Mineralogical and geochemical characterization of the Riópar non-sulfide Zn-(Fe-Pb) deposits (Prebetic Zone,SE Spain)

The present paper reports the first detailed petrological and geochemical study of non-sulfide Zn–(FePb) deposits in the Riópar area (Prebetic Zone of the Mesozoic Betic Basin, SE Spain), constraining the origin and evolution of ore-forming fluids. In Riópar both sulfide and non-sulfide Zn–(FePb) (“calamine”) ores are hosted in hydrothermally dolomitized Lower Cretaceous limestones. The hypogene sulfides comprise sphalerite, marcasite and minor galena. Calamine ores consist of Zn-carbonates (smithsonite and scarce hydrozincite), associated with abundant Fe-(hydr)oxides (goethite and hematite) and minor Pb-carbonates (cerussite). Three smithsonite types have been recognized: i) Sm-I consists of brown anhedral microcrystalline aggregates as encrustations replacing sphalerite; ii) Sm-II refers to brownish subhedral aggregates of rugged appearance related with Fe oxi-hydroxides in the surface crystals, which replace extensively sphalerite; and iii) Sm-III smithsonite appears as coarse grayish botryoidal aggregates in microkarstic cavities and porosity. Hydrozincite is scarce and appears as milky white botryoidal encrustations in cavities replacing smithsonite. Also, two types of cerussite have been identified: i) Cer-I cerussite consists of fine crystals replacing galena along cleavage planes and crystal surfaces; and ii) Cer-II conforms fine botryoidal crystals found infill porosity. Calcite and thin gypsum encrustations were also recognized. The field and petrographic observations of the Riópar non-sulfide Zn–(FePb) revealed two successive stages of supergene ore formation under meteoric fluid processes: i) “gossan” and “red calamine” formation in the uppermost parts of the ore with deposition of Fe-(hydr)oxides and Zn- and Pb-carbonates (Sm-I, Sm-II and Cer-I), occurring as direct replacements of ZnPb sulfides; and ii) “gray calamine” ore formation with deposition of Sm-III, Cer-II and hydrozincite infilling microkarst cavities and porosity. The stable isotope variation of Riópar smithsonite is very similar to those obtained in other calamine-ore deposits around the world. Their CO isotope data (δ¹⁸O: + 27.8 to + 29.6‰ V-SMOW; δ¹³C: − 6.3 to + 0.4‰ V-PDB), puts constrains on: i) the oxidizing fluid type, which was of meteoric origin with temperatures of 12 to 19 °C, suggesting a supergene weathering process for the calamine-ore formation under a temperate climate; and ii) the carbon source, that resulted from mixing between two CO₂ components derived from: the dissolution of host-dolomite (¹³C-enriched source) and vegetation decomposition (¹³C-depleted component).     

The Hakkari nonsulfide Zn–Pb deposit in the context of other nonsulfide Zn–Pb deposits in the Tethyan Metallogenic Belt of Turkey

The Hakkari nonsulfide zinc deposit is situated close to the southeastern border of Turkey. Here both sulfide and nonsulfide Zn ≫ Pb ores are hosted in carbonate rocks of the Jurassic Cudi Group with features typical of carbonate-hosted supergene nonsulfide zinc mineralization. The regional strike extent of the mineralized district is at least 60 km. The age of the supergene deposit has not been determined, but it is probable that the main weathering happened during Upper Tertiary, possibly between Upper Miocene and Lower Pliocene. The Hakkari mineralization can be compared to other carbonate-hosted Zn–Pb deposits in Turkey, and an interpretation made of its geological setting. The zinc mineral association at Hakkari typically comprises smithsonite and hemimorphite, which apparently replace both sulfide minerals and carbonate host rock. Two generations of smithsonite are present: the first is relatively massive, the second occurs as concretions in cavities as a final filling of remnant porosity. Some zinc is also hosted within Fe–Mn-(hydr)oxides. Lead is present in cerussite, but also as partially oxidized galena. Lead can also occur in Mn-(hydr)oxides (max 30% PbO). The features of the supergene mineralization suggest that the Hakkari deposit belongs both to the “direct replacement” and the “wall-rock replacement” types of nonsulfide ores. Mineralization varies in style from tabular bodies of variable thickness (< 0.5 to 13 m) to cross-cutting breccia zones and disseminated ore minerals in pore spaces and fracture planes. At Hakkari a As–Sb–Tl(≫ Hg) geochemical association has been detected, which may point to primary sulfide mineralization, quite different from typical MVT.     

A review of major non-sulfide zinc deposits in Iran

The numerous non-sulfide zinc ore deposits were the historical basis for the development of zinc mining in Iran.They include the Mehdiabad,Irankouh and Angouran world-class deposits,as well as the Zarigan and Haft-har deposits.These deposits were formed by supergene oxidation of primary sulfide minerals during the complex interplay of tectonic uplift,karst development,changes in the level of the water table,and weathering.Zn(Pb)carbonates,Zn-hydrosilicates and associated hydrated phases directly replace the primary ore bodies or fill cavities along fractures related to uplift tectonics.Direct replacement of primary sulfides is accompanied by distal precipitation of zinc non-sulfide minerals in cavities or internal sediments filling.The mineralogy of the non-sulfide mineralization in all six deposits is generally complex and consists of smithsonite,hydrozincite,and hemimorphite as the main economic minerals,accompanied by iron and manganese oxy-hydroxides and residual clays.Commonly,non-sulfide minerals in these deposits consist of two types of ore:red zinc ore(RZO),rich in Zn,Fe,Pb-(As)and white zinc ore(WZO),typically with very high zinc grades but low concentrations of iron and lead.Typical minerals of the RZO are Fe-oxyhydroxides,goethite,hematite,hemimorphite,smithsonite and/or hydrozincite and cerussite.Common minerals of the WZO are smithsonite or hydrozincite and only minor amounts of Fe-oxyhydroxides and hemimorphite.     

Mineralization age and geodynamic background for the Shangjiazhuang Mo deposit in the Jiaodong gold province,China

The Shangjiazhuang Mo deposit is located on the Jiaodong Peninsula in eastern China, which is famous for the ca. 120 Ma “Jiaodong-type” Au deposits with total Au endowment of over 3000 t. In this paper, we discuss the deposit geology, mineralization age, and geochemical features of the host granodiorite of the Shangjiazhuang Mo orebody. Using this information, we aim to clarify the time and geodynamic mechanism for the Mo deposit, which is another constraint to understand the genesis of Au deposits. The Mo mineralization generally occurs as quartz–sulfide veins within the medium-grained Yashan granodiorite. The alteration consists of potassic alteration, silicification, sericitization, chloritization, and carbonatization with a weak unclear zonation. The ore minerals mainly include molybdenite, chalcopyrite, and pyrite. We measured Re–Os isotopes of molybdenite grains, which yielded a weighted mean model age of 116.9 ± 0.81 (MSWD = 1.03) and a well-constrained ¹⁸⁷Re–¹⁸⁷Os isochron age of 117.1 ± 1.4 Ma (MSWD = 1.6). These ages are slightly younger than the age of Au mineralization on the Jiaodong Peninsula. Rhenium contents of 5.84–29.99 ppm with an average of 16.4 ppm in molybdenites indicate a crustal source. Whole-rock geochemical compositions show that the granodiorite is high-K calc-alkaline and metaluminous to peraluminous. The samples show low Y contents from 8.2 to 10.5 ppm and Sr/Y ratios from 48.2 to 58.8, displaying an adakitic affinity. The Yashan granodiorite has high initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7101 to 0.7104, low ε_Nd(t) values of − 17.6 to − 16.7, and zircon ε_Hf(t) values from − 24.8 to − 17.1, with corresponding Hf model ages of 2.7 to 2.2 Ga. These isotopic data, together with the adakitic affinity of the granodiorite, indicate that the parental magma was derived from ancient crust. Mafic microgranular enclaves (MME) that are contemporaneous with the host granodiorite show SiO₂ contents of 57.98–58.41 wt% and depletion in Nb–Ta. The MMEs show enriched initial ⁸⁷Sr/⁸⁶Sr ratios of 0.7102 to 0.7106 and low ε_Nd(t) values of − 17.3 to − 16.3. The MMEs are the products of mixing between the metasomatized lithospheric mantle-derived mafic magma and the ancient crust-derived felsic magma. The Early Cretaceous Mo mineralization (120–110 Ma) is slightly younger than the peak time of Au mineralization (126–120 Ma) on the Jiaodong Peninsula, but have a different spatial distribution which suggests different sources of Au and Mo. The “Jiaodong-type” Au deposits were probably related to the upwelling of metasomatized lithospheric mantle, while the Mo mineralization on the Jiaodong Peninsula may delineate a 120–110 Ma Mo metallogenic belt along the southern margin of the North China Craton with the East Qinling, which is related to the melting of ancient crustal sources. The subduction of the Paleo-Pacific slab and accompanying asthenospheric upwelling triggered upwelling of metasomatized lithospheric mantle, forming “Jiaodong-type” Au deposits. Subsequently, the ponding of mantle-derived magmas resulted in partial melting of ancient crust and associated Mo deposits.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Geochemical constraints on Cu–Fe and Fe skarn deposits in the Edong district,Middle–Lower Yangtze River metallogenic belt,China

Copper and iron skarn deposits are economically important types of skarn deposits throughout the world, especially in China, but the differences between Cu and Fe skarn deposits are poorly constrained. The Edong ore district in southeastern Hubei Province, Middle–Lower Yangtze River metallogenic belt, China, contains numerous Fe and Cu–Fe skarn deposits. In this contribution, variations in skarn mineralogy, mineralization-related intrusions and sulfur isotope values between these Cu–Fe and Fe skarn deposits are discussed.The garnets and pyroxenes of the Cu–Fe and Fe skarn deposits in the Edong ore district share similar compositions, i.e., dominantly andradite (Ad_29–100Gr_0–68) and diopside (Di_54–100Hd_0–38), respectively. This feature indicates that the mineral compositions of skarn silicate mineral assemblages were not the critical controlling factors for variations between the Cu–Fe and Fe skarn deposits. Intrusions associated with skarn Fe deposits in the Edong ore district differ from those Cu–Fe skarn deposits in petrology, geochemistry and Sr–Nd isotope. Intrusions associated with Fe deposits have large variations in their (La/Yb)_N ratios (3.84–24.6) and Eu anomalies (δEu = 0.32–1.65), and have relatively low Sr/Y ratios (4.2–44.0) and high Yb contents (1.20–11.8 ppm), as well as radiogenic Sr–Nd isotopes (εNd(t) = − 12.5 to − 9.2) and (⁸⁷Sr/⁸⁶Sr)_i = 0.7067 to 0.7086. In contrast, intrusions associated with Cu–Fe deposits are characterized by relatively high Sr/Y (35.0–81.3) and (La/Yb)_N (15.0–31.6) ratios, low Yb contents (1.00–1.62 ppm) without obvious Eu anomalies (δEu = 0.67–0.97), as well as (⁸⁷Sr/⁸⁶Sr)_i = 0.7055 to 0.7068 and εNd(t) = − 7.9 to − 3.4. Geochemical evidence indicates a greater contribution from the crust in intrusions associated with Fe skarn deposits than in intrusions associated with Cu–Fe skarn deposits. In the Edong ore district, the sulfides and sulfates in the Cu–Fe skarn deposits have sulfur isotope signatures that differ from those of Fe skarn deposits. The Cu–Fe skarn deposits have a narrow range of δ³⁴S values from − 6.2‰ to + 8.7‰ in sulfides, and + 13.2‰ to + 15.2‰ in anhydrite, while the Fe skarn deposits have a wide range of δ³⁴S values from + 10.3‰ to + 20.0‰ in pyrite and + 18.9‰ to + 30.8‰ in anhydrite. Sulfur isotope data for anhydrite and sedimentary country rocks suggest that the formation of skarns in the Edong district involved the interaction between magmatic fluids and variable amounts of evaporites in host rocks.     

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.     

Nakhlak carbonate-hosted Pb(Ag) deposit,Isfahan province,Iran: a geological,mineralogical, geochemical,fluid inclusion,and sulfur isotope study

The Upper Cretaceous Nakhlak epigenetic vein-type Pb(Ag) deposit is located 55 km northeast of the town of Anarak in Isfahan Province, Iran. The deposit contains 7 Mt of galena-barite ore with an average grade of 8.33% Pb, 0.38% Zn, and 72 ppm Ag. The ore mineralization occurs as stratabound, epigenetic, steeply dipping, east-west–trending veins in faulted- or fracture-controlled Upper Cretaceous Sadar carbonates. Galena and barite are the primary minerals. Minor sphalerite, tennantite-tetrahedrite, pyrite, and chalcopyrite occur as inclusions in galena. Cerussite with minor amounts of anglesite and plattnerite formed in the oxidized supergene zone. The ore and ore-related minerals were deposited in the hydrothermally dolomitized carbonate host rock containing saddle-shaped dolomite. Geochemically, the dolomitized carbonate host rocks are enriched in MgO, Fe₂O₃, MnO, Pb, Zn, and Ba, but depleted in CaO. The galena concentrate contains high values of Ag (932 ppm), Sb (342 ppm), Cu (422 ppm), As (91 ppm), and Zn (296 ppm); the presence of these trace elements indicates a low-temperature type of galena mineralization. This interpretation is corroborated by fluid inclusions containing 12.98 wt.% NaCl equivalent salinity; the inclusions homogenize at the low temperature of about 152.1 °C. The similarity between δ³⁴S_(V-CDT) values in Nakhlak barite and Permian–Triassic δ³⁴S marine sulfate values indicates that the Nakhlak sulfur was probably provided from evaporates of Permian–Triassic age. The δ³⁴S_(V-CDT) values of galena and barite samples occupy the ranges of − 1.04‰ to + 8.62‰ and + 10.95‰ to + 13.71‰, respectively, and are similar to Mississippi Valley–type (MVT) deposits. The low-temperature basinal fluids, evaporate-originated sulfur, and fault- or fracture-controlled galena-rich veins in the Nakhlak deposit resemble the type of geological features documented in Pb-rich MVT deposits.     

Likely “mantle plume” activity in the Skellefte district,Northern Sweden. A reexamination of mafic/ultramafic magmatic activity: Its possible association with VMS and gold mineralization

Most attention has been given to the geology of the extensive VMS and subordinate precious metals mineralization in the Skellefte district. Less attention has been given to indications of deep-seated origins of felsic and mafic/ultramafic volcanic rocks; of VMS and precious metals mineralizing fluids; and the primary origins of these metals. A holistic view of the significance of mafic/ultramafic volcanic rocks to both the geotectonic evolution of the area and the existence of its important base and precious metals deposits has never been presented. These subjects are discussed in this investigation.Primitive mantle normalized spider diagrams of rare-earth-elements (REE) distinguish two groups of mafic/ultramafic volcanic rocks, each with distinct geochemical characteristics: a mid-ocean-ridge “MORB”-type, and a geochemically unusual and problematic calc–alkaline–basalt “CAB”-type which is the main subject of this investigation. The “MORB”-type mafic volcanic rocks are mostly older than the Skellefte Group felsic volcanic rocks hosting the VMS deposits, whereas the more primitive “CAB”-type mafic/ultramafic volcanic rocks are mostly younger.A common source for these “CAB”-type, mafic-(MgO wt.% < 14%) and ultramafic-(MgO wt.% > 14%) volcanic rocks is suggested by their similar and distinctive geochemical features. These are near-chondritic (Al-undepleted) Al₂O₃/TiO₂ ratios; moderate to strong high-field-strength-element (HFSE) depletion; light-rare-earth-element (LREE) enrichment and moderate heavy-rare-earth-element (HREE) depletion. They outcrop throughout an area of at least 100 × 100 km. Gold mineralization is spatially associated with ultramafic volcanic rocks.Zr and Hf depletion has been shown to be associated with Al-depletion in mafic/ultramafic volcanic rocks elsewhere, and has been attributed to deep-seated partial melting in ascending mantle plumes. Zr and Hf depletion in “CAB”-type Al-undepleted mafic/ultramafic volcanic rocks is therefore unusual. The solution to this dilemma is suggested to be contamination of an Al-depleted mantle plume by felsic crustal rocks whereby Al-depleted ultramafic magmas become Al-undepleted. It will be argued that this model has the potential to explain previous observations of deep-seated origins; the spatial association of ultramafic volcanic rocks with occurrences of gold mineralization; and even the primary origin of metals in VMS deposits.     

Re–Os isochron ages for arsenopyrite from Carlin-like gold deposits in the Yunnan–Guizhou–Guangxi “golden triangle”, southwestern China

The Yunnan–Guizhou–Guangxi “golden triangle” is considered to be one of the regions hosting Carlin-like gold deposits in China. Gold deposits in this region can be grouped into lode type that are controlled by faults and layer-like type controlled by stratigraphy. Arsenopyrite is one of the major gold-bearing minerals in these deposits. Rhenium–Os isotopic dating of arsenopyrite from the lode type Lannigou and Jinya and the layer-like type Shuiyindong gold deposits yields isochron ages of 204 ± 19 Ma, 206 ± 22 Ma, and 235 ± 33 Ma, respectively. The data suggest that the Carlin-like gold deposits formed in Late Triassic to Early Jurassic, which is clearly earlier than the ca. 100–80 Ma acid to ultra-basic magmatism in this part of southwestern China. The ages are consistent with ore formation during a period of post-collisional lateral transpression, which is similar to that of the Carlin-like gold deposits in western Qinling of China, but quite different from Carlin-type gold deposits in Nevada, U.S.A.     

REE and isotope (Sr,S, and Pb) geochemistry to constrain the genesis and timing of the F–(Ba–Pb–Zn) ores of the Zaghouan District (NE Tunisia)

The F–(Ba–Pb–Zn) ore deposits of the Zaghouan District, located in NE Tunisia, occur as open space fillings or stratabound orebodies, hosted in Jurassic, Cretaceous and Tertiary layers. The chondrite-normalized rare earth element (REE) patterns may be split into three groups: (i) “Normal marine” patterns characterizing the wallrock carbonates; (ii) light REE (LREE) enriched (slide-shaped) patterns with respect to heavy REE (HREE), with small negative Ce and Eu anomalies, characteristic of the early ore stages; (iii) Bell-shaped REE patterns displaying LREE depletion, as well as weak negative Ce and Eu anomalies, characterizing residual fluids of subsequent stages. The ⁸⁷Sr/⁸⁶Sr ratios (0.707654–0.708127 ± 8), show that the Sr of the epigenetic carbonates (dolomite, calcite) and ore minerals (fluorite, celestite) are more radiogenic than those of the country (Triassic, Jurassic, Cretaceous, lower Miocene) sedimentary rocks. The uniformity of this ratio, throughout the District, provides evidence for the isotopic homogeneity and, consequently, the identity of the source of the mineralizing fluids. This signature strongly suggests that the radiogenic Sr is carried by Upper Paleozoic basinal fluids.The δ³⁴S values of barite, associated to mineralizations, are close to those of the Triassic sea water (17‰). The δ³⁴S values of sulfide minerals range from − 13.6‰ to + 11.4‰, suggesting two sulfur-reduced end members (BSR/TSR) with a dominant BSR process.Taking account of the homogeneity in the Pb-isotope composition of galenas (18.833–18.954 ± 0.001, 15.679–15.700 ± 0.001 and 38.690–38.880 ± 0.004, for the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios respectively), a single upper crustal source for base-metals is accepted. The Late Paleozoic basement seems to be the more plausible source for F–Pb–Zn concentrated in the deposits. The genesis of the Zaghouan District ore deposits is considered as the result of the Zaghouan Fault reactivation during the Late Miocene period.     

Formation of carbon nano-balls and carbon nano-tubes from northeast Indian Tertiary coal: Value added products from low grade coal

The paper reports the presence of carbon nano-balls and nano-tubes in the clean coal product during our experiments on desulfurization and deashing of northeast Indian high-sulfur Tertiary coal by molten caustic leaching (MCL) method. The Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HR-TEM), X-ray Diffraction (XRD), Raman and Fourier Transform Infrared (FT-IR) spectroscopy analyses revealed the formation of varied sizes of carbon nanomaterials in the clean coal product (MCL product). The nano-balls are in the range of 5–10 nm with nominal areas in the range of 40–100 nm², 160–220 nm², and 550–650 nm². The diameters of the carbon nano-tubes (CNTs) formed are in the range of 18–24 nm. The diameters of the branch carbon nano-tubes (BCNTs) are in the range of 35–92 nm. It is further observed that the alkaline treatment followed by acid treatment favored the formation of the carbon nano-balls, carbon nano-tubes (CNTs), and branch carbon nanotubes (BCNTs) in the coal product. The low-grade coals could also be used for the preparation of nano-carbon-based high value added products.     

The trinity pattern of Au deposits with porphyry,quartz–sulfide vein and structurally-controlled alteration rocks in Ciemas,West Java,Indonesia

The Ciemas gold mining area is located in the Sunda arc volcanic rock belt, West Java, Indonesia. Ore bodies are associated with Miocene andesite, dacite and quartz diorite porphyrite. To constrain ore genesis and mineralization significance, a detailed study was recently conducted examining these deposits, which included detailed field observation, petrographic study, petrochemistry, sulfur isotope analyses, zircon U–Pb dating, and fluid inclusion analysis. The results include the following findings. 1) Ore types have been identified as porphyry, a quartz–sulfide vein, and structure-controlled alteration rocks. 2) In host rocks, zircon LA–ICP-MS U–Pb dating of quartz diorite porphyrite, amphibole tuff breccia and andesite yield ages of 17.1 ± 0.4 Ma, 17.1 ± 0.4 Ma and 17.5 ± 0.3 Ma, respectively. 3) Fluid inclusions in the quartz from ore are given priority to liquid and gas–liquid phases, and their components are of the NaCl–H₂O system with homogenization temperatures of 240–320 °C, salinities of 14–17%, densities of 0.85–0.95 g/cm³, and fluid pressure values between 4.1 and 46.8 MPa, corresponding to metallogenic depths from 150 to 1730 m. Fluid characteristics are identified as similar to those of high sulfur epithermal deposits. 4) The sulfur isotopic compositions are notably uniform, the δ³⁴S values of wall rocks range from 3.71 to 3.85‰, and the δ³⁴S values of ores vary from 4.90‰ to 6.55‰. The sulfur isotopic composition of ores is similar to that of the wall rocks, indicating a mixed origin of mantle with a sedimentary basement. 5) The trace element patterns of different ore types are similar, which indicates that they originate from the same source. Au deposits primarily occurred during the late magmatic activity. Finally, we have set up the regional metallogenic model, confirming that this gold deposit in the Sunda arc volcanic rock belt belongs to a metallogenic system from porphyry to epithermal type.     

Magnetite geochemistry of the Longqiao and Tieshan Fe–(Cu) deposits in the Middle-Lower Yangtze River Belt: Implications for deposit type and ore genesis

Magnetite is a common mineral in many ore deposits and their host rocks, and contains a wide range of trace elements (e.g., Ti, V, Mg, Cr, Mn, Ca, Al, Ni, Ga, Sn) that can be used for deposit type fingerprinting. In this study, we present new magnetite geochemical data for the Longqiao Fe deposit (Luzong ore district) and Tieshan Fe–(Cu) deposit (Edong ore district), which are important magmatic-hydrothermal deposits in eastern China.Textural features, mineral assemblages and paragenesis of the Longqiao and Tieshan ore samples have suggested the presence of two main mineralization periods (sedimentary and hydrothermal) at Longqiao, among which the hydrothermal period comprises four stages (skarn, magnetite, sulfide and carbonate); whilst the Tieshan Fe–(Cu) deposit comprises four mineralization stages (skarn, magnetite, quartz-sulfide and carbonate).Magnetite from the Longqiao and Tieshan deposits has different geochemistry, and can be clearly discriminated by the Sn vs. Ga, Ni vs. Cr, Ga vs. Al, Ni vs. Al, V vs. Ti, and Al vs. Mg diagrams. Such difference may be applied to distinguish other typical skarn (Tieshan) and multi-origin hydrothermal (Longqiao) deposits in the MLYRB. The fluid–rock interactions, influence of the co-crystallizing minerals and other physicochemical parameters, such as temperature and fO₂, may have altogether controlled the magnetite trace element contents of both deposits. The Tieshan deposit may have had higher degree of fO₂, but lower fluid–rock interactions and ore-forming temperature than the Longqiao deposit. The TiO₂–Al₂O₃–(MgO + MnO) and (Ca + Al + Mn) vs. (Ti + V) magnetite discrimination diagrams show that the Longqiao Fe deposit has both sedimentary and hydrothermal features, whereas the Tieshan Fe–(Cu) deposit is skarn-type and was likely formed via hydrothermal metasomatism, consistent with the ore characteristics observed.     

Mineral chemistry and geochemical behavior of hydrothermal alterations associated with mafic intrusive-related Au deposits at the Atud area,Central Eastern Desert,Egypt

Vein-type gold deposits in the Atud area are related to the metagabbro–diorite complex that occurred in Gabal Atud in the Central Eastern Desert of Egypt. This gold mineralization is located within quartz veins and intense hydrothermal alteration haloes along the NW–SE brittle–ductile shear zone, as well as along the contacts between them. By using the mass balance calculations, this work is to determine the mass/volume gains and losses of the chemical components during the hydrothermal alteration processes in the studied deposits. In addition, we report new data on the mineral chemistry of the alteration minerals to define the condition of the gold deposition and the mineralizing fluid based on the convenient geothermometers. Two generations of quartz veins include the mineralized grayish-to-white old vein (trending NW–SE), and the younger, non-mineralized milky white vein (trending NE–SW). The ore minerals associated with gold are essentially arsenopyrite and pyrite, with chalcopyrite, sphalerite, enargite, and goethite forming during three phases of mineralization; first, second (main ore), and third (supergene) phases. Three main hydrothermal alteration zones of mineral assemblages were identified (zones 1–3), placed around mineralized and non-mineralized quartz veins in the underground levels. The concentrations of Au, Ag, and Cu are different from zone to zone having 25–790 ppb, 0.7–69.6 ppm, and 6–93.8 ppm; 48.6–176.1 ppb, 0.9–12.3 ppm, and 39.6–118.2 ppm; and 53.9–155.4 ppb, 0.7–3.4 ppm, and 0.2–79 ppm for zones 1, 2, and 3, respectively.The mass balance calculations and isocon diagrams (calculated using the GEOISO-Windows program) revealed the gold to be highly associated with the main mineralized zone as well as sericitization/kaolinitization and muscovitization in zone 1 more than in zones 2 and 3. The sericite had a higher muscovite component in all analyzed flakes (average X_Ms = 0.89), with 0.10%–0.55% phengite content in wall rocks and 0.13%–0.29% phengite content in mineralized quartz veins. Wall rocks had higher calcite (CaCO₃) contents and lower MgCO₃ and FeCO₃ contents than the quartz veins. The chlorite flakes in the altered wall rocks were composed of pycnochlorite and ripidolite, with estimated formation temperatures of 289–295 °C and 301–312 °C, respectively. Albite has higher albite content (95.08%–99.20%) which occurs with chlorite in zone 3.     

Ore minerals down to the nanoscale: Cu-(Fe)-sulphides from the iron oxide copper gold deposit at Olympic Dam,South Australia

Cu-Fe-sulphide mineral assemblages from the Olympic Dam (OD) Fe-oxide Cu-U-Au-Ag deposit, South Australia, are studied down to the nanoscale to explore the potential these minerals have for understanding genetic processes such as primary deposit zonation. Cu-Fe-sulphide pairs: ‘brown’ bornite associated with chalcopyrite (bornite-chalcopyrite zone); and symplectites of ‘purple’ bornite with species from the chalcocite group, Cu_2 − xS (bornite-chalcocite zone), co-define an upwards and inwards deposit-scale zonation at OD. In the bornite-chalcocite zone, there is also an increase in the proportion of chalcocite relative to bornite within the symplectites towards upper levels. In this case, two-phase Cu_2 − xS assemblages are also present, as anisotropic, hexagonal chalcocite (CcH) with lamellar exsolutions of digenite, distinguishable at the μm-scale. Using compositional data (electron microprobe) combined with Transmission Electron Microscopy (TEM) study of foils prepared in–situ via Focused Ion Beam (FIB)-SEM, we show that Cu-Fe-sulphides from different ore zones feature nanoscale intergrowths, lattice defects, superstructure domains (na) and antiphase boundary domains (APBs) that can be interpreted as due to exsolution, coarsening and phase transformation during cooling from high-T solid solutions in the system Cu-Fe-S and sub-systems according to published phase diagrams. ‘Brown’ bornite [(Cu + Fe)/S > 5] contains pervasive lamellae of chalcopyrite which extend down to the nanoscale; such specimens appear homogeneous at the μm-scale. ‘Purple bornite’ [(Cu + Fe)/S < 5] in high-bornite symplectites is associated with chalcocite that shows APBs with 6a digenite and low-T chalcocite. Comparable APBs are also found in the ‘chalcocite’ zone with apparent homogeneity at the μm-scale. Both bornites contain exsolutions of djurleite. Systematic variation of Me/S and Cu/Fe in the two types of bornite points, however, to distinct origins from different bornite solid-solutions in the system Cu-Fe-S. Both show 2a and 4a intermediate superstructures. High-order superstructures (6a and incommensurate na) are restricted to the ‘purple’ bornite whereas the 2a4a low-T superstructure is found in both cases. Me/S ratios in the chalcocite group are variable; lower ratios (down to 1.8; digenite) are more common in chalcocite from symplectites with ‘purple’ bornite. Me/S can be as low as 1.4 where associated with ‘blue’ varieties (‘blaubleibender covellin’) of replacement origin. The two-phase Cu_2 − xS associations contain hexagonal chalcocite (Me/S = 1.95), lamellae of Cu-rich digenite (Me/S = 1.92), and anilite (Cu₇S₄) as nm-scale lamellae. Digenite shows 3a and 6a superstructures and CcH shows transition to pseudo-orthorhombic chalcocite. The presence of superstructures, high-T species and APBs is evidence for Cu-(Fe)-sulphide formation from high-T solid solutions at T > 300 °C (high-T phases, Cu-poor digenite), followed by cooling along distinct paths down to < 120 °C (APBs). The scenario of ‘exsolution from primary solid-solution’, corroborated by the consistency in phase relations within each zone across different scales of observation from deposit scale to nanoscale, backs up a model of primary hypogene ore precipitation rather than replacement, and accounts for the observed vertical zoning at OD. The FIB-TEM approach here is readily applicable to other deposits and shows that nanoscale observations are a valuable, although often overlooked, source of information to constrain ore genesis.     

Mineralogy,fluid inclusions,and isotopes of the Cihai iron deposit,eastern Tianshan,NW China: Implication for hydrothermal evolution and genesis of subvolcanic rocks-hosted skarn-type deposits

Most skarn deposits are closely related to granitoids that intruded into carbonate rocks. The Cihai (>100 Mt at 45% Fe) is a deposit with mineral assemblages and hydrothermal features similar to many other typical skarn deposits of the world. However, the iron orebodies of Cihai are mainly hosted within the diabase and not in contact with carbonate rocks. In addition, some magnetite grains exhibit unusual relatively high TiO₂ content. These features are not consistent with the typical skarn iron deposit. Different hydrothermal and/or magmatic processes are being actively investigated for its origin. Because of a lack of systematic studies of geology, mineral compositions, fluid inclusions, and isotopes, the genetic type, ore genesis, and hydrothermal evolution of this deposit are still poorly understood and remain controversial.The skarn mineral assemblages are the alteration products of diabase. Three main paragenetic stages of skarn formation and ore deposition have been recognized based on petrographic observations, which show a prograde skarn stage (garnet-clinopyroxene-disseminated magnetite), a retrograde skarn stage (main iron ore stage, massive magnetite-amphibole-epidote ± ilvaite), and a quartz-sulfide stage (quartz-calcite-pyrite-pyrrhotite-cobaltite).Overall, the compositions of garnet, clinpyroxene, and amphibole are consistent with those of typical skarn Fe deposits worldwide. In the disseminated ores, some magnetite grains exhibit relatively high TiO₂ content (>1 wt.%), which may be inherited from the diabase protoliths. Some distinct chemical zoning in magnetite grains were observed in this study, wherein cores are enriched in Ti, and magnetite rims show a pronounced depletion in Ti. The textural and compositional data of magnetite confirm that the Cihai Fe deposit is of hydrothermal origin, rather than associated with iron rich melts as previously suggested.Fluid inclusions study reveal that, the prograde skarn (garnet and pyroxene) formed from high temperature (520–600 °C), moderate- to high-salinity (8.1–23.1 wt.% NaCl equiv, and >46 wt.% NaCl equiv) fluids. Massive iron ore and retrograde skarn assemblages (amphibole-epidote ± ilvaite) formed under hydrostatic condition after the fracturing of early skarn. Fluids in this stage had lower temperature (220°–456 °C) and salinity (8.4–16.3 wt.% NaCl equiv). Fluid inclusions in quartz-sulfide stage quartz and calcite also record similar conditions, with temperature range from 128° to 367 °C and salinity range from 0.2 to 22.9 wt.% NaCl equiv. Oxygen and hydrogen isotopic data of garnet and quartz suggest that mixing and dilution of early magmatic fluids with external fluids (e.g., meteoric waters) caused a decrease in fluid temperature and salinity in the later stages of the skarn formation and massive iron precipitation. The δ¹⁸O values of magnetite from iron ores vary between 4.1 and 8.5‰, which are similar to values reported in other skarn Fe deposits. Such values are distinct from those of other iron ore deposits such as Kiruna-type and magmatic Fe-Ti-V deposits worldwide. Taken together, these geologic, geochemical, and isotopic data confirm that Cihai is a diabase-hosted skarn deposit related to the granitoids at depth.     

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.     

Timing of supergene enrichment of low-grade sedimentary manganese ores in the Kalahari Manganese Field,South Africa

Low-grade carbonate-rich manganese ore of sedimentary origin in the giant Kalahari Manganese Field, South Africa, is upgraded to high-grade todorokite–manganomelane manganese ore by supergene alteration below the unconformity at the base of the Cenozoic Kalahari Formation. Incremental laser-heating ⁴⁰Ar/³⁹Ar dating of samples from the supergene altered manganese ore suggest that chemical weathering processes below the Kalahari unconformity peaked at around 27.8 Ma, 10.1 Ma and 5.2 Ma ago. Older ages are dominant in the upper part of the weathering profile, while younger ages are characteristic of the deeper part of the profile. Younger ages partially overprint older ages in the upper part of the weathering profile and demonstrate the downward progression of the weathering front by as little as 10 cm per million years. The oldest age obtained in the weathering profile, namely 42 Ma, is considered a minimum estimate for the onset of the post African I cycle of weathering and erosion that followed the break up of Gondwanaland and formation of the Cretaceous to early Cenozoic African land surface. The youngest ages, recorded at around 5 Ma, in turn, correspond well to the Pliocene transition from humid to arid climatic conditions in Southern Africa.     

Focussed ion beam–transmission electron microscopy applications in ore mineralogy: Bridging micro- and nanoscale observations

Focussed ion beam–scanning electron microscopy (FIB–SEM) is a relatively new analytical tool that has been little applied to problems of ore genesis. The technique enables high-resolution (cross-section) imaging and can be used to prepare thinned foils for study by transmission electron microscopy (TEM). FIB–SEM methods applied to sulphides and related compounds represent an in-situ approach for sample characterisation and thus provides for crystal–chemical data that can be placed into the geological context of a given ore deposit.We present four study cases: these deal with minor element incorporation and release in ZnS; intergrowths and replacement among Cu–(Fe)-sulphides; fabrics in Au-bearing, As-free pyrite; and symplectites of Bi-sulphosalts within galena. The data is discussed in the context of polytypism and planar defects for minor element incorporation and release, superstructure ordering and formation of fine particles (100–2500 nm) or nanoparticles (< 100 nm) during replacement processes. Several analytical difficulties encountered when preparing FIB–TEM samples from sulphides are discussed, in particular mechanical and chemical damage to the surface. The FIB–TEM foils are difficult to thin for direct high-resolution TEM imaging but are usable for Scanning Transmission Electron Microscopy (STEM) and High-Angle Annular Dark Field (HAADF)-STEM imaging.