Silver sulfotellurides from volcanic-hosted massive sulfide deposits in the Southern Urals

Summary This paper addresses Ag-sulfotellurides occurring in volcanic-hosted massive sulfide deposits of the Southern Urals. Cervelleite-like minerals were identified in ores from the Gayskoe, Yaman-Kasy, Severo-Uvaryazhskoe, Tash-Tau, and Babaryk deposits, where they occur in ores containing chalcopyrite, galena, sphalerite, tennantite ± bornite. Other Ag- and Te-bearing minerals (electrum, hessite, stromeyerite and Ag-bearing chalcocite) are present in the association. A benleonardite-like mineral associated with sylvanite and native tellurium was found as a metastable phase in paleohydrothermal tubes relics from the Yaman-Kasy deposit. Formation of the sulfotellurides indicates relative low fTe₂ in the hydrothermal systems, insufficient for formation of most S-free tellurides. The significant Cu enrichment in cervelleite relates to the association with bornite. Broad variations in composition and physical properties of cervelleite-like sulfotellurides allow the supposition of the presence of several, as yet unnamed mineral species, which can be distinguished by Cu contents, Te/S ratios, and presumably by crystal structure.     

Precious metals in massive base metal sulfide deposits

Gold and silver are ubiquitous, sometimes minor but economically important metals in massive base metal sulfide ores. Their content, proportions and distribution in the ores depend on complex, interrelated factors of their source, mobilization, transport and deposition.Different types of these deposits are formed by similar seafloor hydrothermal systems operating, however, in widely differing tectono-stratigraphic environments which span a spectrum from ensimatic-oceanic, through continent-margin to ensialic-continental ones. Like those of the base metals, the proportions and distribution of the precious metals in the ores vary regionally with these changing depositional environments. This suggests that precious metal content of the sub-seafloor rocks in which the generative fluids circulate is one factor that governs the amounts and distribution in the ores. The lithology of these source-rocks is also important. Pillowed, tholeiitic basalts have high permeability, golddepleted crystalline pillow interiors and relatively gold-rich palagonitic rims, and are consequently particularly favorable sources.Mobilization of gold from the sub-seafloor rocks may require basalt-water, and/or carbonaceous sediment-water reactions to produce strongly reduced bisulfide, carbonyl or cyanide complexes that promote gold transport. Chloride complexing and transport are less important for gold but more so for silver and the base metals.Seafloor hydrothermal discharge at shallow depth is commonly accompanied by boiling, steamblast explosions in the vent and resulting deep penetration and mixing of cool, oxygenated seawater with rising hot, reduced metalliferous fluid. This results in deposition of both chloride- and isulfide-complexed gold at depth and centrally in the footwall stockwork or in copper ore in the base of the massive body. Chloride-complexed silver, stable to lower temperatures, is carried farther and deposited with higher-level and more distal, massive zinc-lead ores. Boiling in deep water, however, although possible, is rare. This fact minimizes deep fluid mixing and allows transport of lower temperaturestable, bisulfide-complexed gold to the seafloor and outward from the vent. Gold too, is then deposited with the shallower, distal, massive zinc-lead-silver ore. Late-stage changes in fluid Eh, salinity and activity of sulfur during evolution of the generative hydrothermal system, and by discharge through previously deposited, early stage sulfides around the vent also cause diagenetic remobilization of gold, moving it to shallower, more distal locations in the system. In combination, these relationships explain the three associations of gold in primary, in-situ massive sulfide deposits; in central, deep footwall stockwork mineralization with or without copper, in central copper ore in the base of the massive body and in shallow, peripheral pyritic zinclead-silver ore.Primary, in-situ ore near the vent is sometimes reworked by seafloor density flows which transport clasts of the primary sulfides down-slope, mix them with rock and sedimentary detritus and redeposit them to form secondary, transported ore. Gold, like iron and the base metals, is diluted during this clastic transport. But silver and barite may be enriched indicating transport in the density flows not only as clasts of primary ore but partly also m solution in the hydrothermal fluids that, in this case, must have lubricated the density flows.

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Zusammenfassung Gold- und Silbervorkommen in massiven Metallsulfid-Lagerstätten sind stets ökonomisch wichtige Metalle, auch wenn sie nur in geringen Konzentrationen vorliegen. Der Gehalt an diesen Metallen und ihre Verteilung innerhalb der Lagerstätte hängt von komplexen, sich gegenseitig beeinflussenden Faktoren wie Metallquelle, Art der Mobilisation, Transport und Fällung ab.Unterschiedliche Lagerstättentypen werden von ähnlichen hydrothermalen Systemen auf den Ozeanböden gebildet. Die tektonostratigraphischen Environments unterscheiden sich dabei allerdings beträchtlich; sie befinden sich in ensimatisch-ozeanischen, kontinentalrandlichen und ensialischkontinentalen Bereichen. Innerhalb dieser regional wechselnden Ablagerungsbedingungen variiert Konzentration und Verteilung der Edelmetalle in den Lagerstätten wie bei den einfachen Metallen. Dies bedeutet, daß der Gehalt an Edelmetallen der Gesteine, die den Meeresboden unterlagern und durch die die metallhaltigen Lösungen zirkulieren, ein Faktor ist, der Menge und Verteilung der Metalle in der Lagerstätte steuert. Ebenso ist die Lithologie dieser Gesteine von Bedeutung. Als besonders gut geeignete Quellen gelten kissenartige tholeitische Basalte mit hoher Permeabilität, goldarmen Kisseninneren und relativ goldreichem palagonitischem Rand.Um das Gold aus diesen Gesteinen mobilisieren zu können, bedarf es einer Reaktion zwischen Basalt und Wasser und/oder eines karbonatischen Sediments mit Wasser, um stark reduziertes Bisulfid, Carbonyl-oder Cyanidkomplexe zu bilden, die den Goldtransport ermöglichen. Chlorid-Komplexbildung und -Transport sind zwar wichtig für Silber und einfache Metalle, für Gold spielen sie nur eine untergeordnete Rolle.Der Austritt hydrothermaler Lösungen an Ozeanböden in geringer Tiefe wird in der Regel von Sieden und explosionsartigem Dampfaustritt begleitet und führt deshalb zu einem tiefen Eindringen und Durchmischen von kaltem, sauerstoffreichen Meereswasser mit den aufsteigenden heißen, reduzierten metallischen Lösungen. Daher kommt es zur Fällung von sowohl an Chloridkomplexe als auch an Bisulfidkomplexe gebundenem Gold. Diese Ausfällung findet in größerer Tiefe statt und zwar hauptsächlich im liegenden Stockwerk oder mit Kupfer zusammen an der Basis der massiven Lagerstätte. An Chloridkomplexe gebundenes Silber ist auch bei niedrigeren Temperaturen stabil, wird also weiter transportiert und in einem höheren Niveau in distal gelegenen Blei-Zink-Lagerstätten gefällt. In größeren Wassertiefen kommt es seltener zu dem beobachteten Sieden der austretenden Lösungen. Diese Tatsache reduziert das Durchmischen der Lösungen in größeren Tiefen und ermöglicht den Transport von Gold, das an Bisulfidkomplexe gebunden ist. In diesem Fall ist die Verbindung auch bei niedrigeren Temperaturen noch stabil also transportfähig und kann bis zum Meeresboden oder außerhalb des Schlotes in Lösung bleiben. Dabei kann das Gold zusammen mit Blei, Zink und Silber in mehr distalen Lagerstätten angereichert werden. Späte Änderungen in Eh, Salinität und Schwefelaktivität der Lösungen während der Entwicklung des hydrothermalen Systems, sowie der Austritt durch früher abgelagerte den Schlot umgebende Sulfide, können eine diagenetische Gold-Remobilisation auslösen. Auch dabei kann das Metall zu in geringer Tiefe liegenden, distalen Ablagerungsorten transportiert werden. Berücksichtigt man alle Faktoren, so erklären diese Verhältnisse die drei möglichen Goldvorkommen in primären, in-situ vorliegenden Sulfid-Lagerstätten: Mit Kupfer vergesellschaftet, allerdings nicht unbedingt, zentral im liegenden Stockwerk; an der Basis der Kupferlagerstätte und in geringer Tiefe in Verbindung mit peripheren Blei-Zink-Silber-Vorkommen.Primäre, in-situ neben Schloten vorkommende Lagerstätten werden in einigen Fällen von meeresbodennahen Masseströmen aufgearbeitet. Diese transportieren Sulfidkomponenten, die während des Transports mit Sediment und Gesteinsbruchstücken vermischt und schließlich als sekundäre sedimentäre Lagerstätte abgelagert werden. Durch diesen Transport und die Mischung der Klastika wird die Goldkonzentration in der späteren Lagerstätte stark reduziert. Silber und Barit können dagegen in Ausnahmefällen während des Transports angereichert werden, da diese Komponenten nicht nur als Sulfidbruchstücke transportiert werden, sondern auch in Lösung in den hydrothermalen Lösungen vorhanden sein können. Diese Lösungen dienen in solchen Fällen den Masseströmen als Gleithorizont.

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Résumé Dans les gisements de sulfures métalliques massifs, l'or et l'argent sont des métaux ubiquistes, parfois mineurs, mais toujours d'importance économique. Leur teneur et leur distribution dans les corps minéralisés dépendent de facteurs complexes, en relation les uns avec les autres, tels que: leur source, leur mobilité, leurs modalités de transport et de dépôt.A partir des mêmes systèmes hydrothermaux en action sur le fond de la mer, divers types de gisements peuvent être engendrés, selon leur environnement tectono-stratigraphique: océanique ensimatique, de marge continentale ou continental ensialique. Les teneurs et la répartition des métaux précieux, comme celle des autres métaux varient régionalement selon ces divers milieux. Ceci suggère que le contenu en métaux précieux dans les roches sous-jacentes au fond marin à travers lesquelles circulent les solutions minéralisantes est un facteur qui détermine leurs teneurs et leurs répartitions dans les minerais. La lithologie de ces roches-sources est également importante. Une source particulièrement significative est représentée par les coussins des basaltes tholéiitiques, très perméables, avec leur coeur pauvre en or et leur couronne palagonitique relativement riche.Le lessivage de l'or dans les roches situées sous le fond marin peut impliquer des réactions eau-basalte et/ou eausédiments carbonatés, réactions susceptibles d'engendrer les bisulfures très réduits et les complexes carbonés ou cyanurés qui permettent le transport de l'or. Le transport par complexes chlorurés joue un rôle subordoné dans le cas de l'or, mais important dans le cas de l'argent et des autres métaux.L'arrivée de solutions hydrothermales sur les fonds marins peu profonds est d'ordinaire accompagnée d'ébullitons et d'émissions explosives de vapeur, ce qui provoque la pénétration profonde d'eau de mer froide et oxygénée et son mélange avec les fluides métallifères chauds et réducteurs ascendants. Il en résulte le dépôt de complexes aurifères bisulfurés et chlorurés. Cette précipitation s'opère en profondeur, particulièrement dans les roches sous-jacentes ou dans le minerai de cuivre, à la base des corps minéralisés massifs. L'argent des complexes chlorurés, stables à plus basse température, est transporté plus loin et se dépose, en situation plus distale, dans les minerals massifs de Pb-Zn. Dans les mers profondes, l'ébullition, sans être impossible, est néanmoins un phénomène rare; cette circonstance minimise le mélange des fluides en profondeur et permet le transport de l'or jusqu'à la surface du fond et même loin des évents sous la forme de complexes bisulfurés stables à basse température. L'or est alors déposé en situation distale peu profonde avec les minerals massifs de Zn-Pb-Ag. Des modifications tardives d'Eh, de salinité et d'activité du soufre dans les solutions au cours de l'évolution du système hydrothermal, de même que le lessivage des sulfures déjà accumulés autour des évents entraînent une remobilisation diagénétique de l'or vers des situations distales d'eau peu profonde. La combinaison de ces divers facteurs permet d'expliquer les trois occurrences de l'or dans les dépôts in situ de sulfures massifs primaires: dans les parties centrales des masses sous-jacentes en association ou non avec le Cu, à la base des corps minéralisés en Cu, et à faible profondeur, en liaison avec les gisements périphériques de Pb-Zn-Ag.Les gisements primaires, formés in situ près des évents sont parfois remaniés par des courants de densité, qui emportent des clastes de sulfures, les mélangent aux débris sédimentaires et les redéposent sous forme de minerais secondaires. De tels transports provoquent la dilution de l'or, en même temps que celle du fer et des autres métaux. Par contre, l'argent et la barite peuvent subir un enrichissement car leur transport dans les courants de densité ne s'effectue pas seulement sous forme de clastes, mais également en solution dans des fludies hydrothermaux, lesquels, dans ce cas, contribuent à lubrifier le courant de densité.

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Subsea-floor replacement in volcanic-hosted massive sulfide deposits

Recent research on volcanic-hosted massive sulfide (VMS) deposits indicates that syngenetic subsea-floor replacement ores form an important component of many deposits. In the context of VMS deposits, subsea-floor replacement can be defined as the syn-volcanic formation of sulfide minerals within pre-existing volcanic or sedimentary deposits by infiltration and precipitation in open spaces (fractures, inter- and intra-granular porosity) as well as replacement of solid materials.There are five criteria for distinguishing subsea-floor replacement in massive sulfide deposits: (1) mineralized intervals are enclosed within rapidly emplaced volcanic or sedimentary facies (lavas, intrusions, subaqueous mass-flow deposits, pyroclastic fallout); (2) relics of the host facies occur within the mineral deposit; (3) replacement fronts occur between the mineral deposit and the host lithofacies; (4) the mineral deposit is discordant to bedding; and (5) strong hydrothermal alteration continues into the hanging wall without an abrupt break in intensity. Criteria 1–3 are diagnostic of replacement, whereas criteria 4 and 5 may suggest replacement but are not alone diagnostic. Because clastic sulfide ores contain accessory rock fragments collected by the parent sediment gravity flow(s) during transport, criteria 2 can only be applied to massive, semi-massive, disseminated or vein style deposits, and not clastic ores.The spectrum of VMS deposit types includes deposits that have accumulated largely subsea-floor, and others in which sedimentation and volcanism were synchronous with hydrothermal activity, and precipitation of sulfides occurred at and below the sea floor over the life of the hydrothermal system. Deposits that formed largely subsea-floor are mainly hosted by syn-eruptive or post-eruptive volcaniclastic facies (gravity flow deposits, water-settled fall, autoclastic breccia). However, some subsea-floor replacement VMS deposits are hosted by lavas and syn-volcanic intrusions (sills, domes, cryptodomes). Burial of sea-floor massive sulfide by lavas or sediment gravity flow deposits can interrupt sea-floor mineralization and promote subsea-floor replacement and zone-refining.The distance below the sea floor at which infiltration and replacement took place is rarely well constrained, with published estimates ranging from less than 1 to more than 500 m, but mainly in the range 10–200 m. The upper few tens to hundreds of metres in the volcano-sedimentary pile are the favoured position for replacement, as clastic facies are wet, porous and poorly consolidated in this zone, and at greater depths become progressively more compacted, dewatered, altered, and less amenable to large scale infiltration and replacement by hydrothermal fluids. Furthermore, sustained mixing between the upwelling hydrothermal fluid and cold seawater is regarded as a major cause of sulfide precipitation in VMS systems, and this mixing process generally becomes less effective with increasing depth in the volcanic pile.The relative importance of subsea-floor replacement in VMS systems is related principally to four factors: the permeability and porosity patterns of host lithofacies, sedimentation rate, the relative ease of replacement of host lithofacies (especially glassy materials) and early formed alteration minerals during hydrothermal attack, and physiochemical characteristics of the hydrothermal fluid.     

Hydrogeochemical exploration for volcanic-hosted massive sulfide deposits in semi-arid Australia

Research on hydrogeochemistry for mineral exploration for inland Australia includes development of weathering models and extensive mine-scale and regional groundwater data. Mineral saturation indices for groundwater, activity–activity plots and reaction modelling simulate weathering of volcanic-hosted massive sulfide (VHMS) deposits in deeply weathered environments. At 10 m or more below surface, dissolved O₂ is very low and other solutes such as sulfate, carbonate and nitrate are more likely oxidants. Modelling indicates that these processes differ from oxic weathering of highly eroded terrains, and provide the framework to develop robust hydrogeochemical exploration procedures in covered terrains. Sulfide weathering potentially occurs in two or more phases that effect surrounding groundwaters in differing manners. Deeper oxidative alteration of sulfides (e.g. bornite to chalcopyrite), occurring tens to hundreds of metres below surface, uses sulfate and carbonate as oxidants, causing neutral to alkaline conditions. In this zone, only pyritic massive sulfides potentially generate acidic conditions. Thus, deep sulfide-rich rocks are indicated by sulfate-depleted groundwater. Closer to the surface, sulfides are oxidised to soluble sulfates by dissolved nitrate, with much less acid production than if dissolved oxygen was the main oxidant. Thus, in shallow groundwater, sulfides are indicated by sulfate enrichment and nitrate depletion. Elements are released from sulfides and wall rocks by acid or alkaline conditions. The derived FeS (pH–Eh + Fe + Mn) and AcidS (Li + Mo + Ba + Al) indices distinguish sulfide systems through tens of metres of cover. VHMS systems are distinguished from other non-economic sulfide deposits where there is little transported cover, using various dissolved elements, including Zn, Pb and Cu. Elsewhere, ‘patchiness’ and limited aerial extent of metal signals are due to adsorption effects, that intensify with depth. Other elements such as Mn and Co have lesser diminution effects, but are less selective indicators for VHMS. There is exploration potential for elements such as Pt or Ag. These varying sulfide indicators have moderate utility, even for large-scale (～5 km spacing) sampling. Results indicate that hydrogeochemistry can add value to greenfields exploration for VHMS ore deposits in deeply weathered terrains. It is also moderately successful at indicating the presence of sulfide-rich systems (whether magmatic or hydrothermal) under >100 m cover, thus providing a rapid and cost-effective regional prospectivity tool for deeply buried terrains. Such mineral exploration tools will encourage exploration investment for more difficult regions of Australia and in other deeply weathered regions of the world.     

The use of fluorine as a pathfinder for volcanic-hosted massive sulfide ore deposits

A multi-element geochemical study of the wall rocks of intermediate to felsic volcanic-hosted massive sulfide deposits was carried out to identify pathfinder elements which significantly enlarge the size of exploration targets. Drill core samples from the Crandon massive sulfide deposit in Wisconsin, and outcrop samples from the United Verde and Iron King deposits in Arizona, and from the Captains Flat, Mt. Costigan, and Wiseman Creek deposits in New South Wales, Australia were analyzed. Because anomalously high fluorine values have been described in several volcanic-hosted ore systems, fluorine was included in the study.All of the above deposits have patterns of fluorine enrichment around ore. Drill core samples from two noneconomic prospects within ten miles of the Crandon deposit contain background to only weakly anomalous fluorine values.At the large Crandon deposit (> 50 million tons of zinc, copper ore), fluorine enrichment extends approximately 320 m into the footwall rocks and at least 220 m into the hanging wall rocks. At the large United Verde deposit (> 50 million tons of copper, zinc ore), fluorine enrichment is recognizable in the footwall rocks at least 650 m from the ore. At the smaller Iron King deposit (five million tons production of zinc, lead, copper ore), fluorine enrichment extends for a distance of approximately 60 m into the footwall rocks. At the small deposits in New South Wales (< five million tons production of zinc, lead, copper ore), fluorine enrichment is easily recognizable, but with the samples collected, the limits of the anomalous patterns cannot be defined.Fluorine occurs in some hydrothermal systems unassociated with mineralization and is therefore not a specific signature of ore-forming processes. From the work completed, many massive sulfide deposits in volcanic rocks occur in hydrothermal systems which contain fluorine. On the basis of the data presented, if anomalously high fluorine values do exist in an exploration search area, the chances of finding a massive sulfide ore deposit are improved.Genetic models for volcanic-hosted massive sulfide ore deposits have concentrated on rock textures, alteration mineralogy, and geochemistry of the ore metals. From the data presented, fluorine should be considered as a component of massive sulfide systems in intermediate to felsic volcanic rocks, and should be considered as a possible complexing agent for the ore metals.     

Cyclic-facies analysis of geological sections at massive sulfide deposits of the Urals

Cyclic-facies analysis of stratified volcanic sequences in the ore-controlling depressions makes it possible to recognize the recurrent and genetically related sets of rock layers that make up micro-, meso-, and mega-scale eruptive cycles (elementary cycle, mesocycle, and megacycle). Massive sulfide ores occupy a specific position in geological sections. They are confined to the upper portions of elementary eruptive cycles and hosted in volcanosedimentary units, indicating their formation during the periods of waning volcanic activity. The elementary cycles are not all accompanied by ore mineralization. The mineralization is most complete in the upper elementary cycles of each eruptive meso- and megacycles.Translated from Litologiya i Poleznye Iskopaemye, No. 1, 2005, pp. 78–96.Original Russian Text Copyright © 2005 by Rudnitskii.     

Tellurium-bearing minerals in zoned sulfide chimneys from Cu-Zn massive sulfide deposits of the Urals, Russia

Tellurium-bearing minerals are generally rare in chimney material from mafic and bimodal felsic volcanic hosted massive sulfide (VMS) deposits, but are abundant in chimneys of the Urals VMS deposits located within Silurian and Devonian bimodal mafic sequences. High physicochemical gradients during chimney growth result in a wide range of telluride and sulfoarsenide assemblages including a variety of Cu-Ag-Te-S and Ag-Pb-Bi-Te solid solution series and tellurium sulfosalts. A change in chimney types from Fe-Cu to Cu-Zn-Fe to Zn-Cu is accompanied by gradual replacement of abundant Fe-, Co, Bi-, and Pb- tellurides by Hg, Ag, Au-Ag telluride and galena-fahlore with native gold assemblages. Decreasing amounts of pyrite, both colloform and pseudomorphic after pyrrhotite, isocubanite ISS and chalcopyrite in the chimneys is coupled with increasing amounts of sphalerite, quatz, barite or talc contents. This trend represents a transition from low- to high sulphidation conditions, and it is observed across a range of the Urals deposits from bimodal mafic- to bimodal felsic-hosted types: Yaman-Kasy → Molodezhnoye → Uzelga → Valentorskoye → Oktyabrskoye → Alexandrinskoye → Tash-Tau → Jusa.     

New insights into the genesis of volcanic-hosted massive sulfide deposits on the seafloor from numerical modeling studies

Numerical computer simulations have been used to gain insight into the evolution of marine hydrothermal systems and the formation conditions of massive sulfide deposits in ancient and modern submarine volcanic terrains. Simulation results have been used to gain a better understanding of the formation of massive sulfide ore deposits, their location, zonation, size, and occurrence in various geotectonic settings.Most hydrothermal fluid discharging at the seafloor exhibits temperatures ranging from 200 °C to about 410 °C and average fluid discharge velocities of 1 to 2 m/s in agreement with seafloor observations. Mass calculations imply that average massive sulfide deposits may form in ~ 5000 years while giant deposits take longer than 5000 years to accumulate; supergiant deposits either need much longer time to form (> 35,000 years) or at least 100 ppm of metal in solution. Results indicate that supergiant deposits may only form in certain geotectonic environments where longevity and preservation potential of the hydrothermal system are high. An additional process (mineral precipitate cap) is proposed here to explain the zinc content of massive sulfide deposits. This cap would prevent the widespread dissolution of anhydrite and the ‘wash-out’ of zinc by subsequent hydrothermal fluid discharge.     

Types of massive sulphide deposits in the Urals

Massive sulphide deposits in the Urals are found within volcanic and volcanic-sedimentary sequences of Ordovician to Middle Devonian ages. Four types of economic sulphide deposits have been recognized: Cyprus, Besshi, Urals and Baimak. The Cyprus-type copper sulphide deposits are hosted by mafic volcanites that occur in the basal parts of Palaeozoic volcanic sequences. The Besshi-type copper-zinc deposits are located within clastic sedimentary rocks intercalated with basalts and andesites. Zinc-copper deposits of the Urals-type are hosted by bimodal rhyolite-basalt assemblages, which occur at a higher stratigraphic level than those of Cyprus- and Besshi-types. The Baimak-type zinc-copper-barite deposits are associated with intrusive quartz porphyries which occur in the upper parts of bimodal volcanic successions. In addition there are some sulphide deposits of zinc-lead-barite and zinc-copper composition hosted by Ordovician terrigenous sequences which occur within depressions in Precambrian blocks. These types of sulphide deposits have been formed at various stages of divergence and convergence of the Earth's crust during the orogenic history of the Urals. Received: 27 June 1997 / Accepted: 14 May 1998     

Criteria for the detection of hydrothermal ecosystem faunas in ores of massive sulfide deposits in the Urals

The ore-formational, ore-facies, lithological, and mineralogical-geochemical criteria are defined for the detection of hydrothermal ecosystem fauna in ores of the volcanic-hosted massive sulfide deposits in the Urals. Abundant mineralized microfauna is found mainly in massive sulfide mounds formed in the jasperous basalt (Buribai, Priorsk, Yubileinoe, Sultanov), rhyolite–basalt (Yaman-Kasy, Blyava, Komosomol’sk, Sibai, Molodezhnoe, Valentorsk), and the less common serpentinite (Dergamysh) formations of the Urals (O–D2). In the ore-formational series of the massive sulfide deposits, probability of the detection of mineralized fauna correlates inversely with the relative abundance of felsic volcanic rocks underlying the ores. This series is also marked by a gradual disappearance of colloform pyrite, marcasite, isocubanite, pyrrhotite, and pyrite pseudomorphoses after pyrrhotite; increase of the amount of bornite, fahlores, and barite; decrease of contents of Se, Te, Co, and Sn in chalcopyrite and sphalerite; and decrease of Tl, As, Sb, and Pb in the colloform pyrite. Probability of the detection of mineralized fauna in the morphogenetic series of massive sulfide deposits decreases from the weakly degraded sulfide mounds to the clastic stratiform deposits. The degradation degree of sulfide mounds and fauna preservation correlates with the attenuation of volcanic intensity, which is reflected in the abundance of sedimentary and volcanosedimentary rocks and the depletion of effusive rocks in the geological sections.     

Geochemical behavior during mineralization and alteration events in the Baiyinchang volcanic-hosted massive sulfide deposits,Gansu Province,China

The Zheyaoshan deposit is the largest within the Baiyinchang (BYC) volcanic-hosted massive sulfide (VHMS) district, located in the northern Qilian orogenic belt of North China. The deposit is hosted by quartz keratophyre tuffs, with wall-rock alteration mainly comprising chlorite, sericite, quartz, pyrite and epidote. Mineral assemblages within the altered host rocks can be divided into a sericite-quartz-dominant assemblage (sericite-silicified zone), a chlorite-dominant assemblage (chlorite-dominant zone) and a pyrite-dominant assemblage (mineralized zone) based on geochemical analysis and alteration characteristics. We have conducted detailed processing and critical analysis of the geochemical data of both the altered and least-altered host rocks in order to investigate the problem of closure in the geochemical dataset to eliminate the influence that each component has on the other in terms of mass change, and have applied the standardized method of the mass change calculation to analyze this data. The results show that: (1) the sericite-silicified zone formed along fissures due to the ingress of hydrothermal fluids, with MnO₂, Na₂O and CaO being mobilized into the hydrothermal fluids leached and MgO, Fe₂O₃, SiO₂, K₂O, BaO deposited. Additionally, Ag, Cu and chalcophile elements (Ag, As and Bi) were enriched while Pb, Zn and large ion lithophile elements (LILEs) (Cs, Sr, Eu, Be) were mobilized into hydrothermal fluids; (2) the physiochemical conditions and pH levels of the hydrothermal fluids changed during sericitization, with MgO, Fe₂O₃, BaO being further enriched and MnO, Na₂O, CaO further depleted, leading to formation of chlorite and the initial precipitation of metallogenic the (Cu, Zn, Pb) and chalcophile elements (Ag, As, Bi); (3) the negative Eu anomaly was mainly due to its strong activity when Eu is mobilized into the hydrothermal fluids during since plagioclase break-down during the sericite-silicification process; (4) AI and CCPI values gradually increase towards the orebody. The chlorite-dominant assemblage and sericite-quartz-dominant assemblage on the periphery of the chlorite-dominant zone can all be used as vectors towards the volcanic massive sulfide orebody and for regional-scale mineral exploration. Either leached elements or enriched elements can be considered as significant indicator elements and as prospective indicators for geochemical exploration within the BYC district. The Eu anomaly may be especially useful as an indicator for distinguishing the least-altered rocks which has great significance for exploration on the regional scale.     

Correlation between compositions of ore and host rocks in volcanogenic massive sulfide deposits of the Southern Urals

The geology and typification of volcanogenic massive sulfide (VMS) deposits of the Southern Urals are considered. The mineralogical-geochemical types of these deposits correlate with the composition of the underlying igneous rocks: Ni-Co-Cu deposits correlatedwith serpentinites (Ivanovka type); (Co)-Cu deposits, with basalts (Dombarovka type); Cu-Zn deposits, with basalt-rhyolite and basalt-andesite-rhyolite complexes (Ural type); and Au-Ba-Pb-Zn-Cu deposits, with basalt-andesite-rhyolite complexes with predominance of andesitic and felsic volcanics (Baimak type). The Ural-type deposits are subdivided into three subtypes: I, underlain by basalts (Zn-Cu deposits); II, hosted in felsic volcanic rocks of bimodal complexes (Cu-Zn deposits); and III, hosted in felsic volcanic rocks of continuously differentiated complexes (Zn-Cu deposits with Ba, Pb, and As). The above types and subtypes bearing local names are compared with global types of VMS deposits (MAR, Cyprus, Noranda, and Kuroko), to which they are close but not identical.     

Geodynamic conditions of formation of massive sulfide deposits in the Magnitogorsk Megazone,Southern Urals,and prospection criteria

The zoned composition changes of the massive sulfide deposits in the major massive sulfide zone of the Southern Urals such as the Magnitogorsk Megasynclinorium are considered. The zoning is expressed as the trend of Ni–Co–Cu → Zn–Cu → Cu–Zn → Au–Ba–Pb–Cu–Zn. This trend is related to two basic factors: (1) the subduction process with the slab’s eastward subsidence preconditioned the formation (from the west to the east) of the following massive sulfide zones: accretionary prism, frontal island arc, developed island arc, inter-arc spreading zone, split back arc, and back-arc spreading; (2) the longitudinal zoning of the massive sulfide paleovolcanic belts related to changes in the thickness of the crust’s basaltic layer and an inclination of the subducting plate in transverse blocks of the belt. The first factor affects the general paleovolcanic and metallogenic latitudinal zoning of the studied region, while the second factor defines the local meridional zoning. The composition of ore-bearing solutions is dependent on the formation depth of the subduction fluids, magma differentiation type, and the ratio of deep fluids to solutions of near-surface convective cells. The combination of the geodynamic factors expressed in the composition of ore-bearing volcanic complexes and the specific geological settings defines the massive sulfide mineralization composition and productivity criteria. The most productive structures include the frontal island-arc and inter-arc spreading zones and within them, the central-type volcanic edifices whose basalts are referred to as the island-arc tholeiite series and are characterized by the minimum TiO₂ and Zr content and low La/Yb ratios.     

Ferruginous and manganiferous haloes around massive sulphide deposits of the Urals

Proximal brecciform ferruginous and manganiferous rocks related to VMS deposits of the Urals are subdivided into jasperites, gossanites, and umbers, in addition to thin-bedded jaspers and cherts. The coherence of host rock composition and Mn–Fe-fertility of the sediments have been established. Fe-poor pink hematitic and gray sulphidic chert are typical of the felsic class of VMS deposits. In contrast the contents of Fe vary from high to moderate in ferruginous rocks enclosed in basaltic units associate with VMS deposits. Fe- and Mn-rich ferruginous rocks and umbers occur in association with limestones and calcareous sedimentary rocks in both types of volcanic sequences. A common feature of jasperites and umbers is the abundance of replacement textures of hyaloclastites and carbonates by hematite and silica. In addition, replacement of clastic sulphides by hematite and magnetite is a characteristic genetic feature of gossanites. All of these sedimentary rocks are accompanied by pseudomorphs of hematite and quartz formed after bacterial filaments. The abundance of replacement textures are supportive of the halmyrolysis model, in addition to hydrothermal sedimentary and sub-seafloor hydrothermal replacement theories. Study of chemical zonation of altered hyaloclasts shows depletion of their rims, not only in mobile Na, K, Mg, but also in immobile Al, Ti, and REE; whereas Si and Fe are concentrated in situ. The halmyrolysis model presented here, involving organic-rich calcareous hyaloclastic sediments, resolves the problem of subtraction of Al, Ti, REE and other elements, which are commonly immobile under hydrothermal conditions. The evolution of the halmyrolysis process from acidic reducing to alkaline oxidized conditions infers a possible range in transformation from Fe^II–Mg smectites to Fe-silicates and Fe-Si oxides as precursors of brecciform jasperite and thin-bedded jasper. The higher acidic, initial stage, of gossanite formation seems to be required for oxidation of organic matter and/or pyrite. The acidic condition facilitates the temporal preservation of “immobile” elements (Al, Ti, REE) in “immature”chlorite–hematite gossanites. Another peculiarity of the gossanite-forming processes is the likely sorption of P, U and V by iron hydroxides displacing sulphides. The general evolution of all ferruginous sediments results in complete Fe²⁺ oxidation and silicification accompanied by subtraction of other elements. The vertical diagenetic differentiation leads to concentration of Mn-carbonates, silicates and oxyhydroxides into the tops of jasperite and gossanite layers. Mn oxyhydroxides scavenge positively charged hydrated cations like Co and Ni. Near-vent bacterial communities may activate the processes of volcanic glass and sulphide degradation. The proposed processes of halmyrolysis followed by silicification, in situ, may resolve the enigma of silica-rich sediment formation in a silica undersaturated ocean. The discrimination between gossanite and jasperite is useful for elaboration of new criteria for local exploration of VMS- and Mn-deposits. Halo dispersion of gossanites covering an area about two to three times that of the massive sulphide deposit is a good vector for ore body discovery. Proximal gossanites can be differentiated from jasperites by presence of relic sulphide clasts or elevated contents of chalcophile elements (Cu, Fe, Zn, Pb, Bi, Te, As, Sb, Ba), noble metals (Au, Ag) and distinct REE patterns with La and Eu positive anomalies. The development of halmyrolysis and biomineralization models merit further elaboration and testing in on-going research, in order to add or revise theories of iron and manganese deposit formation.     

Two genetic types of volcanic-hosted massive sulfide mineralizations from the Eastern Desert of Egypt

Volcanic-hosted (Cu–Zn–Pb) massive sulfide mineralizations are described from four prospects in the Eastern Desert: Helgate, Maaqal, Derhib, and Abu Gurdi. Helgate and Maaqal prospects are hosted in island arc volcanics in a well-defined stratigraphic level. Massive sulfides form veins and lenses. Although these veins and lenses are locally deformed, sulfides from Helgate and Maaqal prospects show primary depositional features. They form layers and colloidal textures. Sphalerite, pyrite, chalcopyrite, and galena are the major sulfides. Gangue minerals are represented by chlorite, quartz, and calcite. The sulfide mineralizations at Helgate and Maaqal are Zn-dominated. Derhib and Abu Gurdi prospects occur as disseminations, small massive lenses, and veins along shear zones in talc tremolite rocks at the contact between metavolcanics and metasedimentary rocks. The host rocks at Derhib and Abu Gurdi are metamorphosed to lower amphibolite facies as revealed by silicate mineral assemblage and chemistry. Chalcopyrite, pyrite, sphalerite, and galena are the major sulfide minerals while pyrrhotite is less common. Recrystallization, retexturing and remobilization of sulfide minerals are reflecting postdepositional metamorphic and structural modifications. Electrum and Ag–Pb–Bi tellurides are common accessories. Gangue minerals comprise amphiboles of actinolite and actinolitic hornblende composition, talc, and chlorite. The ores at Derhib and Abu Gurdi are Cu–Zn and Zn-dominated, respectively. The distinct geological, petrographical, and geochemical differences between sulfide mineralizations at Helgate–Maaqal on one hand and Derhib and Abu Gurdi on the other hand suggest two genetic types of sulfide mineralizations; Helgate–Maaqal prospects (type 1) are similar to the Archean analogs from Canada (Noranda type), while Derhib and Abu Gurdi (type 2) show similarity to ophiolite-associated deposits similar to those described from Cyprus, Oman, and Finland. In genetic type 1, ore minerals were deposited on the seafloor; the role of postdepositional hydrothermal activity is limited. In genetic type 2, base metals were part of the ultramafic rocks and were later redistributed and mobilized during deformation to be deposited along shear zones. The dominance and diversity of tellurides in genetic type 2 highlight the role of metamorphic–hydrothermal fluids.     

Volcanogenic massive sulfide deposits of ophiolite associations

Volcanogenic massive sulfide deposits in ophiolite complexes are usually attributed to the Cyprus type. They associate with basaltic volcanics that are formed in mid-ocean or back-arc spreading centers and much less frequently in intra-plate settings. The deposits are characterized by copper or copper-zinc ores that are enriched in Ni, Co, and in places Mn and As, but are very poor in Pb and demonstrate a low to moderate content of Ag and Au. Typically, the deposits are low to very low in ore and metal reserves. Cyprus-type deposits were irregularly distributed during geological history. The most ancient of them were formed in the Neoproterozoic, while the bulk of the deposits are Ordovician or Cretaceous in age. Their possible Paleoproterozoic analogues can be found in the Svecofennian belt (Outokumpu ore district), while modern ones are confined to the Explorer and Endeavour Ridges and southern segment of the Juan de Fuca Ridge.     

Metamorphism of volcanogenic massive sulphide deposits in the Urals. Ore geology

The Urals VMS province comprises a broad spectrum of variably metamorphosed deposits, from unmetamorphosed to those without any primary ore textures, which are the results of high-grade metamorphic processes. Contact metamorphism near large granite and granodiorite plutons caused the most significant changes of ores, with coarse-grained to pegmatoidal ores with magnetite closest to its contact with the intrusion, followed by pyrrhotite-enriched copper ores, and more distal zinc (± Pb ± Ag) mineralisation. Koktau, Tarnyer and Vesenneye deposits are metamorphosed to the hornblende-hornfels and pyroxene-hornfels facies (t = 400–800 °C, P = 1–6 kbar). Metamorphism of Tash-Yar, Dzhusinskoe and Krasnogvardeiskoe deposits corresponds to the greenschist and albite-epidote-hornfels facies (t = 250–450 °C, P = 1–4 kbar).The regional metamorphism of VMS ores varies from prehnite-pumpellyite facies (t = 150–300 °C, P = 0.5–4 kbar) in the South Urals to the epidote-amphibolite and amphibolite facies (t = 400–600 °C (up to 700 °C), P = 1–6 kbar) in the Karabash area in the Middle Urals. In the Magnitogorsk zone, the metamorphism of host rocks and VMS bodies increases to the north, reaching its peak near the Ufa promontory of the East European platform. With increased metamorphism, the morphology of orebodies evolves from gently dipping thick lenses (Alexandrinskoe and Uzelga fields), to subvertical and folded (Uchaly and Novo-Uchaly deposits) and pseudomonoclinal steeply-dipping vein-like bodies (Karabash district).The massive sulphide transformation in PTX-gradient fields led to partial redistribution of ore material. An enrichment in Cu, Zn, Ag and Au, ± Pb occur in the uppermost parts of large steeply-dipping massive sulphide lenses in wide tectonic zones (e.g., Gai deposit) or as gold-sulphide disseminated bodies near large metamorphosed VMS lenses, distal to a granite pluton (Tarnyer deposit). Partial melting probably occurred in some highly metamorphosed deposits (Tarnyer, Koktau and Mauk). Redeposition of base metals sulphides (chalcopyrite, tennantite, sphalerite, ± bornite, galena), as well as the presence of “visible” gold and tellurides, took place during retrograde metamorphism, which produced a transfer of ore matter towards the low stress areas, such as the outer parts of shear zones, the uppermost parts of steeply-dipping ore lenses, pressure shadows, hinge zones of small folds, and small extension fractures (i.e., Alpine-type veins) in deformed ore body or its immediate surroundings.     

The volcanic-hosted massive sulphide deposits of the Iberian Pyrite Belt Review and preface to the Thematic Issue

The Iberian Pyrite Belt (IPB) has, over the past decade, been an area of renewed mining activity and scientific research that has resulted in a wealth of new data and new geological and metallogenic concepts that are succinctly presented in this Thematic Issue. The reason for this interest in the IPB, which forms part of the Hercynian orogenic belt, is that its Late Devonian to Middle Carboniferous rocks host a huge quantity of volcanic-hosted massive sulphide (VMS) mineralization (1700 Mt of sulphides, totalling 14.6 Mt Cu, 13.0 Mt Pb, 34.9 Mt Zn, 46100 t Ag and 880 t Au). The mineralization and its environment display a number of typical signatures that can be related to the mineralogy and zoning of the sulphide orebodies, to the lead isotopes of the mineralization, to the geochemical and mineralogical variations in the hydrothermal alteration halos surrounding the orebodies, to the geochemical characteristics of the bimodal volcanics hosting the VMS, to the complex structural evolution during the Hercynian orogeny, to the presence of palaeofaults and synsedimentary structures that acted as channels and discharge traps for the metalliferous fluids, and to the gossans developed over VMS. Discriminant geological criteria have been deduced for each domain which can be helpful in mineral exploration, complementing the more traditional prospecting techniques. Although the question of the IPB's geodynamic setting is still under debate, any interpretation must now take into account some incontrovertible constraints: for example, the geochemical characteristics of a large part of the basic lavas are comparable to those of mantle-derived basalts emplaced in extensional tectonic settings, and the associated acidic rocks were produced by melting of a basic crustal protolith at low- to medium-pressures and a steep geothermal gradient, thus, the sulphide-bearing volcano-sedimentary sequence differs strongly from recent arc-related series. It is considered here that the tectonic setting was extensional and epicontinental and that it developed during the Hercynian plate convergence, that culminated in thin-skinned deformation and accretion of the South Portuguese terrane to the Iberian Paleozoic continental block.

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Resumen (translated by E. Pascual) Durante la década pasada, la Faja Pirítica Ibérica (FPI) ha sido un área de actividad minera e investigación cientifica renovadas, lo que ha conducido a la obtención de nuevos datos y conceptos geológicos y metalogénicos, que se exponen sucintamente en este Número Especial. La razón de este interés en la FPI, que forma parte del cinturón orogénico hercínico, es que sus rocas, cuyas edades abarcan desde el Devónico tardío al Carbonífero Medio, albergan una enorme cantidad de mineralizaciones de sulfuros masivos ligados a vulcanismo (1700 millones de toneladas de sulfuros, que totalizan 14,6 Mt de Cu, 13,0 Mt de Pb, 34,9 Mt de Zn, 46100 toneladas de Ag y 880 toneladas de Au). Las mineralizaciones y su entorno muestran signaturas que se pueden relacionar con la mineralogía y la zonación de las masas de sulfuros, con los isótopos de plomo de la mineralización, con las variaciones en los halos de alteración hidrotermal alrededor de las mineralizaciones, con los caracteres geoquímicos de las rocas volcánicas bimodales que albergan los sulfuros masivos, con la compleja evolución tectónica del conjunto durante la orogenia hercínica, con la existencia de paleofallas y estructuras sinsedimentarias que actuaron como canales y trampas de descarga para los fluidos metalíferos y los gossans que se desarrollaron sobre los sulfuros. Se han deducido criterios geológicos discriminantes para cada área de conocimiento, que pueden ser útiles para la exploración minera, complementando las técnicas más tradicionales de prospección. Aunque la cuestión del entorno geodinámico de la FPI todavía es materia de debate, cualquier interpretación tiene que tener ahora en cuenta algunas restricciones incontrovertibles: por ejemplo, los caracteres geoquímicos de una gran parte de las rocas básicas son comparables a los de basaltos derivados del manto y emplazados en entornos tectónicos extensionales, y las rocas ácidas asociadas se produjeron a partir de un protolito cortical básico, a presiones bajas o intermedias y asociadas a un abrupto gradiente térmico. Por consiguiente, la secuencia vulcanosedimentaria que contiene los sulfuros masivos difiere claramente de las series recientes relacionadas con entornos de arco. Consideramos aquí que el entorno tectónico fue extensional y epicontinental y que tuvo lugar durante la convergencia de placas hercínica, que culminó en deformación “thin-skinned” y acreción del terreno constituído por la Zona Sudportuguesa al bloque continental paleozoico ibérico.

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Received: 4 April 1996 / Accepted: 10 April 1997