyritic quartz and porphyritic granite, as well as gold mineralization, might be products of a late replacement of tectonic-hydrothermal fluid, which was rich in Si, Na and K originally and later yielded gold-forming fluids. Full article
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21 pages, 2437 KiB  
Article
Numerical Modeling of REE Fractionation Patterns in Fluorapatite from the Olympic Dam Deposit (South Australia)
by Sasha Krneta, Cristiana L. Ciobanu, Nigel J. Cook and Kathy J. Ehrig
Minerals 2018, 8(8), 342; https://doi.org/10.3390/min8080342 - 8 Aug 2018
Cited by 27 | Viewed by 5654
Abstract
Trace element signatures in apatite are used to study hydrothermal processes due to the ability of this mineral to chemically record and preserve the impact of individual hydrothermal events. Interpretation of rare earth element (REE)-signatures in hydrothermal apatite can be complex due to [...] Read more.
Trace element signatures in apatite are used to study hydrothermal processes due to the ability of this mineral to chemically record and preserve the impact of individual hydrothermal events. Interpretation of rare earth element (REE)-signatures in hydrothermal apatite can be complex due to not only evolving fO2, fS2 and fluid composition, but also to variety of different REE-complexes (Cl-, F-, P-, SO4, CO3, oxide, OH etc.) in hydrothermal fluid, and the significant differences in solubility and stability that these complexes exhibit. This contribution applies numerical modeling to evolving REE-signatures in apatite within the Olympic Dam iron-oxide-copper-gold deposit, South Australia with the aim of constraining fluid evolution. The REE-signatures of three unique types of apatite from hydrothermal assemblages that crystallized under partially constrained conditions have been numerically modeled, and the partitioning coefficients between apatite and fluid calculated in each case. Results of these calculations replicate the measured data well and show a transition from early light rare earth element (LREE)- to later middle rare earth element (MREE)-enriched apatite, which can be achieved by an evolution in the proportions of different REE-complexes. Modeling also efficiently explains the switch from REE-signatures with negative to positive Eu-anomalies. REE transport in hydrothermal fluids at Olympic Dam is attributed to REE–chloride complexes, thus explaining both the LREE-enriched character of the deposit and the relatively LREE-depleted nature of later generations of apatite. REE deposition may, however, have been induced by a weakening of REE–Cl activity and subsequent REE complexation with fluoride species. The conspicuous positive Eu-anomalies displayed by later apatite with are attributed to crystallization from high pH fluids characterized by the presence of Eu3+ species. Full article
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18 pages, 5703 KiB  
Article
Physicochemical Model of Formation of Gold-Bearing Magnetite-Chlorite-Carbonate Rocks at the Karabash Ultramafic Massif (Southern Urals, Russia)
by Valery Murzin, Konstantin Chudnenko, Galina Palyanova, Aleksandr Kissin and Dmitry Varlamov
Minerals 2018, 8(7), 306; https://doi.org/10.3390/min8070306 - 20 Jul 2018
Cited by 6 | Viewed by 4783
Abstract
We present a physicochemical model for the formation of magnetite-chlorite-carbonate rocks with copper gold in the Karabash ultramafic massif in the Southern Urals, Russia. The model was constructed based on the formation geotectonics of the Karabash massif, features of spatial distribution of metasomatically [...] Read more.
We present a physicochemical model for the formation of magnetite-chlorite-carbonate rocks with copper gold in the Karabash ultramafic massif in the Southern Urals, Russia. The model was constructed based on the formation geotectonics of the Karabash massif, features of spatial distribution of metasomatically altered rocks in their central part, geochemical characteristics and mineral composition of altered ultramafic rocks, data on the pressure and temperature conditions of formation, and composition of the ore-forming fluids. Magnetite-chlorite-carbonate rocks were formed by the hydrothermal filling of the free space, whereas chloritolites were formed by the metasomatism of the serpentinites. As the source of the petrogenic and ore components, we considered rocks (serpentinites, gabbro, and limestones), deep magmatogenic fluids, probably mixed with metamorphogenic fluids released during dehydration and deserpentinization of rocks in the lower crust, and meteoric waters. The model supports the involvement of sodium chloride-carbon dioxide fluids extracting ore components (Au, Ag, and Cu) from deep-seated rocks and characterized by the ratio of ore elements corresponding to Clarke values in ultramafic rocks. The model calculations show that copper gold can also be deposited during serpentinization of deep-seated olivine-rich rocks and ore fluids raised by the tectonic flow to a higher hypsometric level. The results of our research allow predicting copper gold-rich ore occurrences in ultramafic massifs. Full article
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15 pages, 3593 KiB  
Article
Stability of AuCl2 from 25 to 1000 °C at Pressures to 5000 bar and Consequences for Hydrothermal Gold Mobilization
by Alexander V. Zotov, Nikolai N. Kuzmin, Vladimir L. Reukov and Boris R. Tagirov
Minerals 2018, 8(7), 286; https://doi.org/10.3390/min8070286 - 4 Jul 2018
Cited by 22 | Viewed by 4690
Abstract
Gold is transported in high-temperature chloride-bearing hydrothermal fluids in the form of AuCl2. The stability of this complex has been extensively studied, but there is still considerable disagreement between available experimental data on the temperature region 300–500 °C. To solve [...] Read more.
Gold is transported in high-temperature chloride-bearing hydrothermal fluids in the form of AuCl2. The stability of this complex has been extensively studied, but there is still considerable disagreement between available experimental data on the temperature region 300–500 °C. To solve this problem, we measured the solubility of gold in HCl/NaCl fluids (NaCl concentration varied from 0.1 to 3 mol·(kg·H2O)−1) at 450 °C and pressures from 500 to 1500 bar (1 bar = 105 Pa). The experiments were performed using a batch autoclave method at contrasting redox conditions: in reduced experiments hydrogen was added to the autoclave, and in oxidized experiments the redox state was controlled by the aqueous SO2/SO3 buffer. Hydrogen pressure in the autoclaves was measured after the experiments in the reduced system. The gold solubility constant, Au(cr) + HCl°(aq) + Cl = AuCl2 + 0.5 H2°(aq), was determined for the experimental T-P parameters as log Ks° = −4.77 ± 0.07 (500 bar), −5.11 ± 0.08 (1000 bar), and −5.43 ± 0.09 (1500 bar). These data, together with values from the literature for temperatures from 25 to 1000 °C, were fitted to the simple equation log Ks° = 4.302 − 7304∙T(K)−1 − 4.77∙log d(w) + 11080∙(log d(w))∙T(K)−1 − 6.94 × 106∙(log d(w)) T(K)−2, where d(w) is the pure water density. This equation can be used together with the extended Debye–Hückel equation for activity coefficients to calculate gold solubility at pressures up to 5000 bar at fluid chlorinities at least up to 30 wt %. The speciation of gold in natural chloride-bearing fluids is discussed. Full article
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27 pages, 4076 KiB  
Article
Trace Element Partitioning Dualism under Mineral–Fluid Interaction: Origin and Geochemical Significance
by Vladimir L. Tauson, Sergey V. Lipko, Nikolay V. Smagunov and Raisa G. Kravtsova
Minerals 2018, 8(7), 282; https://doi.org/10.3390/min8070282 - 30 Jun 2018
Cited by 23 | Viewed by 4264
Abstract
Trace element (TE) partitioning in the system “mineral-hydrothermal solution” is studied by the method of thermo-gradient crystal growth coupled with internal sampling of a fluid phase. The analytical procedure used enables evaluating of structurally bound and superficially bound modes of TE in crystals [...] Read more.
Trace element (TE) partitioning in the system “mineral-hydrothermal solution” is studied by the method of thermo-gradient crystal growth coupled with internal sampling of a fluid phase. The analytical procedure used enables evaluating of structurally bound and superficially bound modes of TE in crystals and determining corresponding dual partition coefficients. The case of precious metals (PM—Au, Pt, Pd) at 450 and 500 °C and 100 MPa pressure is considered. The minerals are pyrite, As-pyrite, magnetite, Mn-magnetite and hematite and fluids are ammonium chloride-based hydrothermal solutions. The partition coefficients for structural and surficial modes, Dpstr and Dpsur, are found to be unexpectedly high (except for Au in pyrite). High concentrations of PM are attributed to superficial nonautonomous phases (NAPs), which can be considered as primary concentrators of PM. We also have studied the co-crystallization (exchange) coefficients (De) of REE (Ce, Eu, Er, Yb) and Fe in magnetite and hematite at 450 °C and 100 MPa. Desur is elevated to two orders of magnitude as compared to Destr. It is shown that not only physicochemical parameters affect REE distribution in hydrothermal systems, but also NAP presence and its composition. The crystal growth mechanism specified by the agency of NAP is suggested. The study of PM distribution in natural pyrite of gold-ore deposits supported the importance of differentiating between structurally and superficially bound TE modes for correct use of experimental D values to determining element concentrations in ore-forming fluids. Full article
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20 pages, 5542 KiB  
Article
Geochronology, Petrology, and Genesis of Two Granitic Plutons of the Xianghualing Ore Field in South Hunan Province: Constraints from Zircon U–Pb Dating, Geochemistry, and Lu–Hf Isotopic Compositions
by Lizhi Yang, Xiangbin Wu, Jingya Cao, Bin Hu, Xiaowen Zhang, Yushuang Gong and Weidong Liu
Minerals 2018, 8(5), 213; https://doi.org/10.3390/min8050213 - 15 May 2018
Cited by 33 | Viewed by 4474
Abstract
Two small-sized granitic plutons, outcropped in Xianghualing ore field, South Hunan (South China), have a close relationship with the super large-scale Sn–W polymetallic mineralization in this ore field. The Laiziling and Jianfengling plutons are composed of medium- to coarse-grained two-mica and coarse-grained biotite [...] Read more.
Two small-sized granitic plutons, outcropped in Xianghualing ore field, South Hunan (South China), have a close relationship with the super large-scale Sn–W polymetallic mineralization in this ore field. The Laiziling and Jianfengling plutons are composed of medium- to coarse-grained two-mica and coarse-grained biotite granites, respectively, and have zircon U–Pb ages of 156.4 ± 1.4 Ma and 165.2 ± 1.4 Ma, respectively. Both of the Laiziling and Jianfengling granites are characterized by extremely similar elemental and Lu–Hf isotopic compositions with high contents of SiO2, Al2O3, Na2O, K2O, high A/CNK ratios, negative εHf(t) values (ranging from −3.86 to −1.38 and from −5.44 to −3.71, respectively), and old TDMC ages (ranging from 1.30 to 1.47 Ga and from 1.32 to 1.56 Ga, respectively). These features indicate that they both belong to highly fractionated A-type granites, and were formed in an extensional setting and from the same magma chamber originated from the Paleoproterozoic metamorphic basement of South China with a certain amount of mantle-derived magma involved with temperatures of ca. 730 °C and low oxygen fugacity. Full article
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23 pages, 11563 KiB  
Article
Geochronology and Genesis of the Xitian W-Sn Polymetallic Deposit in Eastern Hunan Province, South China: Evidence from Zircon U-Pb and Muscovite Ar-Ar Dating, Petrochemistry, and Wolframite Sr-Nd-Pb Isotopes
by Jingya Cao, Qianhong Wu, Xiaoyong Yang, Hua Kong, Huan Li, Xiaoshuang Xi, Qianfeng Huang and Biao Liu
Minerals 2018, 8(3), 111; https://doi.org/10.3390/min8030111 - 8 Mar 2018
Cited by 53 | Viewed by 6224
Abstract
The recently explored Xitian tungsten-tin (W-Sn) polymetallic ore field, located in Hunan province, South China, is one of the largest ore fields in the Nanling Range (NLR). Two major metallogenic types appeared in this ore field, skarn- and quartz vein-type. They are distributed [...] Read more.
The recently explored Xitian tungsten-tin (W-Sn) polymetallic ore field, located in Hunan province, South China, is one of the largest ore fields in the Nanling Range (NLR). Two major metallogenic types appeared in this ore field, skarn- and quartz vein-type. They are distributed within Longshang, Heshuxia, Shaiheling, Hejiangkou, Goudalan, and so on. Hydrothermal zircons from two altered granites yielded U-Pb ages of 152.8 ± 1.1 Ma, and 226.0 ± 2.8 Ma, respectively. Two muscovite samples from ore-bearing quartz vein yielded 40Ar/39Ar plateau ages of 156.6 ± 0.7 Ma, 149.5 ± 0.8 Ma, respectively. Combined with the geological evidence, two metallogenic events are proposed in the Xitian ore field, with skarn-type W-Sn mineralization in Late Triassic (Indosinian) and quartz vein/greisen type W-Sn mineralization in Late Jurassic (Yanshanian). The relatively low Ce/Ce* ratios and high Y/Ho ratios in zircons from two altered granites indicate that the hydrothermal fluids of two metallogenic events are characterized by low oxygen fugacities and enrichment in F. The similar chondrite-normalized patterns between the skarn and Xitian Indosinian granites and Sr-Nd-Pb isotopic compositions of wolframite suggest that the metal sources for both types W-Sn mineralization are derived from a crustal source. Full article
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