Supergene and hypogene alteration in the dual-use kaolin-bearing coal deposit Angren, SE Uzbekistan

The Jurassic Angren coal–kaolin deposit, Uzbekistan, is one of the largest producers of coal and kaolin suitable for refractories and industrial ceramics in central Asia. The Major coal seam, attaining a thickness between 4 and 24 m, is encased by kaolin-bearing bedsets which have been derived from supergene pre- and hypogene post coal kaolinization. Joint clay-mineralogical and coal petrographic analyses formed the basis of the environment analysis of this coal–kaolin series and constrained the physico-chemical conditions existing during the Triassic through Jurassic period of time. Massive kaolin I underneath the coal seam is a typical residual kaolin or underclay with arsenic Fe-disulfides and siderite indicative of a reducing swampy depositional environment developing under moderately hot climatic conditions. Towards the top, kaolin I became reworked fluvial by processes. The Major coal seam developed in swamps interfingering with a fluvial drainage system of suspended to mixed-load deposits. The maximum temperature for the post-depositional alteration of the carbonaceous material is 70 °C. Post-coal kaolinization (kaolin II) affecting trachyandesites and trachytes is of low-temperature origin and low-sulphidation-type. The temperature of formation was well below 200 °C, deduced from the absence of dickite in the clay mineral assemblage. Basaltic dykes intersected the coal–kaolin series and account for contact metamorphic reactions in the proximal parts of the aluminum-bearing wall rocks reaching sanidinite-facies conditions with temperatures around 1000 °C.     

Geochemical characteristics of the Arabshah kaolin deposit,Takab geothermal field,NW Iran

The Arabshah kaolin deposit (Takab geothermal field, NW Iran) is the product of alteration of Miocene dioritic rocks. According to mineralogical data, the rock-forming minerals in this deposit include kaolinite, quartz, muscovite-illite, pyrophyllite, accompanied by lesser amounts of rutile, chlorite, anatase, albite, gypsum, nontronite, and pyrite. Consideration of elemental ratios and geochemical indices such as TiO₂, Nb + Cr, Ti + Fe, Sr + Ba, and La + Ce + Y demonstrated that both hypogene and supergene processes played a significant role in the development of this deposit. The mass change calculations revealed that elements like Zr, Ga, Hf, REEs, and Th which are normally immobile in ordinary alteration processes had both incremental and decremental trends during the development of this deposit. The Eu and Ce anomaly values (normalized to chondrite) in kaolinized samples vary within the range of 0.65–1.13 and 0.91–1.05, respectively. It seems that the variation of negative Eu anomaly values was controlled by kaolinization of feldspars by hypogene solutions and by scavenging of this element by Fe oxides and hydroxides (formed during oxidation of hypogene pyrite by supergene solutions). Variation of Ce anomalies also unravels the effective role of reducing hypogene fluids and to some extent of supergene solutions during kaolinization. Combination of the results obtained from mineralization considerations, mass change calculations of elements, and correlation coefficients illustrate that distribution and concentration of major, minor, and rare earth elements during kaolinization at Arabshah were affected by the function of factors such as changes in physico-chemical conditions of altering solutions (e.g., Eh and pH), adsorption, accessibility to complex-forming ligands, water-rock ratios, existing in resistant (to alteration) mineral phases, and scavenging by Fe and Mn oxides.     

Cu, Mn, and Ag mineralization in the Quebrada Marquesa Quadrangle, Chile: the Talcuna and Arqueros districts

The Quebrada Marquesa Quadrangle in Chile exhibits a series of mineralizations comprising manto-type manganese and copper deposits of Lower Cretaceous age, and copper and silver veins of Tertiary age. The deposits are hosted by volcanic and volcaniclastic units of the Arqueros (Hauterivian-Barremian) and Quebrada Marquesa (Barremian-Albian) Formations. Three episodes of manganese mineralization (Mn_1-3) are recognized within the study area. Hydrothermal activity leading to episodes 1 and 3 was of minor importance, while the second one (Mn₂) gave rise to major manto-type deposits of both manganese and copper in the Talcuna mining district. Extensional faulting during Tertiary time resulted in block faulting and the unroofing of the oldest andesitic volcanics and marine sediments (Arqueros Formation). This episode was accompanied by magmatic and hydrothermal activity leading to vein formation in the Arqueros (Ag) and Talcuna (Cu) districts. The latter veins cross-cut the previous manto-type copper deposits. Ore mineralogy is similar in both styles of mineralization (manto- and vein-type) and consists mainly of chalcopyrite and bornite, with variable amounts of galena, tetrahedrite (vein-related), chalcocite, sphalerite, pyrite, hematite, digenite and covellite. Alteration processes at Talcuna can be divided into two categories, those related to the Lower Cretaceous manto-type episode (LK alteration: chlorite-epidote-calcite-albite, prehnite, zeolite), and those associated with the locally mineralized normal faults of Tertiary age (Tt alteration: chlorite-calcite, sericite). The Arqueros silver veins display an ore mineralogy consisting of arquerite, argentite, native silver, polybasite, cerargyrite and pyrargyrite-proustite; associated alteration includes strong chloritization of the country rock. The manto-type deposits formed from fluids of salinity between 11 and 19 wt.% NaCl equivalent and temperatures between 120 and 205 °C. Mineralizing fluids during the vein-type stage circulated at lower temperatures, between 70 and 170 °C, with salinity values in a wide range from 3 to 27 wt.% NaCl equivalent. This distribution of salinities is interpreted as the result of the complex interplay of two different processes: boiling and fluid mixing; the former is considered to control the major mineralogical, textural and fluid inclusion features of the vein-type deposits. We suggest that the Lower Cretaceous mineralization (manto-type stage) developed in response to widespread hydrothermal activity (geothermal field-type) involving basinal brines. Received: 18 July 1997 / Accepted: 28 January 1998     

Detrital chromites in metasediments of the East-Arabian continental margin in the Saih Hatat area: constraints for the palaeogeographic setting of the Hawasina and Semail basins (Oman Mountains)

 In Oman, the convergence between Arabia and Eurasia resulted in the Late Cretaceous overthrusting of oceanic crust and mantle lithosphere onto the Arabian continental margin. During this compressional event, a part of the continental plate was subducted to a depth of more than 60 km (0.5 GPa, 250–350  °C to more than 2.0 GPa, 550  °C) resulting in progressive metamorphism of the continental margin sediments, well exposed in the Saih Hatat tectonic window, northeastern Oman Mountains. We attempt to constrain the possibility of one continuous history of extension (starting along the east Arabian continental margin in the Permian) that was followed by one continuous history of convergence starting at 90 Ma near a dead oceanic ridge. This compression resulted in the observed progressive metamorphism by ophiolite overthrusting onto the continental margin. Constraining arguments are the palaeogeographic setting before ophiolite obduction of the As Sifah units and the Hawasina Complex near Ghurba. Detrital chromites in the Triassic–Cretaceous metasediments of the Hawasina Complex are compared with magmatic Semail chromites, and the whole-rock chemistry of these metasediments and associated metabasites are investigated. In contrast to former hypotheses, differences in the chemical composition between detrital and magmatic chromites, and the probable origin of all detrital chromites in the Hawasina Basin from Permian age oceanic rocks, suggest that the high-pressure metamorphic sediments of As Sifah can be considered as part of the basal deposits of the Hawasina Basin. Received: 1 September 1998 / Accepted: 18 January 1999     

Pleistocene recycling of copper at a porphyry system,Atacama Desert,Chile: Cu isotope evidence

We present Cu isotope data of hypogene and supergene minerals from the Late Paleocene Spence Cu-Mo porphyry in the Atacama Desert of northern Chile. Chalcopyrite displays a restricted range of δ⁶⁵Cu values within the values reported for primary porphyry Cu sulfides (+ 0.28‰ to + 0.34‰, n = 6). Supergene chalcocite samples show heavier and remarkably homogeneous δ⁶⁵Cu values, between + 3.91‰ and + 3.95‰ (n = 6), consistent with previous models of Cu leaching and enrichment in porphyry systems. Secondary Cu minerals from the oxide zone show a wider range of composition, varying from + 1.28‰ and + 1.37‰ for chrysocolla (n = 6) to very light Cu isotope signatures reported for atacamite between -5.72‰ to -6.77‰ (n = 17). These data suggest redox cycling of Cu during supergene enrichment of the Spence Cu deposit, characterized by a first stage of supergene chalcocite formation from acidic, isotopically-heavy leach fluids of meteoric origin down-flowing in a semi-arid climate (44 to ~ 15-9 Ma). Reworking of the initial supergene copper assemblage, during the Pleistocene, by rising neutral and chlorine-rich deep formation waters under well-established hyper-arid climate conditions lead to the formation of atacamite with extremely fractionated Cu compositions. Essentially coeval chrysocolla formed by dissolution of atacamite during short episodes of wetter climatic conditions occurring in the latest Pleistocene.     

Geochemistry and mineralization age of magnesian skarn-type iron deposits of the Janggun mine, Republic of Korea

The Janggun iron deposits, Republic of␣Korea, occur as lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. Mineralization stage of the deposits can be divided into two separate events. The skarn stage (107 Ma) consists of magnetite, pyrrhotite, base-metal sulfides, carbonates and magnesian skarn minerals. The hydrothermal stage (70 Ma) consists of base-metal sulfides, native bismuth, bismuthinite, tetrahedrite, boulangerite, bournonite and stannite. Mineral assemblages, chemical compositions and thermodynamic considerations indicate that formation temperatures, −log fs₂ and −log fo₂ values of ore fluids from the skarn stage were 433 to 345 °C, 8.1 to 9.7 bar and 29.4 to 31.6 bar, and the hydrothermal stage was 245 to 315 °C, 10.4 to 13.2 bar and 33.6 to 35.4 bar, respectively. Thermochemical considerations indicate that the XCO₂ during magnesian skarnization ranged from 0.06 to 0.09, and the activity of H⁺ presumably decreased when the fluids equilibrated with host dolomitic limestone which resulted in a pH change from about 6.1 to 7.8, and decreases in fo₂ and fs₂. The δ³⁴S values of ore sulfides have a wide range from 3.2 to 11.6 ‰ (CDT). Calculated ³⁴SH_{2 S} values of ore fluids are 2.9 to 5.4 ‰ (skarn stage) and 8.7 to 13.5 ‰ (hydrothermal stage). These are interpreted to represent an initial deep-seated, igneous source of sulfur which gave way to influence of oxidized sedimentary sulfur to hydrothermal stage. The δ¹³C values of carbonates in ores range from −4.6 to −2.5 ‰ (PDB). It is likely that carbon in the ore fluids was a mixture of deep-seated magmatic carbon and dissolved carbon of dolomitic limestone. The δ¹⁸OH_{2 O} and δD values (SMOW) of water in the ore fluids were 14.7 to 1.8 and −85 to −73 ‰ during the skarn stage and 11.1 to −0.2 and −87 to −80 ‰ in the hydrothermal stage. Received: 5 March 1997 / Accepted: 28 August 1997     

Volcanic domes and gold mineralization in the Pueblo Viejo district, Dominican Republic

Gold mineralization in the Pueblo Viejo district, Dominican Republic, is spatially and temporally related to a series of Early Cretaceous volcanic domes. Separate but overlapping hydrothermal cells, centered on the domes, together deposited more than 40 million oz. of gold, 240 million oz. of silver, 3 million tonnes of zinc, and 0.4 million tonnes of copper. Two principal deposits (Moore and Monte Negro) and a number of smaller deposits (Cumba, Mejita, Upper Mejita, Banco V, Arroyo Hondo I and II) have contributed ore since mining commenced in 1975. New geologic mapping has identified a series of previously unrecognized volcanic domes that vary from andesite to dacite in composition. A dacite porphyry dome intrudes epiclastic sediments in the Moore deposit and is surrounded by a baked contact metamorphic aureole. Crumble breccias of mixed epiclastic and pyroclastic origin mantle andesite domes in the Monte Negro, Cumba, and Mejita deposits. Epiclastic volcanic sediments surrounding each of the domes reflect the composition of the local source rock. Andesite domes of the Monte Negro deposit are surrounded by andesitic volcaniclastic sediments. Epiclastic sediments surrounding a dacite porphyry dome in the Moore deposit contain detrital quartz eyes and debris flows of dacite porphyry. A series of at least seven volcanic centers interfinger, overlap, and are interbedded with locally derived epiclastic sediments. Field relations indicate that volcanic dome emplacement, epiclastic sediment accumulation, hydrothermal alteration, and gold mineralization were coeval events. Domes were emplaced in a shallow subaqueous environment on the flanks of an emergent volcanic edifice. Hydrothermal cells responsible for gold mineralization are controlled by high-angle faults. These same faults influenced the emplacement of volcanic domes, an essential step in the development of gold ore in the Pueblo Viejo district. Received: 15 March 1999 / Accepted: 29 September 1999     

Metamorphism and metallogeny in the Eastern Alps

The two Alpine orogenic phases of the Eastern Alps, in the Cretaceous and in the Tertiary, were both accompanied by the formation of mineral deposits. However, subduction-related magmatic belts as well as the typical “Andean” ore deposits are missing. Therefore, the role of metamorphism in East Alpine metallogeny was tentatively explored for more than 60 y, although for a long time without tangible results. Microthermometric, geochemical and isotopic investigations of fluid inclusions from selected Alpine mineral deposits presented allow a preliminary confirmation of the involvement of metamorphic fluids in their origin. Deposits which were formed immediately after the first, Cretaceous orogeny, were produced at high pressures by fluids of very high salinity and high density, and with an isotopic composition of the water falling into the metamorphic field. These fluids are best understood as products of metamorphic de-volatilization of rocks of the subducted South Pennine domain. In contrast to this, the deposits formed after the second, Tertiary orogeny, originated at relatively low pressures from fluids with an appreciable content of CO₂ and of low to moderate salinities. Isotopic compositions of this carbon indicate a deep crustal or even mantle source for CO₂, while the water is isotopically more heterogeneous and may have mixed sources, both surficial and metamorphic. Tectonic control of these mineralizations is late-orogenic trans-tensional faulting, which exposed hot metamorphic rocks to fluid convection along brittle structures. These deposits conform best to the model of metamorphogenic metallogenesis by retrograde leaching, although ponded metamorphic fluids and mantle volatiles may also have been involved. Received: 4 August 1998 / Accepted: 5 January 1999     

BIF-hosted iron mineral system: A review

The BIF-hosted iron ore system represents the world's largest and highest grade iron ore districts and deposits. BIF, the precursor to low- and high-grade BIF hosted iron ore, consists of Archean and Paleoproterozoic Algoma-type BIF (e.g., Serra Norte iron ore district in the Carajás Mineral Province), Proterozoic Lake Superior-type BIF (e.g., deposits in the Hamersley Province and craton), and Neoproterozoic Rapitan-type BIF (e.g., the Urucum iron ore district).The BIF-hosted iron ore system is structurally controlled, mostly via km-scale normal and strike-slips fault systems, which allow large volumes of ascending and descending hydrothermal fluids to circulate during Archean or Proterozoic deformation or early extensional events. Structures are also (passively) accessed via downward flowing supergene fluids during Cenozoic times.At the depositional site the transformation of BIF to low- and high-grade iron ore is controlled by: (1) structural permeability, (2) hypogene alteration caused by ascending deep fluids (largely magmatic or basinal brines), and descending ancient meteoric water, and (3) supergene enrichment via weathering processes. Hematite- and magnetite-based iron ores include a combination of microplaty hematite–martite, microplaty hematite with little or no goethite, martite–goethite, granoblastic hematite, specular hematite and magnetite, magnetite–martite, magnetite-specular hematite and magnetite–amphibole, respectively. Goethite ores with variable amounts of hematite and magnetite are mainly encountered in the weathering zone.In most large deposits, three major hypogene and one supergene ore stages are observed: (1) silica leaching and formation of magnetite and locally carbonate, (2) oxidation of magnetite to hematite (martitisation), further dissolution of quartz and formation of carbonate, (3) further martitisation, replacement of Fe silicates by hematite, new microplaty hematite and specular hematite formation and dissolution of carbonates, and (4) replacement of magnetite and any remaining carbonate by goethite and magnetite and formation of fibrous quartz and clay minerals.Hypogene alteration of BIF and surrounding country rocks is characterised by: (1) changes in the oxide mineralogy and textures, (2) development of distinct vertical and lateral distal, intermediate and proximal alteration zones defined by distinct oxide–silicate–carbonate assemblages, and (3) mass negative reactions such as de-silicification and de-carbonatisation, which significantly increase the porosity of high-grade iron ore, or lead to volume reduction by textural collapse or layer-compaction. Supergene alteration, up to depths of 200 m, is characterised by leaching of hypogene silica and carbonates, and dissolution precipitation of the iron oxyhydroxides.Carbonates in ore stages 2 and 3 are sourced from external fluids with respect to BIF. In the case of basin-related deposits, carbon is interpreted to be derived from deposits underlying carbonate sequences, whereas in the case of greenstone belt deposits carbonate is interpreted to be of magmatic origin. There is only limited mass balance analyses conducted, but those provide evidence for variable mobilization of Fe and depletion of SiO₂. In the high-grade ore zone a volume reduction of up to 25% is observed.Mass balance calculations for proximal alteration zones in mafic wall rocks relative to least altered examples at Beebyn display enrichment in LOI, F, MgO, Ni, Fe₂O_3total, C, Zn, Cr and P₂O₅ and depletions of CaO, S, K₂O, Rb, Ba, Sr and Na₂O. The Y/Ho and Sm/Yb ratios of mineralised BIF at Windarling and Koolyanobbing reflect distinct carbonate generations derived from substantial fluid–rock reactions between hydrothermal fluids and igneous country rocks, and a chemical carbonate-inheritance preserved in supergene goethite.Hypogene and supergene fluids are paramount for the formation of high-grade BIF-hosted iron ore because of the enormous amount of: (1) warm (100–200 °C) silica-undersaturated alkaline fluids necessary to dissolve quartz in BIF, (2) oxidized fluids that cause the oxidation of magnetite to hematite, (3) weakly acid (with moderate CO₂ content) to alkaline fluids that are necessary to form widespread metasomatic carbonate, (4) carbonate-undersaturated fluids that dissolve the diagenetic and metasomatic carbonates, and (5) oxidized fluids to form hematite species in the hypogene- and supergene-enriched zone and hydroxides in the supergene zone.Four discrete end-member models for Archean and Proterozoic hypogene and supergene-only BIF hosted iron ore are proposed: (1) granite–greenstone belt hosted, strike-slip fault zone controlled Carajás-type model, sourced by early magmatic (± metamorphic) fluids and ancient “warm” meteoric water; (2) sedimentary basin, normal fault zone controlled Hamersley-type model, sourced by early basinal (± evaporitic) brines and ancient “warm” meteoric water. A variation of the latter is the metamorphosed basin model, where BIF (ore) is significantly metamorphosed and deformed during distinct orogenic events (e.g., deposits in the Quadrilátero Ferrífero and Simandou Range). It is during the orogenic event that the upgrade of BIF to medium- and high-grade hypogene iron took place; (3) sedimentary basin hosted, early graben structure controlled Urucum-type model, where glaciomarine BIF and subsequent diagenesis to very low-grade metamorphism is responsible for variable gangue leaching and hematite mineralisation. All of these hypogene iron ore models do not preclude a stage of supergene modification, including iron hydroxide mineralisation, phosphorous, and additional gangue leaching during substantial weathering in ancient or Recent times; and (4) supergene enriched BIF Capanema-type model, which comprises goethitic iron ore deposits with no evidence for deep hypogene roots. A variation of this model is ancient supergene iron ores of the Sishen-type, where blocks of BIF slumped into underlying karstic carbonate units and subsequently experienced Fe upgrade during deep lateritic weathering.     

Mobility of components in metasomatic transformation and partial melting of gneisses: an example from Sri Lanka

Reaction textures, fluid inclusions, and metasomatic zoning coupled with thermodynamic calculations have allowed us to estimate the conditions under which a biotite–hornblende gneiss from the Kurunegala district, Sri Lanka [hornblende (N_Mg=38–42) + biotite (N_Mg=42–44) + plagioclase + quartz + K-feldspar + ilmenite + magnetite] was transformed into patches of charnockite along shear zones and foliation planes. Primary fluid inclusion data suggest that two immiscible fluids, an alkalic supercritical brine and almost pure CO₂, coexisted during the charnockitisation event and subsequent post-peak metamorphic evolution of the charnockite. These metasomatic fluids migrated through the amphibolite gneiss along shear zones and into the wallrock under peak metamorphic conditions of 700–750 °C, 5–6 kbar, and a^fl _H2O=0.52–0.59. This resulted in the formation of charnockite patches containing the assemblage orthopyroxene (N_Mg=45–48) + K-feldspar (Or_70–80) + quartz + plagioclase (An₂₈) in addition to K-feldspar microveins along quartz and plagioclase grain boundaries. Remnants of the CO₂-rich fluid were trapped as separate fluid inclusions. The charnockite patches show the following metasomatic zonation patterns: – a transition zone with the assemblage biotite (N_Mg= 49–51) + hornblende (N_Mg = 47–50) + plagioclase + quartz + K-feldspar + ilmenite + magnetite; – a KPQ (K-feldspar–plagioclase–quartz) zone with the assemblage K-feldspar + plagioclase + orthopyroxene (N_Mg=45–48) + quartz + ilmenite + magnetite; – a charnockite core with the assemblage K-feldspar + plagioclase + orthopyroxene (N_Mg = 39–41) + biotite (N_Mg=48–52) + quartz + ilmenite + magnetite. Systematic changes in the bulk chemistry and mineralogy across the four zones suggest that along with metasomatic transformation, this process may have been complicated by partial melting in the charnockite core. This melting would have been coeval with metasomatic processes on the periphery of the charnockite patch. There is also good evidence in the charnockitic core that a second mineral assemblage, consisting of orthopyroxene (N_Mg= 36–42) + biotite (N_Mg=50–51) + K-feldspar (Or_70–80) + quartz + plagioclase (An_28–26), could have crystallised from a partial melt during cooling from 720 to 660 °C at decreasing a^fl _H2O from 0.67 to 0.5. Post-magmatic evolution of charnockite at T < 700 °C resulted in fluids being released during the crystallisation of the charnockitic core. These gave rise to the formation of late stage rim myrmekites along K-feldspar grain boundaries as well as late stage biotite, cummingtonite, and carbonates. Received: 15 September 1999 / Accepted: 8 June 2000     

SHRIMP U–Pb dating of the Antucoya porphyry copper deposit: new evidence for an Early Cretaceous porphyry-related metallogenic epoch in the Coastal Cordillera of northern Chile

The Antucoya porphyry copper deposit (300 Mt at 0.45% total Cu) is one of the largest deposits of a poorly known Early Cretaceous porphyry belt in the Coastal Cordillera of northern Chile. It is related to a succession of granodioritic and tonalitic porphyritic stocks and dikes that were emplaced within Jurassic andesitic rocks of the La Negra Formation immediately west of the N–S trending sinistral strike-slip Atacama Fault Zone. New zircon SHRIMP U–Pb data indicate that the porphyries of Antucoya crystallized within the time span from 142.7 ± 1.6 to 140.6 ± 1.5 Ma (±2 σ), and late, unmineralized, NW–SE trending dacite dikes with potassic alteration and internal deformation crystallized at 141.9 ± 1.4 Ma. The Antucoya porphyry copper system appears to be formed after a change of stress conditions along the magmatic arc from extensional in the Late Jurassic to transpressive during the Early Cretaceous and provides support for an Early Cretaceous metallogenic episode of porphyry-type mineralization along the Coastal Cordillera of northern Chile.     

Discriminant diagrams for iron oxide trace element fingerprinting of mineral deposit types

Magnetite and hematite are common minerals in a range of mineral deposit types. These minerals form partial to complete solid solutions with magnetite, chromite, and spinel series, and ulvospinel as a result of divalent, trivalent, and tetravalent cation substitutions. Electron microprobe analyses of minor and trace elements in magnetite and hematite from a range of mineral deposit types (iron oxide-copper-gold (IOCG), Kiruna apatite–magnetite, banded iron formation (BIF), porphyry Cu, Fe-Cu skarn, Fe-Ti, V, Cr, Ni-Cu-PGE, Cu-Zn-Pb volcanogenic massive sulfide (VMS) and Archean Au-Cu porphyry and Opemiska Cu veins) show compositional differences that can be related to deposit types, and are used to construct discriminant diagrams that separate different styles of mineralization. The Ni + Cr vs. Si + Mg diagram can be used to isolate Ni-Cu-PGE, and Cr deposits from other deposit types. Similarly, the Al/(Zn + Ca) vs. Cu/(Si + Ca) diagram can be used to separate Cu-Zn-Pb VMS deposits from other deposit types. Samples plotting outside the Ni-Cu-PGE and Cu-Zn-Pb VMS fields are discriminated using the Ni/(Cr + Mn) vs. Ti + V or Ca + Al + Mn vs. Ti + V diagrams that discriminate for IOCG, Kiruna, porphyry Cu, BIF, skarn, Fe-Ti, and V deposits.     

Origin and evolution of high-salinity, Zn–Pb mineralising fluids in the Variscides of Belgium

High-salinity, Na–Ca–Cl-rich fluids (˜20 wt% salts) in inclusions in gangue and ore minerals from Mesozoic Mississippi Valley-type (MVT) deposits in the Verviers Synclinorium (eastern Belgium) and in Cretaceous vein calcites at the Variscan front were investigated by microthermometric and crush-leach analysis. The MVT deposits formed at temperatures of ˜110 °C while the Cretaceous vein calcites were precipitated at temperatures <50 °C. Their Cl–Br content (Cl/Br ratio between 246 and 458) suggests that the fluids probably originated by the evaporation of seawater during basin development at the southern margin of the Caledonian Brabant Massif in the Late Palaeozoic. The Na–Ca–K content (Na: 29,700–49,600 ppm, Ca: 25,700–46,200 ppm, K: 1,000–5,620 ppm) is similar to that of the mineralising fluids in other Pb–Zn districts, interpreted to be of evaporative origin (e.g. Newfoundland, East Tennessee, Polaris). Furthermore, comparison of the Na–Ca–K content of the fluids with that of an evolved evaporitic brine enables the recognition of major water–rock interactions that modified the fluid composition. It indicates that the ambient fluids participated in the early diagenetic dolomitisation of Upper Palaeozoic carbonates and also in the albitisation of plagioclase in Lower Palaeozoic siliciclastics of the Caledonian basement. Illitisation of smectites or dissolution of K-feldspar probably controlled the K-content of the fluids. A model is proposed where the bittern brines migrated down into the deep subsurface because of their density during extension. After the Variscan orogeny, these fluids were finally expelled along extensional faults, resulting in the formation of Zn–Pb deposits. Received: 26 April 2000 / Accepted: 22 November 2000     

An experimental investigation on diffusion of water in haplogranitic melts

  The diffusivity of water has been investigated for a haplogranitic melt of anhydrous composition Qz₂₈Ab₃₈Or₃₄ (in wt %) at temperatures of 800–1200°C and at pressures of 0.5–5.0 kbar using the diffusion couple technique. Water contents of the starting glass pairs varied between 0 and 9 wt %. Concentration-distance profiles for the different water species (molecular water and hydroxyl groups) were determined by near-infrared microspectroscopy. Because the water speciation of the melt is not quenchable (Nowak 1995; Nowak and Behrens 1995; Shen and Keppler 1995), the diffusivities of the individual species can not be evaluated directly from these profiles. Therefore, apparent chemical diffusion coefficients of water (D _water) were determined from the total water profiles using a modified Boltzmann-Matano analysis. The diffusivity of water increases linearly with water content <3 wt % but exponentially at higher water contents. The activation energy decreases from 64 ± 10 kJ/mole for 0.5 wt % water to 46 ± 5 kJ/mole for 4 wt % water but remains constant at higher water contents. A small but systematic decrease of D _water with pressure indicates an average activation volume of about 9 cm³/mole. The diffusivity (in cm²/s) can be calculated for given water content (in wt %), T (in K) and P (in kbar) by

Genesis of superimposed hypogene and supergene Fe orebodies in BIF at the Madoonga deposit, Yilgarn Craton, Western Australia

The Madoonga iron ore body hosted by banded iron formation (BIF) in the Weld Range greenstone belt of Western Australia is a blend of four genetically and compositionally distinct types of high-grade (>55 wt% Fe) iron ore that includes: (1) hypogene magnetite–talc veins, (2) hypogene specular hematite–quartz veins, (3) supergene goethite–hematite, and (4) supergene-modified, goethite–hematite-rich detrital ores. The spatial coincidence of these different ore types is a major factor controlling the overall size of the Madoonga ore body, but results in a compositionally heterogeneous ore deposit. Hypogene magnetite–talc veins that are up to 3 m thick and 50 m long formed within mylonite and shear zones located along the limbs of isoclinal, recumbent F₁ folds. Relative to least-altered BIF, the magnetite–talc veins are enriched in Fe₂O_3(total), P₂O₅, MgO, Sc, Ga, Al₂O₃, Cl, and Zr; and depleted in SiO₂ and MnO₂. Mafic igneous countryrocks located within 10 m of the northern contact of the mineralised BIF display the replacement of primary igneous amphibole and plagioclase, and metamorphic chlorite by hypogene ferroan chlorite, talc, and magnetite. Later-forming, hypogene specular hematite–quartz veins and their associated alteration halos partly replace magnetite–talc veins in BIF and formed during, to shortly after, the F₂-folding and tilting of the Weld Range tectono-stratigraphy. Supergene goethite–hematite ore zones that are up to 150 m wide, 400 m long, and extend to depths of 300 m replace least-altered BIF and existing hypogene alteration zones. The supergene ore zones formed as a result of the circulation of surface oxidised fluids through late NNW- to NNE-trending, subvertical brittle faults. Flat-lying, supergene goethite–hematite-altered, detrital sediments are concentrated in a paleo-topographic depression along the southern side of the main ENE-trending ridge at Madoonga. Iron ore deposits of the Weld Range greenstone belt record remarkably similar deformation histories, overprinting hypogene alteration events, and high-grade Fe ore types to other Fe ore deposits in the wider Yilgarn Craton (e.g. Koolyanobbing and Windarling deposits) despite these Fe camps being presently located more than 400 km apart and in different tectono-stratigraphic domains. Rather than the existence of a synchronous, Yilgarn-wide, Fe mineralisation event affecting BIF throughout the Yilgarn, it is more likely that these geographically isolated Fe ore districts experienced similar tectonic histories, whereby hypogene fluids were sourced from commonly available fluid reservoirs (e.g. metamorphic, magmatic, or both) and channelled along evolving structures during progressive deformation, resulting in several generations of Fe ore.     

Implications from inclusions in topaz for greisenisation and mineralisation in the Hensbarrow topaz granite, Cornwall, England

Textural and geochemical studies of inclusions in topaz from greisens in the Hensbarrow topaz granite stock (St. Austell, Cornwall) are used to constrain the composition of fluids responsible for late stage greisening and mineralisation. The topaz contains an abundant and varied suite of inclusions including aqueous liquid + vapour (L + V), quartz, zinnwaldite, albite, K-feldspar, muscovite, ilmenorutile, apatite, columbite, zircon, varlamoffite [(Sn, Fe)(O, OH)₂] and qitianlingite [(Fe⁺²,Mn⁺²)₂(Nb,Ta)₂W⁺⁶O₁₀]. Primary L + V inclusions in topaz show relatively high T _h (mainly 300 to >500 °C) and a narrow range of salinities (23–30 wt % NaCl equivalent) compared with those in greisen quartz (150–450 °C, 0–50 wt % NaCl equivalent). Textures indicate that topaz formed earlier than quartz and the fluid inclusion data are interpreted as indicating a cooling of the hydrothermal fluids during greisenisation, mixing with meteoric waters and a decrease in pressure causing intermittent boiling. The presence of early-formed albite and K-feldspar as inclusions in the topaz is likely to indicate that the greisen-forming fluid became progressively more acid during greisenisation. The most distinctive inclusions in the topaz are wisp- and bleb-shaped quartz, < 50 μm in size, which show textural characteristics indicating former high degrees of plasticity. They often have multiple shrinkage bubbles at their margins rich in Sn, Fe, Mn, S and Cl and, more rarely, contain euhedral albite, K-feldspar, stannite or pyrrhotite crystals up to 40 μm in size. The quartz inclusions show similar morphologies to inclusions in topaz from quartz-topaz rocks elsewhere which have been interpreted as trapped “silicate melt”. Their compositions are, however, very different to those expected for late stage topaz-normative granitic melts. From their textural and chemical characteristics they are interpreted as representing crystallised silica colloid, probably trapped as a hydro gel during greisenisation. There is also evidence for the colloidal origin of inclusions of varlamoffite in the topaz. These occurrences offer the first reported evidence in natural systems for the formation of colloids in high temperature hydrothermal fluids. Their high ore carrying potential is suggested by the presence of varlamoffite and the occurrence of stannite, pyrrhotite and SnCl within the quartz inclusions. Received: 9 April 1996 / Accepted: 12 November 1996     

Hydrothermal origin for the 2 billion year old Mount Tom Price giant iron ore deposit, Hamersley Province, Western Australia

Giant iron-ore deposits, such as those in the Hamersley Province of northwestern Australia, may contain more than a billion tonnes of almost pure iron oxides and are the world's major source of iron. It is generally accepted that these deposits result from supergene oxidation of host banded iron formation (BIF), accompanied by leaching of silicate and carbonate minerals. New textural evidence however, shows that formation of iron ore at one of those deposits, Mount Tom Price, involved initial high temperature crystallisation of magnetite-siderite-iron silicate assemblages. This was followed by development of hematite- and ferroan dolomite-bearing assemblages with subsequent oxidation of magnetite, leaching of carbonates and silicates and crystallisation of further hematite. Preliminary fluid inclusion studies indicate both low and high salinity aqueous fluids as well as complex salt-rich inclusions with the range of fluid types most likely reflecting interaction of hydrothermal brines with descending meteoric fluids. Initial hematite crystallisation occurred at about 250 °C and high fluid pressures and continued as temperatures decreased. Although the largely hydrothermal origin for mineralisation at Mount Tom Price is in conflict with previously proposed supergene models, it remains consistent with interpretations that the biosphere contained significant oxygen at the time of mineralisation. Received: 16 February 1999 / Accepted: 14 May 1999     

Geochemistry of the kaolin deposits of Swat (Pakistan)

Kaolin deposits of the Swat District in Pakistan are indicated to have derived by hydrothermal alteration of more feldspathic parts of felsic intrusives, which occur enclosed in orthoamphibolites and orthogneisses of the Cretaceous Kohistan Island Arc terrane. These latter “country rocks” formed under epidote–amphibolite conditions that prograde northwards to amphibolite facies, and locally manifest slight metamorphic differentiation. The felsic intrusives exhibit a general decrease in siliceous character from west to east, but are less siliceous than most hosts of world kaolins. They are composed of chemically allied quartz diorite, tonalite, trondhjemite and pegmatoids, which evolved mainly by an orthomagmatic crystal fractionation. These parental rocks are calc-alkaline in nature, and kaolinization has proceeded in Ca-richer environment. This is in variance with the occurrence of most known kaolin deposits over potassic granites or rhyolites. Ca-metasomatism of the “host rocks” is in evidence. Kaolin formation by a supergene process is not displayed.The raw kaolin with contained unaltered plagioclase is characterized by a rather low silica (46.54–50.93%) and potash (<1%), and high alumina (23.54–26.77%), Fe₂O₃ (1.73–5.45%) and lime (8.13–16.93%) content. Kaolinization proceeded with a decrease in SiO₂ and concomitant increase in Al₂O₃. The same trend is followed with fineness of grain size of washed fractions, in resemblance to other known kaolin deposits of primary as well as secondary origin.     

The crystal chemistry of roméite

Roméite (Ca, Fe, Mn, Na)₂(Sb⁵⁺, Ti⁴⁺)₂(O, OH, F)₇ is a rare mineral found in metamorphic iron-manganese deposits and in hydrothermal Sb-bearing veins. It is isostructural with the pyrochlore-group minerals of the general formula A_2–mB₂X_6–wY_1–n · pH₂O. The pyrochlore-group minerals are important Nb and Ta ores, and are also used as an actinide host phase in␣radioactive waste. The crystal chemistry of roméite from the type locality Praborna (Italy), from Massiac (France), and from four newly discovered localities in␣the Swiss Alps, and of “lewisite”, a questionable species related to roméite from Tripuhy (Brazil), is compared to that of pyrochlore. A wide range of substitutions has been observed including (1) independent substitutions on the A- and B-sites, and (2) coupled substitutions between the A- and B- and between the A- and Y- sites. Only the roméite from Massiac, derived from weathering of stibnite, contains significant H₂O (up to 14 wt %). The A-site vacancies in roméite appear to be controlled by the primary conditions of crystallization, and not by post-crystallization alteration. The Y-site chemistry of roméite varies from locality to locality; it can be dominated by F, OH, or be fully vacant. The “lewisite” octahedral crystals studied are a sub-microscopic mixture of roméite with a mineral structurally related to pyrochlore, which grows at the expense of roméite. Received: 5 March 1996 / Accepted: 18 October 1996     

An experimental investigation on the P-T stability of Mg-staurolite in the system MgO-Al2O3-SiO2-H2O

The pressure-temperature stability field of Mg-staurolite, ideally Mg₄Al₁₈Si₈O₄₆(OH)₂, was bracketed for six possible breakdown reactions in the system MgO-Al₂O₃-SiO₂-H₂O (MASH). Mg-staurolite is stable at water pressures between 12 and 66 kbar and temperatures of 608–918 °C, requiring linear geotherms between 3 and 18 °C/km. This phase occurs in rocks that were metamorphosed at high-pressure, low-temperature conditions, e.g. in subducted crustal material, provided they are of appropriate chemical composition. Mg-staurolite is formed from the assemblage chlorite + kyanite + corundum at pressures <24 kbar, whereas at pressures up to 27 kbar staurolite becomes stable by the breakdown of the assemblage Mg-chloritoid + kyanite + corundum. Beyond 27 kbar the reaction Mg-chloritoid + kyanite + diaspore = Mg-staurolite + vapour limits the staurolite field on its low-temperature side. The upper pressure limit of Mg-staurolite is marked by alternative assemblages containing pyrope + topaz-OH with either corundum or diaspore. At higher temperatures Mg-staurolite breaks down by complete dehydration to pyrope + kyanite + corundum and at pressures below 14 kbar to enstatite + kyanite + corundum. The reaction curve Mg-staurolite = talc + kyanite + corundum marks the low-pressure stability of staurolite at 12 kbar. Mg-staurolite does not coexist with quartz because alternative assemblages such as chlorite-kyanite, enstatite-kyanite, talc-kyanite, pyrope-kyanite, and MgMgAl-pumpellyite-kyanite are stable over the entire field of Mg-staurolite. Received: 16 April 1997 / Accepted: 24 September 1997