Geochemical assessment and speciation of metals in sediments of Osun and Erinle Rivers,Southwestern Nigeria

Fifty sediment samples were collected from Osun (urban) and Erinle (suburban) rivers in addition to ten samples of the underlying rock types (schist and gneiss) and analyzed for elemental constituents while speciation of metals was determined by sequential analysis. Data were geochemically evaluated and ArcGIS was used to generate geochemical maps. Metal concentrations (ppm) in sub-urban and urban areas were Cd (0.2–0.2, 0.2–1.1), Cu (37.0–272.0, 49.0–970.0), Ni (6.0–27.0, 3.0–43.0), Pb (16.0–67.0, 15.0–2650.0), Zn (32.0–170.0, 50.0–987.0), Co (8.0–60.0, 2.0–86.0), Cr (26.0–153.0, 9.0–128.0), V (30.0–142.0, 9.0–135.0), and Mn (442.0–5100.0, 107.0–3930.0), respectively. In the rocks, Cu, Ni, Pb, Co, Cr, V, and Zn, concentrations (ppm) were below detection limit (BDL)-0.05, BDL-38.00; 6.23–12.00, BDL-20.00; 3.78–6.23, BDL-5.00; BDL-0.20, BDL-4.00; 5.00–9.00, BDL-66.00; 15.99–32.00, BDL-130.00; and 18.00–26.00, BDL-48.00, respectively, with Cu, Pb, Zn, Cd, and Mn of elevated concentrations in sediments compared with that of the rocks, being indication of additional anthropogenic sourcing. Calculated contamination indices revealed contamination for sediment from the urban areas compared to those from the sub-urban. High percentage of Pb (2.94–81.92%), Cu (31.69–45.95%), Zn (49.2–65.5%), Cd (31.69–45.95%), and Mn (12.13–37.50%) are hosted by the bio-available phases (carbonate, organic, and sulfide). The geochemical distribution of metals in the sediments of the Osun and Erinle rivers is governed by both geogenic (Ni-Cr-Co-V) and anthropogenic (Pb-Cd-Zn) activities. Elevated concentration and occurrences of the selected metals in the bio-available phases pose potential health risk to people in the urban area.     

Permian ultrahigh–temperature reworking in the southern Chinese Altai: Evidence from petrology,P–T estimates,zircon and monazite U–Th–Pb geochronology

The Chinese Altai orogen formed in the Paleozoic is an important part of the Central Asian Orogenic Belt (CAOB), and the study on the metamorphism will provide novel and robust constraints on its tectonic evolution. In this study, we investigate our newly recognized garnet–orthopyroxene–cordierite granulites at Wuqiagou area in the southern Chinese Altai. Detailed petrographic study and P–T estimates suggest four distinct metamorphic stages of mineral assemblages: (1) pre–peak (M1) stage containing the spinel–cordierite–bearing association or biotite–plagioclase–quartz–bearing inclusion–phase assemblage, with P–T conditions of 3.0–4.0 kbar/700–750 °C; (2) peak ultrahigh–temperature (UHT) (M2) stage represented by relatively coarse–grained garnet–orthopyroxene–cordierite–bearing porphyroblastic assemblage, with high–Al₂O₃ contents (up to ∼8.7 wt%) in orthopyroxene and P–T conditions of ∼8.0 kbar/∼980 °C; (3) post–peak high–temperature granulite facies (M3) stage consisted of orthopyroxene–cordierite and cordierite–quartz corona assemblages, formed during cooling and moderate decompression; and (4) post–peak upper amphibolite facies (M4) stage represented by retrograde biotite–plagioclase–quartz intergrowths. These four discrete metamorphic stages define an anticlockwise P–T path involving a post–peak moderate decompression followed by nearly isobaric cooling process. LA–ICP–MS U–Pb age dating results of metamorphic zircons for UHT samples show two weighted mean ages of ∼390 Ma and ∼280 Ma. We propose that the M1 stage might occur in the middle Devonian, whereas the near–peak UHT stage probably occurred in the early Permian. The Permian UHT metamorphism was further supported by the monazite U–Th–Pb dating results (287.9 ± 2.1 Ma), reflecting a prominent HT–UHT reworking event in the late Paleozoic. We proposed that the Permian UHT reworking event in the southern Chinese Altai probably occurred in a post–orogenic or intraplate extensional tectonic setting associated with the input of external heat, related to the underplating of deep–derived magma as a result of the Tarim mantle plume activity.     

Sulfur Isotope Variations of Metallic Ore Deposits in the Gyeongsang Basin,South Korea

Many metallic ore deposits of the Late Cretaceous to Early Tertiary periods are distributed in the Gyeongsang Basin. Previous and newly analyzed sulfur isotope data of 309 sulfide samples from 56 ore deposits were reviewed to discuss the genetic characteristics in relation to granitoid rocks. The metallogenic provinces of the Gyeongsang Basin are divided into the Au–Ag(–Cu–Pb–Zn) province in the western basin where the sedimentary rocks of the Shindong and Hayang groups are distributed, Pb–Zn(–Au–Ag–Cu), Cu–Pb–Zn(–Au–Ag), and Fe–W(–Mo) province in the central basin where the volcanic rocks of the Yucheon Group are dominant, and Cu(–Mo–W–Fe) province in the southeastern basin where both sedimentary rocks of the Hayang Group and Tertiary volcanic rocks are present. Average sulfur isotope compositions of the ore deposits show high tendencies ranging from 2.2 to 11.7‰ (average 5.4‰) in the Pb–Zn(–Au–Ag–Cu) province, ?0.7 to 11.5‰ (average 4.6‰) in the Cu–Pb–Zn(–Au–Ag) province, and 3.7 to 11.4‰ (average 7.5‰) in the Fe–W(–Mo) province in relation to magnetite‐series granitoids, whereas they are low in the Au–Ag(–Cu–Pb–Zn) province in relation to ilmenite‐series granitoids, ranging from ?2.9 to 5.7‰ (average 1.7‰). In the Cu(–Mo–W–Fe) province δ³⁴S values are intermediate ranging from 0.3 to 7.7‰ (average 3.6‰) and locally high δ³⁴S values are likely attributable to sulfur derived from the Tertiary volcanic rocks during hydrothermal alteration through faults commonly developed in this region. Magma originated by the partial melting of the ³⁴S‐enriched oceanic plate intruded into the volcanic rocks and formed magnetite‐series granitoids in the central basin, which contributed to high δ³⁴S values of the metallic deposits. Conversely, ilmenite‐series granitoids were formed by assimilation of sedimentary rocks rich in organic sulfur that influenced the low δ³⁴S values of the deposits in the western and southeastern provinces.     

Material composition and geochemical characteristics of ores of the Malinovskoe gold-ore deposit (Primorskii Krai,Russia)

The mineral composition and geochemical characteristics of the ores of the Malinovskoe gold-ore deposit are studied by the data from mining works (ditches, cleanings, and boreholes). It is found that the ore–magma system of the deposit was formed in several stages of mineralization characterized by two phases of magmatism differing in age. In terms of the set of features (the geological–structural position of the deposit, as well as the material composition and geochemical characteristics of the ores), the deposit is attributed to the gold–tourmaline type of mineralization associated spatially and genetically with the “raremetal” granitoid magmatism. This type has not previously been found in Primorskii Krai. The studies of the material composition and geochemical characteristics of the ores allow us to ascertain the correlations between the elements along with the reasons of their origination. By analogy with other gold-ore formations of the Russian Far East, the mineralogical and geochemical model of the deposit is developed (Be–Sn–Cr–Ba–Au–Cu–Mo–Pb–V–Ti–Co–W–Ag–Bi–Ni–Mn–Sr–Zn–Sb–As modeling element series of vertical zoning), which enables us to estimate the levels of the erosion section of the ore bodies and to evaluate their prospects. It is found that the most productive associations in the deposit are the gold–bismuth geochemical association (Au–Ag–Bi–Cu–As–Co) and, to a lesser degree, the gold–tungsten association (W–Au–Ag–Cu–Bi–As).     

Pro- and retrograde P–T evolution of granulites of the Beit Bridge Complex (Limpopo Belt, South Africa): constraints from quantitative phase diagrams and geotectonic implications

Interpretations based on quantitative phase diagrams in the system CaO–Na₂O–K₂O–TiO₂–MnO–FeO–MgO–Al₂O₃–SiO₂–H₂O indicate that mineral assemblages, zonations and microstructures observed in migmatitic rocks from the Beit Bridge Complex (Messina area, Limpopo Belt) formed along a clockwise P–T path. That path displays a prograde P–T increase from 600 °C/7.0 kbar to 780 °C/9–10 kbar (pressure peak) and 820 °C/8 kbar (thermal peak), followed by a P–T decrease to 600 °C/4 kbar. The data used to construct the P–T path were derived from three samples of migmatitic gneiss from a restricted area, each of which has a distinct bulk composition: (1) a K, Al‐rich garnet–biotite–cordierite–sillimanite–K‐feldspar–plagioclase–quartz–graphite gneiss (2) a K‐poor, Al‐rich garnet–biotite–staurolite–cordierite–kyanite–sillimanite–plagioclase–quartz–rutile gneiss, and (3) a K, Al‐poor, Fe‐rich garnet–orthopyroxene–biotite–chlorite–plagioclase–quartz–rutile–ilmenite gneiss. Preservation of continuous prograde garnet growth zonation demonstrates that the pro‐ and retrograde P–T evolution of the gneisses must have been rapid, occurring during a single orogenic cycle. These petrological findings in combination with existing geochronological and structural data show that granulite facies metamorphism of the Beit Bridge metasedimentary rocks resulted from an orogenic event during the Palaeoproterozoic (c. 2.0 Ga), caused by oblique collision between the Kaapvaal and Zimbabwe Cratons. Abbreviations follow Kretz (1983 ).     

Study on the Cu–As–Sb–Ag–Bi–Pb–Te Sulfosalt Minerals from the Hydrothermal System of Southwestern Hokkaido,Japan

Shin‐Otoyo, Suttsu, Teine, Date, Chitose, and Koryu are sites rich in precious and base metal Miocene–Pleistocene epithermal deposits, and located in southwestern Hokkaido, Japan. The deposits are predominantly hosted by the Green Tuff Formation of Middle Miocene age. Ore petrographic study of these deposits shows the occurrence of variable quantities of Cu–As–Sb–Ag–Bi–Pb–Te sulfosalt minerals. Determination of mineralogical and chemical compositions of the sulfosalt minerals was undertaken to elucidate the time and spatial changes of the sulfide‐sulfosalt minerals. Various types of sulfosalt minerals identified from gold–silver and base metal quartz–sulfide veins represented some sulfosalt mineralization phases, such as the Cu–Fe–Sn–S phase of mawsonite and stannite; Cu–(As,Sb)–S phase of tetrahedrite–tennantite and luzonite–famatinite series minerals; (Cu,Ag)–Bi–Pb–S phase of emplectite, pavonite, friedrichite, aikinite, and lillianite–gustavite series minerals; (Ag,Cu)–(As,Sb)–S phase of proustite–pyrargyrite and pearceite–polybasite series minerals; and Bi–Te–S phase of tetradymite and kawazulite minerals. There are some trends in the paragenetic sequence of sulfosalt mineralization in southwestern Hokkaido (in complete or partial) as follows: sulfide → Cu–Fe–Sn–S → (Cu,Ag)–Bi–Pb–S → (Bi–Te–S) → Cu–(As,Sb)–S → ([Ag,Cu]–[As,Sb]–S). The formation of sulfosalt minerals is characterized by the introduction of some elements such as Sn, Bi, and Te at an earlier stage and an increase or decrease of some elements such as As and Sb, followed by the introduction of Ag at the later stage of ore mineral paragenesis sequence. Mineral composition of the Chitose and Koryu deposits are slightly different from those of Shin‐Otoyo, Suttsu, Teine, and Date due to their lack of Sn (tin) and Bi (bismuth) mineralization. The variable concentrations and relationships are not simply with redistributed trace elements from the original sulfide minerals of chalcopyrite, pyrite, galena, and sphalerite. Some heavier elements were also introduced during the replacement reaction, which is consistent with the occurrence of their associated minerals.     

Trace metal nanoparticles in pyrite

Hydrothermal pyrite contains significant amounts of minor and trace elements including As, Pb, Sb, Bi, Cu, Co, Ni, Zn, Au, Ag, Se and Te, which can be incorporated into nanoparticles (NPs). NP-bearing pyrite is most common in hydrothermal ore deposits that contain a wide range of trace elements, especially deposits that formed at low temperatures. In this study, we have characterized the chemical composition and structure of these NPs and their host pyrite with high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), analytical electron microscopy (AEM), and electron microprobe analysis (EMPA). Pyrite containing the NPs comes from two types of common low-temperature deposits, Carlin-type (Lone Tree, Screamer, Deep Star (Nevada, USA)), and epithermal (Pueblo Viejo (Dominican Republic) and Porgera (Papua New-Guinea)).EMPA analyses of the pyrite show maximum concentrations of As (11.2), Ni (3.04), Cu (2.99), Sb (2.24), Pb (0.99), Co (0.58), Se (0.2), Au (0.19), Hg (0.19), Ag (0.16), Zn (0.04), and Te (0.04) (in wt.%). Three types of pyrite have been investigated: “pure” or “barren” pyrite, Cu-rich pyrite and As-rich pyrite. Arsenic in pyrite from Carlin-type deposits and the Porgera epithermal deposit is negatively correlated with S, whereas some (colloform) pyrite from Pueblo Viejo shows a negative correlation between As + Cu and Fe. HRTEM observations and SAED patterns confirm that almost all NPs are crystalline and that their size varies from 5 to 100 nm (except for NPs of galena, which have diameters of up to 500 nm). NPs can be divided into three groups on the basis of their chemical composition: (i) native metals: Au, Ag, Ag–Au (electrum); (ii) sulfides and sulfosalts: PbS (galena), HgS (cinnabar), Pb–Sb–S, Ag–Pb–S, Pb–Ag–Sb–S, Pb–Sb–Bi–Ag–Te–S, Pb–Te–Sb–Au–Ag–Bi–S, Cu–Fe–S NPs, and Au–Ag–As–Ni–S; and (iii) Fe-bearing NPs: Fe–As–Ag–Ni–S, Fe–As–Sb–Pb–Ni–Au–S, all of which are in a matrix of distorted and polycrystalline pyrite. TEM-EDX spectra collected from the NPs and pyrite matrix document preferential partitioning of trace metals including Pb, Bi, Sb, Au, Ag, Ni, Te, and As into the NPs. The NPs formed due to exsolution from the pyrite matrix, most commonly for NPs less than 10 nm in size, and direct precipitation from the hydrothermal fluid and deposition into the growing pyrite, most commonly for those > 20 nm in size. NPs containing numerous heavy metals are likely to be found in pyrite and/or other sulfides in various hydrothermal, diagenetic and groundwater systems dominated by reducing conditions.     

Neoproterozoic Rare-Metal Subalkali Leucogranite from the Northern Yenisei Ridge

Petrochemical study and U–Pb SIMS (SHRIMP–II) zircon analyses of subalkaline leucogranite of the Khariusikha Massif have been carried out. They have revealed for the first time a rare-metal mineralization. The elevated concentrations of rare elements (wt %) are Nb (0.5–0.7), Ta (0.12–0.16), REEs (0.08–0.24), Y (0.06–0, 1), Zr (2.3–2.6), Hf (0.1–0.12), U (0.05–0.1), and Th (0.08–0.1) and are confined to albitized granites. The main mineral phases concentrating the rare elements, U and Th, are tantalo–niobates: fergusonite, euxenite, U–pyrochlore, tantalite, as well as thorite, monazite, zircon, and sphene. These minerals associate with cassiterite, sulfides, and gold. The simultaneity of the intraplate granitoid magmatism (753 ± 4 Ma) and bimodal rhyolite–basalt volcanism (753 ± 6 Ma) in the neighboring rift structure has been demonstrated. Presumably, the Neoproterozoic rifting and intraplate magmatism relate to the plume activity that caused the supercontinent Rodinia to break up.     

Types,features, and prospecting potential for Mesozoic metal ore deposits in Zhejiang Province,southeast China

The geotectonic units of Zhejiang Province include the Yangtze Plate in the northwest juxtaposed against the South China fold system in the southeast along the Jiangshan–Shaoxing fault. The South China fold system is further divided into the Chencai–Suichang uplift belt and the Wenzhou–Linhai geotectogene belt, whose boundary is the Yuyao–Lishui fault. The corresponding metallogenic belts are the Mo–Au(–Pb–Zn–Cu) metallogenic belt in northwest Zhejiang, the Chencai–Suichang Au–Ag–Pb–Zn–Mo metallogenic belt, and the coastal Ag–Pb–Zn–Mo–Au metallogenic belt. The main Mesozoic metal ore deposits include epithermal Au–Ag(Ag), hydrothermal vein-type Ag–Pb–Zn(Cu), and porphyry–skarn-type Mo and vein-type Mo deposits. These ore bodies are related to the Mesozoic volcanic-intrusive structure: the epithermal Au–Ag(Ag) deposits are represented by the Zhilingtou Au–Ag deposit and Houan Ag deposit and their veins are controlled by volcanic structure; the hydrothermal vein-type Ag–Pb–Zn deposits are represented by the Dalingkou Ag–Pb–Zn deposit and also controlled by volcanic structure; and the porphyry–skarn-type Mo deposits are represented by the Tongcun Mo deposit and the vein-type Mo deposits are represented by the Shipingchuan Mo deposit, all of which are related to granite porphyries. These metal ore deposits have close spatio-temporal relationships with each other; both the epithermal Au–Ag(Ag) deposits and the hydrothermal vein-type Ag–Pb–Zn deposits exhibit vertical zonations of the metallic elements and form a Mo–Pb–Zn–Au–Ag metallogenetic system. These Jurassic–Cretaceous deposits may be products of tectonic-volcanic-intrusive magmatic activities during the westward subduction of the Pacific Plate. Favourable metallogenetic conditions and breakthroughs in the recent prospecting show that there is great resource potential for porphyry-type deposits (Mo, Cu) in Zhejiang Province.     

Shallow submarine epithermal Pb–Zn–Cu–Au–Ag–Te mineralization on western Milos Island,Aegean Volcanic Arc,Greece: Mineralogical,geological and geochemical constraints

Milos Island contains several epithermal deposits (e.g., Profitis Ilias–Chondro Vouno Pb–Zn–Ag–Au–Te–Cu, Triades–Galana–Agathia–Kondaros Pb–Zn–Ag–Bi–W–Mo ± Cu–Au, and Katsimoutis–Kondaros–Vani Pb–Zn–Ag–Mn) of Late Pliocene to Early Pleistocene age. These deposits are hosted in calc-alkaline volcanic rocks emplaced as a result of three successive magma pulses in an emergent volcanic edifice: submarine rhyolitic to rhyodacitic cryptodomes at ca. 2.7. Ma (Profitis Ilias–Chondro Vouno), submarine to subaerial andesite to dacite domes at ca. 2.2 to 1.5 Ma (Triades–Galana–Kondaros–Katsimouti–Vani). Hydrothermal alteration of the volcanic rocks includes advanced argillic- (both hypogene and steam-heated), argillic, phyllic, adularia-sericite and propylitic types. In the northern sector (Triades–Galana–Agathia–Kondaros), initial magma degassing derived from andesitic–dacitic intrusives along NE–SW to E–W trending faults resulted in the development of pre-ore hypogene advanced argillic alteration (dickite, alunite, ± diaspore, pyrophyllite, halite, and pyrite) in a submarine environment. Mineralogical data indicate common features among the Profitis Ilias–Chondro Vouno, Kondaros–Katsimoutis–Vani and Triades–Galana mineralized centers, all of which are characterized by the presence of galena, Fe-poor sphalerite, and chalcopyrite as well as abundant barite, adularia, sericite and, to a lesser extent, calcite, which are typical of intermediate-sulfidation epithermal type deposits. Locally, at Triades–Galana and Kondaros–Agathia, high-sulfidation conditions prevailed as suggested by the presence of coexisting enargite and covellite. The high silver and gold content of the western Milos deposits is derived from Ag-bearing sulfosalts (polybasite, pearceite, pyrargyrite, freibergite) and tellurides. Gold at Profitis Ilias, both as native gold and silver-gold tellurides, is present in base-metal precipitates within multicomponent blebs, which recrystallized to form hessite, petzite, altaite, coloradoite, and native gold. Mineralogical evidence (e.g. microchimney structures, copper sulfides, widespread occurrence of barite, aragonite) suggests that precious metal mineralization in western Milos mineralization formed in a submarine setting.We present information on the surface distribution of Au, Ag, Cu, Pb, Zn, As, Sb, Hg, Mo, Bi, W and Cd at western Milos. Gold is enriched at Profitis Ilias–Chondro Vouno deposits and to a lesser extent at Triades–Galana. Arsenic is absent from the southern sector but shows elevated concentrations together with molybdenum, bismuth and tungsten at the northern sector (Triades–Galana, Vani deposits). The differences in precious and base metal abundances may be related to the depths at which the deposits are exposed, and/or different sources of magma. The metal signatures of the Triades–Galana and Agathia–Kondaros–Katsimouti–Vani (Mo–Bi–W–As–Hg–Ag–Au) occurrences compared to Profitis Ilias (Te–Au–Ag) reflect different sources of magma (dacite–rhyodacite for Profitis Ilias, andesite–dacite for Triades–Galana, and dacite for Kondaros–Katsimoutis). The enrichment of Te, Mo, W, and Bi in the deposits is a strong indication of a direct magmatic contribution of these metals.At western Milos, precious and base-metal vein mineralization was deposited during episodic injection of magmatic volatiles and dilution of the hydrothermal fluids by seawater. The mineralization represents seafloor/sub-seafloor precipitation of sulfides that formed in stockwork zones. Base and precious metal mineralization formed from intermediate- to high-sulfidation state fluids and mostly under boiling conditions as indicated by the widespread occurrence of adularia associated with metallic mineralization. We speculate that the widespread occurrence of boiling and the shallow depth of the precious- and base-metal emplacement prevented the formation of seafloor massive sulfides.     

Composition and evolution of PGE mineralization in chromite ores from the Il’chir ophiolite complex (Ospa–Kitoi and Khara-Nur areas,East Sayan)

Data are presented on chromitites from the northern and southern sheets of the Il’chir ophiolite complex (Ospa–Kitoi and Khara-Nur (Kharanur) massifs). The new and published data are used to consider similarities and differences between ore chrome-spinel from the chromitites of the northern and southern ophiolite sheets as well as the species diversity of PGE minerals and the evolution of PGE mineralization. Previously unknown PGE minerals have been found in the studied chromitites.Ore chrome-spinel in the chromitites from the northern sheet occurs in medium- and low-alumina forms, whereas the chromitites from the southern sheet contain only medium-alumina chrome-spinel. The PGE minerals in the chromitites from the southern sheet are Os–Ir–Ru solid solutions as well as sulfides and sulfoarsenides of these metals. The chromitites from the northern sheet contain the same PGE minerals and diverse Rh–Pt–Pd mineralization: Pt–Ir–Ru–Os and isoferroplatinum with Ir and Os–Ir–Ru lamellae. Areas of altered chromitites contain a wide variety of low-temperature secondary PGE minerals: Pt–Cu, Pt–Pd–Cu, PdHg, Rh2SnCu, RhNiAs, PtAs2, and PtSb2. The speciation of the PGE minerals is described along with multiphase intergrowths. The relations of Os–Ir–Ru solid solutions with laurite and irarsite are considered along with the microstructure of irarsite–osarsite–ruarsite solid solutions. Zoned Os–Ir–Ru crystals have been found. Zone Os82–99 in these crystals contains Ni3S2 inclusions, which mark off crystal growth zones. Different sources of PGE mineralization are presumed for the chromitites from the northern and southern sheets.The stages of PGE mineralization have been defined for the chromitites from the Il’chir ophiolite belt. The Pt–Ir–Ru–Os and (Os, Ru)S2 inclusions in Os–Ir–Ru solid solutions might be relics of primitive-mantle PGE minerals. During the partial melting of the upper mantle, Os–Ir–Ru and Pt–Fe solid solutions formed syngenetically with the chromitites. During the late-magmatic stage, Os–Ir–Ru solid solutions were replaced by sulfides and sulfarsenides of these metals. Mantle metasomatism under the effect of reduced mantle fluids was accompanied by PGE remobilization and redeposition with the formation of the following assemblage: garutiite (Ni,Fe,Ir), zaccariniite (RhNiAs), (Ir,Ni,Cu)S3, Pt–Cu, Pt–Cu–Fe–Ni, Cu–Pt–Pd, and Rh–Cu–Sn–Sb. The zoned Os–Ir–Ru crystals in the chromitites from the northern sheet suggest dissolution and redeposition of Os–Ir–Ru primary-mantle solid solutions by bisulfide complexes. Most likely, the PGE remobilization took place during early serpentinization at 450–600 ºC and 13–16 kbar.During the crustal metamorphic stage, tectonic movements (obduction) and a change from reducing to oxidizing conditions were accompanied by the successive transformation of chrome-spinel into ferrichromite–chrome-magnetite with the active participation of a metamorphic fluid enriched in crustal components. The orcelite–maucherite–ferrichromite–sperrylite assemblage formed in epidote-amphibolitic facies settings during this stage.The PGE mineral assemblage reflects different stages in the formation of the chromitites and dunite-harzburgite host rocks and their transformation from primitive mantle to crustal metamorphic processes.     

Geology, mineralization, stable isotope geochemistry, and fluid inclusion characteristics of the Novogodnee–Monto oxidized Au–(Cu) skarn and porphyry deposit, Polar Ural, Russia

The Novogodnee–Monto oxidized Au–(Cu) skarn and porphyry deposit is situated in the large metallogenic belt of magnetite skarn and Cu–Au porphyry deposits formed along the Devonian–Carboniferous Urals orogen. The deposit area incorporates nearly contemporaneous Middle–Late Devonian to Late Devonian–Early Carboniferous calc-alkaline (gabbro to diorite) and potassic (monzogabbro, monzodiorite- to monzonite-porphyry, also lamprophyres) intrusive suites. The deposit is represented by magnetite skarn overprinted by amphibole–chlorite–epidote–quartz–albite and then sericite–quartz–carbonate assemblages bearing Au-sulfide mineralization. This mineralization includes early high-fineness (900–990?‰) native Au associated mostly with cobaltite as well as with chalcopyrite and Co-pyrite, intermediate-stage native Au (fineness 830–860?‰) associated mostly with galena, and late native Au (760–830?‰) associated with Te minerals. Fluid inclusion and stable isotope data indicate an involvement of magmatic–hydrothermal high-salinity (>20 wt.% NaCl-equiv.) chloride fluids. The potassic igneous suite may have directly sourced fluids, metals, and/or sulfur. The abundance of Au mineralization is consistent with the oxidized character of the system, and its association with Co-sulfides suggests elevated sulfur fugacity.     

Geology and ore genesis of the late Paleozoic Heijianshan Fe oxide–Cu (–Au) deposit in the Eastern Tianshan,NW China

The Heijianshan Fe–Cu (–Au) deposit, located in the Aqishan-Yamansu belt of the Eastern Tianshan (NW China), is hosted in the mafic–intermediate volcanic and mafic–felsic volcaniclastic rocks of the Upper Carboniferous Matoutan Formation. Based on the pervasive alteration, mineral assemblages and crosscutting relationships of veins, six magmatic–hydrothermal stages have been established, including epidote alteration (Stage I), magnetite mineralization (Stage II), pyrite alteration (Stage III), Cu (–Au) mineralization (Stage IV), late veins (Stage V) and supergene alteration (Stage VI). The Stage I epidote–calcite–tourmaline–sericite alteration assemblage indicates a pre-mineralization Ca–Mg alteration event. Stage II Fe and Stage IV Cu (–Au) mineralization stages at Heijianshan can be clearly distinguished from alteration, mineral assemblages, and nature and sources of ore-forming fluids.Homogenization temperatures of primary fluid inclusions in quartz and calcite from Stage I (189–370 °C), II (301–536 °C), III (119–262 °C) and V (46–198 °C) suggest that fluid incursion and mixing probably occurred during Stage I to II and Stage V, respectively. The Stage II magmatic–hydrothermal-derived Fe mineralization fluids were characterized by high temperature (>300 °C), medium–high salinity (21.2–56.0 wt% NaCl equiv.) and being Na–Ca–Mg–Fe-dominated. These fluids were overprinted by the external low temperature (<300 °C), medium–high salinity (19.0–34.7 wt% NaCl equiv.) and Ca–Mg-dominated basinal brines that were responsible for the subsequent pyrite alteration and Cu (–Au) mineralization, as supported by quartz CL images and H–O isotopes. Furthermore, in-situ sulfur isotopes also indicate that the sulfur sources vary in different stages, viz., Stage II (magmatic–hydrothermal), III (basinal brine-related) and IV (magmatic–hydrothermal). Stage II disseminated pyrite has δ³⁴S_fluid values of 1.7–4.3‰, comparable with sulfur from magmatic reservoirs. δ³⁴S_fluid values (24.3–29.3‰) of Stage III Type A pyrite (coexists with hematite) probably indicate external basinal brine involvement, consistent with the analytical results of fluid inclusions. With the basinal brines further interacting with volcanic/volcaniclastic rocks of the Carboniferous Matoutan Formation, Stage III Type B pyrite–chalcopyrite–pyrrhotite assemblage (with low δ³⁴S_fluid values of 4.6–10.0‰) may have formed at low fO₂ and temperature (119–262 °C). The continuous basinal brine–volcanic/volcaniclastic rock interactions during the basin inversion (∼325–300 Ma) may have leached sulfur and copper from the rocks, yielding magmatic-like δ³⁴S_fluid values (1.5–4.1‰). Such fluids may have altered pyrite and precipitated chalcopyrite with minor Au in Stage IV. Eventually, the Stage V low temperature (∼160 °C) and low salinity meteoric water may have percolated into the ore-forming fluid system and formed late-hydrothermal veins.The similar alteration and mineralization paragenetic sequences, ore-forming fluid sources and evolution, and tectonic settings of the Heijianshan deposit to the Mesozoic Central Andean IOCG deposits indicate that the former is probably the first identified Paleozoic IOCG-like deposit in the Central Asian Orogenic Belt.     

Noble-metal ore genesis and mantle–crust interaction

The mineral and geochemical compositions of noble-metal (first of all, gold) deposits of the Fennoscandian, Siberian, and Northeast Asian orogenic belts are considered. These deposits are of several types: Au (disseminated Au–sulfide and Au–quartz), Au–Bi, Au–Ag, Au–Sb, Ag–Sb, Au–Sb–Hg, and Ag–Hg. They formed in different geodynamic settings as a result of the active motion of crustal tectonic blocks of different nature. Subduction processes (both at the front and at the rear of continent-marginal and island-arc magmatic arcs) resulted in Au–Ag, Ag–Sb, Ag–Hg, Au–Sb–Hg, and Au–Bi deposits. Collision events gave rise to Au and Au–Bi deposits. Intraplate continental rifting and formation of orogenic belts along the boundaries of block (plate) sliding led to the origin of Au and Au–Bi ores in association with Au–Ag, Au–Sb–Hg, and complex ores. In all cases, the formation of noble-metal mineralization was accompanied by magmatism of different types and metamorphism. Because of this diversity of ores, there is no single concept of the genesis of noble-metal mineralization. Several competing models of genesis exist: hydrothermal-metamorphic, pluton-metamorphic, plutonic, activity of mantle fluid flows, and multistage concentration during the crust–mantle interaction with the leading role of sedimentary complexes.     

Composition and genesis of the Konevinsky gold deposit,Eastern Sayan,Russia

The Konevinsky gold deposit in southeast Eastern Sayan is distinguished from most known deposits in this region (Zun-Kholba, etc.) by the geological setting and composition of mineralization. To elucidate the cause of the peculiar mineralization, we have studied the composition, formation conditions, and origin of this deposit, which is related to the Ordovician granitoid pluton 445–441 Ma in age cut by intermediate and basic dikes spatially associated with metavolcanic rocks of the Devonian–Carboniferous Ilei Sequence. Four mineral assemblages are recognized: (1) quartz–pyrite–molybdenite, (2) quartz–gold–pyrite, (3) gold–polysulfide, and (4) telluride. Certain indications show that the ore was formed as a result of the superposition of two distinct mineral assemblages differing in age. The first stage dated at ~440 Ma is related to intrusions generating Cu–Mo–Au porphyry mineralization and gold–polysulfide veins. The second stage is controlled by dikes pertaining to the Devonian–Carboniferous volcanic–plutonic association. The second stage is characterized by gain of Hg and Te and formation of gold–mercury–telluride paragenesis.     

Specific genesis of gold and silver sulfides at the Yunoe deposit (Magadan Region,Russia)

Hypogene uytenbogaardtite, acanthite, and native gold parageneses have been revealed at the epithermal Yunoe gold-silver deposit, Magadan Region, Russia. Thermodynamic calculations in the system Si–Al–Mg–Ca–Na–K–Fe–Pb–Zn–Cu–Ag–Au–S–C–Cl–H₂O were carried out at 25–400 °C and 1–1000 bars to elucidate the role of hydrothermal solutions in the formation of gold and silver sulfides. Several most probable scenarios for ore-forming processes in the deposit are considered: (1) interaction between cold and heated meteoric waters percolating along cracks from surface to depth and reacting with the host rock—rhyolite; (2) evolution of ascending postmagmatic fluid resulting in chloride–carbonic acid solution, which interacts with rhyolite at 100–400 °C; (3) stepwise cooling of hydrothermal ore-bearing solutions; (4) rapid cooling of ore-bearing hydrotherms on their mixing with cold surface waters. Rhyolite with Pb, Zn, Cu, Cl, S, Ag, and Au clarke contents was taken as an initial host rock. Calculations by model 3 showed the possible formation of uytenbogaardtite and petrovskaite at low-temperature stages. Gold and silver sulfides can be deposited during the mixing of ore-bearing acid chloride–carbonic acid hydrothermal solutions with surface alkaline waters.     

西准噶尔宝贝金矿地质与容矿火山岩的锆石SHRIMP年龄

位于西准噶尔的宝贝金矿主要由石英脉型矿石组成,主要含金矿物为银金矿,以裂隙金和包裹金的形式赋存在毒砂、黄铁矿和石英中。宝贝金矿的黄铁矿普遍含As（最高达3.88%,平均1.49%）。根据脉穿切和矿物共生组合可将宝贝金矿的成矿作用划分出四个成矿阶段：钠长石–石英阶段（I）、银金矿–黄铁矿–毒砂–石英阶段（II）、多金属硫化物浸染状矿化阶段（III）和碳酸盐化阶段（IV）,其中第II和III阶段为主要成矿期。利用锆石SHRIMP方法测定了赋矿围岩（酸性凝灰岩）的形成时代,其U–Pb谐和年龄为328.1±1.8 Ma（MSWD＝1.6, n＝13）。该年龄代表宝贝金矿赋矿围岩的形成时间,即西准噶尔地区大规模中酸性火山岩的喷发时间。     

First Find of Ga-Bearing Minerals in Ores of Ural Massive Sulfide Deposits

Gallium-containing chlorite, mica, and magnetite (up to 14, 13, and 5–7 wt % of Ga) along with Ga hydroxides (oxyhydroxides?) were found for the first time in massive sulfide deposit in the Urals. The minerals identified within the cement of chalcopyrite–sphalerite breccias of the Shemur copper–zinc–massive sulfide deposit (Northern Urals) are associated with Ga-enriched sphalerite, chalcopyrite, and, less commonly, pyrite (33–364, 67–363, and 4–230 g/t, respectively).     

Mineralization and fluid evolution of the Jiyuan polymetallic Cu–Ag–Pb–Zn–Au deposit,eastern Tianshan,NW China

The newly discovered Jiyuan Cu–Ag–(Pb–Zn–Au) deposit is located in the southern section of the eastern Tianshan orogenic belt, Xinjiang, northwestern China. It is the first documented deposit in the large Aqikekuduke Ag–Cu–Au belt in the eastern Tianshan orogen. Detailed field observations, parageneses, and fluid inclusion studies suggest an epithermal ore genesis for the main Cu–Ag mineralization, accompanied by a complicated hydrothermal alteration history most likely associated with the multi-stage tectonic evolution of the eastern Tianshan. The Jiyuan Cu–Ag ore bodies are located along the EW-striking, south-dipping Aqikekuduke fault and are hosted by Precambrian marble and intercalated siliceous rocks. Early-stage skarn alteration occurred along the contact zone between the marble layers and Early Carboniferous diorite–granodiorite and monzogranite intrusions; the skarns are characterized by diopside–tremolite–andradite–pyrite–(magnetite) assemblages. Local REE-enriched synchysite–rutile–arsenopyrite–(clinochlorite–microcline–albite) assemblages are related to K–Na alteration associated with the monzogranite intrusions and formed under conditions of high temperature (310°C) and high salinity (19.9 wt.% NaCl). Subsequent hydrothermal alteration produced a series of quartz and calcite veins that precipitated from medium- to low-temperature saline fluids. These include early ‘smoky’ quartz veins (190°C; 3.0 wt.% NaCl) that are commonly barren, coarse-grained Cu–Ag mineralized quartz veins (210°C; 2.4 wt.% NaCl), and late-stage unmineralized calcite veins (140°C; 1.1 wt.% NaCl). Tremolite and Ca-rich scapolite veins formed at an interval between early and mineralized quartz veins, indicating a high-temperature, high-salinity (>500°C; 9.5 wt.% NaCl) Ca alteration stage. Fluid mixing may have played an important role during Cu–Ag mineralization and an external low-temperature Ca-rich fluid is inferred to have evolved in the ore-forming system. The Jiyuan auriferous quartz veins possess fluid characteristics distinct from those of the Cu–Ag mineralized quartz veins. CO₂-rich fluid inclusions, fluid boiling, and mixing all demonstrate that these auriferous quartz veins acted as hosts for the orogenic-type gold mineralization, a common feature in the Tianshan orogenic belt.     

Application of K-feldspar–jadeite–quartz barometry to eclogite facies metagranites and metapelites in the Sesia Lanzo Zone (Western Alps, Italy)*

The eclogite facies assemblage K-feldspar–jadeite–quartz in metagranites and metapelites from the Sesia-Lanzo Zone (Western Alps, Italy) records the equilibration pressure by dilution of the reaction jadeite+quartz=albite. The metapelites show partial transformation from a pre-Alpine assemblage of garnet (Alm₆₃Prp₂₆Grs₁₀)–K-feldspar–plagioclase–biotite±sillimanite to the Eo-Alpine high-pressure assemblage garnet (Alm₅₀Prp₁₄Grs₃₅)–jadeite (Jd_80–97Di_0–4Hd_0–8Acm_0–7)–zoisite–phengite. Plagioclase is replaced by jadeite–zoisite–kyanite–K-feldspar–quartz, and biotite is replaced by garnet–phengite or omphacite–kyanite–phengite. Equilibrium was attained only in local domains in the metapelites and therefore the K-feldspar–jadeite–quartz (KJQ) barometer was applied only to the plagioclase pseudomorphs and K-feldspar domains. The albite content of K-feldspar ranges from 4 to 11 mol% in less equilibrated assemblages from Val Savenca and from 4 to 7 mol% in the partially equilibrated samples from Monte Mucrone and the equilibrated samples from Montestrutto and Tavagnasco. Thermodynamic calculations on the stability of the assemblage K-feldspar–jadeite–quartz using available mixing data for K-feldspar and pyroxene indicate pressures of 15–21 kbar (±1.6–1.9 kbar) at 550±50 °C. This barometer yields direct pressure estimates in high-pressure rocks where pressures are seldom otherwise fixed, although it is sensitive to analytical precision and the choice of thermodynamic mixing model for K-feldspar. Moreover, the KJQ barometer is independent of the ratio PH2O/P_T. The inferred limiting a(H₂O) for the assemblage jadeite–kyanite in the metapelites from Val Savenca is low and varies from 0.2 to 0.6.