Geochemical and mineralogical characteristics of weathered ore in the Dalucao REE deposit,Mianning–Dechang REE Belt,western Sichuan Province,southwestern China

The Dalucao deposit in western Sichuan Province, southwest China, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE Belt. Moreover, this is the only deposit identified in the southern part of the belt. The deposit contains the No. 1, 2, and 3 orebodies. The No. 1 and 3 orebodies are hosted in two breccia pipes within syenite–carbonatite rocks that intrude a Proterozoic quartz–diorite pluton. Both breccia pipes have elliptical horizontal cross-sections at the surface, being 200–400 m long, 180–200 m wide, and extending to > 450 m depth. The No. 1 and No. 3 orebodies have total thicknesses of 55–175 m and 14–58 m, respectively. REE mineralization is associated with four brecciation events that are recorded in both pipes. The ore grades in the No. 1 and 3 orebodies are similar, with the rocks containing 1.0–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a mineral assemblage comprising fluorite + barite + celestite + bastnäsite (i.e., Type I), whereas the No. 3 orebody is characterized by an assemblage comprising fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite (i.e., Type II). Significant amounts of weathered high-grade REE ore (up to 60 wt.% of the rock mass) is mainly present in the No. 1 orebody. This is the main ore-type targeted for exploration within the Dalucao deposit, but is rarely present in other deposits in the Mianning–Dechang REE Belt.Faulting and cryptoexplosive breccia events, possibly linked to movement on the Panxi Fault, were more common in the No. 1 orebody than in the No. 3 orebody. This facilitated the introduction of ore-forming hydrothermal fluids and provided space for the precipitation of REE minerals. Based on the present results, we infer that the Dalucao deposit was the product of multiple stages of ore formation. REE minerals formed in envelopes around, or fractures within, quartz, fluorite, calcite, barite, and celestite in the brecciated ores. The main REE minerals were deposited from hydrothermal fluids within cryptoexplosive breccia, followed by weathering that increased the ore grade. Petrographic studies and X-ray powder diffraction (XRD) analyses indicate that the weathered ore contains 5–60% REE minerals (including bastnäsite, parisite, and monazite), together with gangue (quartz, barite, celestite, and fluorite), large amount of clay minerals (smectite, illite, kaolinite, and sepiolite), and relict igneous minerals (quartz, albite, and K-feldspar). The weathered samples are strongly enriched in La (up to 92,390 ppm), Ce (up to 103,500 ppm), Pr (up to 8006 ppm), and Nd (up to 16,690 ppm) compared with the unweathered brecciated ores. Conversely, Sr concentrations are significantly more enriched in the brecciated ores (up to 256,500 ppm) than in the weathered ores (generally less than 2671 ppm with one exception of 37,850 ppm) due to less celestite. Calcite is largely absent from the weathered ores (except one sample with up to 30% mode), which contrasts with the brecciated ores that contain up to 75% calcite. The effects of weathering, oxidation, loss of ions, and hydration on the brecciated ores led to the refertilization of the REEs and an increase in the grade of the ore deposit.     

Indium in cassiterite and ores of tin deposits

The results obtained with LA-ICP-MS by less abundant lighter ¹¹³In isotope and EPMA show that in cassiterite of cassiterite–quartz veins the indium contents do not exceed 160 ppm, while cassiterite from Sn–sulfide veins is characterized by higher indium contents from 40 to 485 ppm; sulfides of Sn–sulfide veins unlike sulfides of cassiterite–quartz veins also have the highest indium contents: Fe-sphalerite (100–25,000 ppm), chalcopyrite (up to 1000 ppm), and stannite (up to 60,000 ppm). Indium contents in the Sn–sulfide ore of the Tigrinoe and Pravourmiiskoe deposits obtained using SR-XRF, ICP-MS and atomic absorption methods range from 10 to 433 ppm with average values of 56–65 ppm. Indium-rich Sn–sulfide mineralization in five large Sn–Ag ore districts of the Far East Russia (Khingansky, Badzhalsky, Komsomolsky, Arminsky, Kavalerovsky) provides the impetus for further exploration of deposits with Sn–sulfide mineralization as the most promising indium resources in Russia. Empirical observations from geology and geochronology of cassiterite–quartz and Sn–sulfide mineralization show that the combined contribution from granite and alkaline–subalkaline mafic sources and multistage ore-forming processes doubled indium resources of deposits being the main factors in the formation of high grade indium mineralization.     

Insights into the extreme PGE enrichment of the W Horizon,Marathon Cu-Pd deposit,Coldwell Alkaline Complex,Canada: Platinum-group mineralogy,compositions and genetic implications

The W Horizon, Marathon Cu-Pd deposit in the Mesoproterozoic Midcontinent rift is one of the highest grade PGE repositories in magmatic ore deposits world-wide. The textural relationships and compositions of diverse platinum-group mineral (PGM) and sulfide assemblages in the extremely enriched ores (>100 ppm Pd-Pt-Au over 2 m) of the W Horizon have been investigated in mineral concentrates with ∼10,000 PGM grains and in situ using scanning electron microprobe and microprobe analyses.Here we show, from ore samples with concentrations up to 23.1 Pd ppm, 8.9 Pt ppm, 1.4 Au ppm and 0.73 Rh ppm, the diversity of minerals (n = 52) including several significant unknown minerals and three new mineral species marathonite (Pd₂₅Ge₉; McDonald et al., 2016), palladogermanide (Pd₂Ge; IMA 2016-086, McDonald et al., 2017), kravtsovite (PdAg₂S, IMA No 2016-092, Vymazalová et al., 2017). The PGM are distributed as PG-, sulfides (52 vol%), -arsenides (34 vol%), -intermetallics of Au-Ag-Pd-Cu and Pd-Ge(10 vol%) and -bismuthides and tellurides (4 vol%). The discovery of abundant (>330 grains) large unknown sulfide minerals with Rh allows us to present analyses three significant potentially new minerals (WUK-1, WUK-2, WUK-3) that are all clearly enriched in Rh (averaging 4.2, 8.5 and 28.21 wt% Rh respectively). Several examples of paragenetic sequences and mineral chemical changes for enrichment of Cu, Pd and Rh with time are revealed in the PGM and base-metal sulfides. We suggest this enhanced metal enrichment formed in response to increasing fO₂ causing the oxidation of Fe²⁺ to Fe³⁺ and to a lesser extent, S.Phase relations in the Ag-Pd-S, Rh-Ni-Fe-S, Pd-Ge, Au-Pd-Cu-Ag, Pd-Ag-Te systems help constrain the crystallization temperatures of the majority of ore minerals in the W Horizon at ∼500 °C or moderate to high subsolidus temperatures (400–600 °C). Local transport by aqueous fluids becomes evident as minerals recrystallize down to <300 °C. The PGE-enriched W Horizon ores exhibit a complex post-magmatic history dominated by the effects of oxidation during cooling of a Cu-PGE enriched magma source from a deep reservoir.     

Genesis of REE minerals in the karstic bauxite in western Guangxi,China, and its constraints on the deposit formation conditions

Karstic bauxites in western Guangxi, China, comprise two subtypes: Permian bauxite and Quaternary bauxite. The Quaternary bauxite originated from the breaking up, rolling, and accumulating of Permian bauxite in karstic depressions in Quaternary. Various types of rare earth element (REE) minerals were discovered during the formation of the Permian and Quaternary bauxites from the Xinxu, Longhe, and Tianyang bauxite deposits in this study. Five types of REE minerals, including bastnäsite, parisite, cerianite, rhabdophane, and churchite, were identified. Bastnäsite and parisite are the most abundant, and they are widely developed in the Permian ore and also present in the Quaternary ore. Obvious variations in bastnäsite and parisite REE compositions were observed, which is ascribed to distinctions in the source materials in the primary weathering profile from different areas. The mode of occurrence of bastnäsite and parisite suggests they were mainly precipitated under alkaline and reducing conditions during the Permian bauxite-forming stage and underwent intensive corrosion in the Quaternary. Churchite was formed during the Permian weathering stage under acidic condition. Both cerianite and rhabdophane occur in fractures within the Permian bauxite ore, indicating that both formed during the Quaternary weathering stage. It is considered that the rhabdophane enriched in Ce have formed locally, in the process of that the Ce^3 +, released from bastnäsite rapidly, entered the rhabdophane lattice before being oxidized to Ce^4 +. Cerianite was mainly found in association with Mn–Al hydroxides, suggesting that the released Ce^3 + was oxidized into Ce^4 + and precipitated cerianite in fractures within the Permian bauxite ore. Mass balance equations reveal a depletion in nearly all REEs during the transformation from the Permian to the Quaternary bauxite ore, mainly caused by the dissolution of bastnäsite and parisite. The genesis of the REE minerals, together with the occurrence of other minerals, indicates that intensively acidic and oxidizing conditions developed before the formation of the Permian bauxite ore. Towards the end of the Permian, the conditions became reducing and alkaline, favorable for the large-scale bauxitization. The Quaternary bauxite-forming stage was characterized by variable pH and Eh conditions, with acidic (pH = 4–6) and oxidizing (Eh > 2) conditions at the surface of the exposed Permian bauxite ore.     

Stability of biological and inorganic hemimorphite: Implications for hemimorphite precipitation in non-sulfide Zn deposits

Hemimorphite, Zn₄Si₂O₇(OH)₂·H₂O, one of the most common minerals in non-sulfide Zn deposits, together with smithsonite and hydrozincite, is one of the most abundant minerals in the “calamine” deposits in SW Sardinia. In spite of their importance for the development of ore genesis models, the stability properties of hemimorphite are poorly known. This paper presents solubility experiments on two different types of hemimorphite: a “geological” hemimorphite from a supergene non-sulfide Zn deposit, of supposed abiotic origin, and a hemimorphite precipitated by bacterial activity. Both specimens were characterized, before and after the experiment, by Synchrotron Radiation X-ray powder diffraction, Scanning Electron Microscopy, and X-ray Absorption Spectroscopy. The calculated solubility product constants (logK_s) are similar for both “geological” and biogenic hemimorphite (30.3 ± 0.4 and 30.5 ± 0.1, respectively). During the solubility experiment, biological hemimorphite undergoes an amorphous to crystalline phase transition, and the distinctive features (mineralized bacterial sheaths and organic filaments), that allowed us to demonstrate its biological origin, are no longer recognizable by Scanning Electron Microscopy.The results of this study may be useful for developing ore genesis models, including evolution in a supergene environment, and in general for performing geochemical speciation and equilibrium calculations. Moreover, our findings open the way for a new interpretation of hemimorphite-forming processes, and suggest the possibility that bacteria may have played a role in the formation of this mineral in ore deposits.     

A combined fluid inclusion and S–Pb isotope study of the Neoproterozoic Pingshui volcanogenic massive sulfide Cu–Zn deposit,Southeast China

The Pingshui Cu–Zn deposit is located in the Jiangshan–Shaoxing fault zone, which marks the Neoproterozoic suture zone between the Yangtze block and Cathaysia block in South China. It contains 0.45 million tons of proven ore reserves with grades of 1.03 wt.% Cu and 1.83 wt.% Zn. This deposit is composed of stratiform, massive sulfide ore bodies, which contain more than 60 vol.% sulfide minerals. These ore bodies are hosted in altered mafic and felsic rocks (spilites and keratophyres) of the bimodal volcanic suite that makes up the Neoproterozoic Pingshui Formation. Metallic minerals include pyrite, chalcopyrite, sphalerite, tennantite, tetrahedrite and magnetite, with minor galena. Gangue minerals are quartz, sericite, chlorite, calcite, gypsum, barite and jasper. Three distinct mineralogical zones are recognized in these massive sulfide ore bodies: a distal zone composed of sphalerite + pyrite + barite (zone I); an intermediate zone characterized by a pyrite + sphalerite + chalcopyrite assemblages (zone II); and a proximal zone containing chalcopyrite + pyrite + magnetite (zone III). A thin, layer of exhalative jaspilite overlies the sulfide ore bodies except in the proximal zone. The volcanic rocks of the Pingshui Formation are all highly altered spilites and keratophyres, but their trace element geochemistry suggests that they were generated by partial melting of the depleted mantle in an island arc setting. Homogenization temperatures of the primary fluid inclusions in quartz from massive sulfide ores are between 217 and 328 °C, and their salinities range from 3.2 to 5.7 wt.% NaCl equivalent. Raman spectroscopy of the fluid inclusions showed that water is the dominant component, with no other volatile components. Fluid inclusion data suggest that the ore-forming fluids were derived from circulating seawater. The δ³⁴S values of pyrite from the massive sulfide ores range from − 3.6‰ to + 3.4‰, indicating that the sulfur was primarily leached from the arc volcanic rocks of the Pingshui Formation. Both pyrite from the massive sulfide ores and plagioclase from the spilites have similar lead isotope compositions, implying that the lead was also derived from the Pingshui Formation. The low lead contents of the massive sulfide ores and the geochemistry of their host rocks are similar to many VMS Cu–Zn deposits in Canada (e.g., Noranda) and thus can be classified as belonging to the bimodal-mafic subtype. The presence of magnetite and the absence of jaspilite and barite at the − 505 m level in the Pingshui deposit suggest that this level is most likely the central zone of the original lateral massive sulfide ore bodies. If this interpretation is correct, the deep part of the Pingshui Cu–Zn deposit may have significant exploration potential.     

The genesis of metal zonation in the Weilasituo and Bairendaba Ag–Zn–Pb–Cu–(Sn–W) deposits in the shallow part of a porphyry Sn–W–Rb system,Inner Mongolia,China

The Weilasituo and Bairendaba Zn–Pb–Ag–Cu–(Sn–W) sulphide deposits are located in the southern part of Great Xing'an Range of Inner Mongolia in China. The deposits are located at shallow depths in the newly discovered Weilasituo porphyry hosting Sn–W–Rb mineralization. The mineralization at Weilasituo and Bairendaba consist of zoned massive sulphide veins within fractures cutting the Xilinhot Metamorphic Complex and quartz diorite. The Weilasituo deposit gradually zones from the Cu-rich Zn–Cu sulphide mineralization in the west to Zn-rich Zn–Cu sulphide mineralization in the east. The Bairendaba deposit has a Cu-bearing and Zn-rich core through a transitional zone devoid of copper to an outer zone of Zn–Pb–Ag mineralization. Three main veins contain more than 50 wt.% of the contained metal in the two deposits with their metal ratios displaying a systematic and gradual increase in Zn/Cu, Pb/Zn and Ag/Zn ratios from the western part of Weilasituo to the eastern part of Bairendaba.Three stages of vein-type mineralization are recognized. Early, sub-economic mineralization consists of a variable proportion of euhedral arsenopyrite, pyrite, quartz, and rare wolframite, scheelite, cassiterite, magnetite and cobaltite. This was succeeded by main stage mineralization with economic concentration of zoned Cu, Zn, Pb and Ag sulphide minerals along strike within the veins. The zones consist of the assemblages: (1) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–quartz–fluorite) at west Weilasituo; (2) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) at east Weilasituo; (3) pyrrhotite–Fe-rich sphalerite–chalcopyrite(–galena–tetrahedrite–quartz–fluorite) in the centre of Bairendaba; (4) pyrrhotite–Fe-rich sphalerite–galena(–chalcopyrite–tetrahedrite–quartz–fluorite) in the transition zone of Bairendaba; and (5) pyrrhotite–Fe-rich sphalerite–galena–tetrahedrite(–chalcopyrite–falkmanite–argentite–pyrargyrite–quartz–fluorite) in the outer zone at Bairendaba. Post-main ore stage is devoid of sulphides and characterized overprinting of fluorite, sericite, chlorite, illite, kaolinite and calcite.Zircon SHRIMP U–Pb dating, Zircon LA–ICP–MS U–Pb dating, molybdenite Re–Os isochron dating, and muscovite Ar–Ar dating indicate the Beidashan granitic batholith was intruded at 140 ± 3 Ma (MSWD = 3.3), the porphyritic monzogranite from marginal facies of the Beidashan batholith was intruded at 139 ± 2 Ma (MSWD = 0.75), the mineralized quartz porphyry was intruded at 135 ± 2 Ma (MSWD = 0.91), the greisen mineralization occurred at 135 ± 11 Ma (MSWD = 7.2), and the post-main ore stage muscovite deposited at 129.5 ± 0.9 Ma. The new geochronology data show the porphyry Sn–W–Rb and vein-type sulphide mineralization are contemporaneous with granitic magmatism in the region.The metal zonation at the Weilasituo and Bairendaba deposits is a result of progressive metal deposition. This was during the evolution of a metal-bearing fluid along the strike of the veins and during the main stage of ore formation at the upper part of the deep-seated porphyry Sn–W–Rb system. This progressive zonation indicates that the deposits represent end-numbers formed from one ore-forming fluid, which moved from west to east from the porphyry. The metal zonation patterns of the major veins are consistent with metal-bearing fluid entering the system with the precipitation of chalcopyrite proximally and sphalerite, galena and Ag-bearing minerals more distally. We show that the mechanism of metal deposition is therefore controlled by thermodynamic conditions resulting in the progressive separation of sulphides from the metal-bearing fluid. The temperature gradient between the inflow zone and the outflow zone appears to be one of the key parameters controlling the formation of the metal zonation pattern. The sulphide precipitation sequence is consistent with a low fS₂ and low fO₂ state of the acidic metal-bearing fluid. The metal zonation pattern provides helpful clues from which it is possible to establish the nature of fluid migration and metal deposition models to locate a possible porphyry mineralization at depth in the Great Xing'an Range, which is consistent with the geology of the newly discovered porphyry Sn–W–Rb system.     

Geochemical and mineralogical evidence for a coal-hosted uranium deposit in the Yili Basin,Xinjiang, northwestern China

The petrological, geochemical, and mineralogical compositions of the coal-hosted Jurassic uranium ore deposit in the Yili Basin of Xinjiang province, northwestern China, were investigated using optical microscopy and field emission-scanning electron microscopy in conjunction with an energy-dispersive X-ray spectrometer, as well as X-ray powder diffraction, X-ray fluorescence, and inductively coupled plasma mass spectrometry. The Yili coal is of high volatile C/B bituminous rank (0.51–0.59% vitrinite reflectance) and has a medium sulfur content (1.32% on average). Fusinite and semifusinite generally dominate the maceral assemblage, which exhibits forms suggesting fire-driven formation of those macerals together with forms suggesting degradation of wood followed by burning. The Yili coals are characterized by high concentrations of U (up to 7207 μg/g), Se (up to 253 μg/g), Mo (1248 μg/g), and Re (up to 34 μg/g), as well as As (up to 234 μg/g) and Hg (up to 3858 ng/g). Relative to the upper continental crust, the rare earth elements (REEs) in the coals are characterized by heavy or/and medium REE enrichment. The minerals in the Yili coals are mainly quartz, kaolinite, illite and illite/smectite, as well as, to a lesser extent, K-feldspar, chlorite, pyrite, and trace amounts of calcite, dolomite, amphibole, millerite, chalcopyrite, cattierite, siegenite, ferroselite, krutaite, eskebornite, pitchblende, coffinite, silicorhabdophane, and zircon. The enrichment and modes of occurrence of the trace elements, and also of the minerals in the coal, are attributed to derivation from a sediment source region of felsic and intermediate petrological composition, and to two different later-stage solutions (a U–Se–Mo–Re rich infiltrational and a Hg–As-rich exfiltrational volcanogenic solution). The main elements with high enrichment factors, U, Se, As, and Hg, overall exhibit a mixed organic–inorganic affinity. The uranium minerals, pitchblende and coffinite, occur as cavity-fillings in structured inertinite macerals. Selenium, As, and Hg in high-pyrite samples mainly show a sulfide affinity.     

Tube fossils from gossanites of the Urals VHMS deposits,Russia: Authigenic mineral assemblages and trace element distributions

The occurrence, types, morphology, and mineralogical characteristics of tube microfossils were studied in gossanites from twelve VHMS deposits of the Urals. Several types of tube microfossils were recognized, including siboglinids, polychaetes and calcerous serpulids, replaced by a variety of minerals (e.g. hematite–quartz, hematite–chlorite, carbonate–hematite) depending on the nature of the substrate prior to the formation of the gossanites. Colonial hematite tube microfossils (~ 150 μm across,1–2 mm long) are composed of hematitic outer and inner walls, and may exhibit a cellular structure within their cavities. Spherical forms are saturated with Fe-oxidizing bacteria inside the tubes – probably analogues of trophosomes. Colloform stromatolitic outer wall surfaces are characterized by the presence of numerous interlaced filaments of hematite (2–3 μm diameter, up to 1–2 mm long). Between tube microfossils, the hematitized cement contains bundles of hematitized filaments with structures similar to the hyphae of fungi. Hematite–chlorite tube microfossils are scattered in gossanites, mostly as biological debris. They are typically 30 to 300 μm in diameter and 1 to 5 mm long. The layered structure of their tube walls is characterized by hematite–quartz and chlorite layers. Abundant filamentous bacteria coated by glycocalix and chlorite stromatolite are associated with hematite–chlorite tubes. The carbonate–hematite tube microfossils (up to 300 μm across, 2–3 mm long) occur in carbonate-rich gossanites. The tubes are characterized by fine (~ 10 μm thick) walls of hematite and cavities dominated by relatively dark carbonate or hematite. Carbonates may be present both in walls and cavities. Stromatolite-like leucoxene or hematite–carbonate aggregates were also found in association with tubes. Randomly oriented filaments are composed of ankerite. Single filaments are composed of individual cells, typically smaller than 100 nm across, similar to that of magnetotactic bacteria.Three dimensional tomographic images of all types of tube microfossils demonstrate a clear wavy microlayering from outer and inner walls, which may reflect segmentation of the tube worms. The traces of burrowing or fragments of glycocalix with relict spheres are typical of tube microfossils from gossanites.The carbon isotopic composition of carbonates associated with tube microfossils from hematite–quartz, hematite–carbonate, and hematite–chlorite gossanites average − 7.2, − 6.8, –22.8‰, PDB, respectively. These values are indicative of a biogenic origin for the carbonates. The oxygen isotopic composition of these carbonates is similar in all three gossanite types averaging + 13.5, + 14.2, + 13.0‰ (relative to SMOW), and indicative of active sulfate reduction during the diagenetic (and anadiagenetic) stages of the sediments evolution. The trace element characteristics of hematite from tube microfossils are characterized by high contents of following trace elements (average, ppm): Mn (1529), As (714), V (540), W (537), Mo (35), and U (5). Such high contents are most likely the result of metal and metalloid sorption by fine particles of precursor iron hydroxides during the oxidation of sulfides and decomposition of hyaloclasts via microbially-mediated reactions.     

Base and precious metal mineralization in Middle Jurassic rocks of the Lesser Caucasus: A review of geology and metallogeny and new data from the Kapan,Alaverdi and Mehmana districts

The polymetallic Cu–Au–Ag–Zn ± Pb, Cu–Au and Cu deposits in the Kapan, Alaverdi and Mehmana mining districts of Armenia and the Nagorno–Karabakh region form part of the Tethyan belt. They are hosted by Middle Jurassic rocks of the Lesser Caucasus paleo-island arc, which can be divided into the Kapan Zone and the Somkheto–Karabakh Island Arc. Mineralization in Middle Jurassic rocks of this paleo-island arc domain formed during the first of three recognized Mesozoic to Cenozoic metallogenic epochs. The Middle Jurassic to Early Cretaceous metallogenic epoch comprises porphyry Cu, skarn and epithermal deposits related to Late Jurassic and Early Cretaceous intrusions. The second and third metallogenic epochs of the Lesser Caucasus are represented by Late Cretaceous volcanogenic massive sulfide (VMS) deposits with transitional features towards epithermal mineralization and by Eocene to Miocene world-class porphyry Mo–Cu and epithermal precious metal deposits, respectively.The ore deposits in the Kapan, Alaverdi and Mehmana mining districts are poorly understood and previous researchers named them as copper–pyrite, Cu–Au or polymetallic deposits. Different genetic origins were proposed for their formation, including VMS and porphyry-related scenarios. The ore deposits in the Kapan, Alaverdi and Mehmana mining districts are characterized by diverse mineralization styles, which include polymetallic veins, massive stratiform replacement ore bodies at lithological contacts, and stockwork style mineralization. Sericitic, argillic and advanced argillic alteration assemblages are widespread in the deposits which have intermediate to high-sulfidation state mineral parageneses that consist of tennantite–tetrahedrite plus chalcopyrite and enargite–luzonite–colusite, respectively. The ore deposits are spatially associated with differentiated calc-alkaline intrusions and pebble dykes are widespread. Published δ³⁴S values for sulfides and sulfates are in agreement with a magmatic source for the bulk sulfur whereas published δ³⁴S values of sulfate minerals partly overlap with the isotopic composition of contemporaneous seawater. Published mineralization ages demonstrate discrete ore forming pulses from Middle Jurassic to the Late Jurassic–Early Cretaceous boundary, indicating time gaps of 5 to 20 m.y. in between the partly subaqueous deposition of the host rocks and the epigenetic mineralization.Most of the described characteristics indicate an intrusion-related origin for the ore deposits in Middle Jurassic rocks of the Lesser Caucasus, whereas a hybrid VMS–epithermal–porphyry scenario might apply for deposits with both VMS- and intrusion-related features.The volcanic Middle Jurassic host rocks for mineralization and Middle to Late Jurassic intrusive rocks from the Somkheto–Karabakh Island Arc and the Kapan Zone show typical subduction-related calc-alkaline signature. They are enriched in LILE such as K, Rb and Ba and show negative anomalies in HFSE such as Nb and Ta. The ubiquitous presence of amphibole in Middle Jurassic volcanic rocks reflects magmas with high water contents. Flat REE patterns ([La/Yb]_N = 0.89–1.23) indicate a depleted mantle source, and concave-upward (listric-shaped) MREE–HREE patterns ([Dy/Yb]_N = 0.75–1.21) suggest melting from a shallow mantle reservoir. Similar trace element patterns of Middle Jurassic rocks from the Somkheto–Karabakh Island Arc and the Kapan Zone indicate that these two tectonic units form part of one discontinuous segmented arc. Similar petrogenetic and ore-forming processes operated along its axis and Middle Jurassic volcanic and volcanosedimentary rocks constitute the preferential host for polymetallic Cu–Au–Ag–Zn ± Pb, Cu–Au and Cu mineralization, both in the Somkheto–Karabakh Island Arc and the Kapan Zone.     

Hydrothermal mineralization in the sandstone–hosted Hangjinqi uranium deposit,North Ordos Basin,China

Tabular–type uranium ore deposits (the Hangjinqi and Daying deposits) have recently been found in the Middle Jurassic Zhiluo Formation, north of the Ordos Basin, China. Petrographic observations, the chemical composition of U minerals determined by EMPA and fs–LA–ICP–MS, whole rock geochemistry and the microthermometric study of fluid inclusions have been integrated to characterize the genetic conditions of the U mineralization in the Hangjinqi sandstone–hosted deposit. Two different groups of U minerals have been identified. One group includes coffinite(I) associated with vanadium–rich micas. Coffinite(I) is enriched in vanadium (V) and devoid of iron (Fe) and yttrium (Y) and has a LREE–enriched chondrite–normalized REE pattern. The U minerals of this group are similar to meteoric fluid infiltration related deposits. The second group has coeval coffinite(II) and coarsely crystalline calcite cement. Coffinite(II) is enriched in Y and Fe and depleted in V and is marked by a flat chondrite–normalized REE pattern, which is compatible with typical hydrothermal genetic deposits with high–salinity mineralizing fluids. The temperature and salinity of the primary aqueous inclusions in the ore–stage calcite are 120–180 °C and 8.00–16.34% (eq. wt% NaCl), respectively. These mineral assemblages, temperatures and salinities indicate that the Hangjinqi deposit was affected by two distinct types of ore–bearing fluids: low–salinity meteoric waters and high–salinity hydrothermal fluids. The meteoric fluids event began at 97 ± 5 Ma with the titling of the northern Ordos Basin and the uplift of the Hetao region to the north. Hydrothermal U mineralization occurred since 39 ± 2 Ma with the rifting of the Hetao graben. Thus, the previous biogenic model for the U mineralization should be modified in the uraniferous region of the north Ordos Basin.     

Water content in minerals of mantle xenoliths from the Udachnaya pipe kimberlites (Yakutia)

Distribution of water among the main rock-forming nominally anhydrous minerals of mantle xenoliths of peridotitic and eclogitic parageneses from the Udachnaya kimberlite pipe, Yakutia, has been studied by IR spectroscopy. The spectra of all minerals exhibit vibrations attributed to hydroxyl structural defects. The content of H₂O (ppm) in minerals of peridotites is as follows: 23–75 in olivine, 52–317 in orthopyroxene, 29–126 in clinopyroxene, and 0–95 in garnet. In eclogites, garnet contains up to 833 ppm H₂O, and clinopyroxene, up to 1898 ppm (~ 0.19 wt.%). The obtained data and the results of previous studies of minerals of mantle xenoliths show wide variations in H₂O contents both within different kimberlite provinces and within the Udachnaya kimberlite pipe. Judging from the volume ratios of mineral phases in the studied xenoliths, the water content varies over narrow ranges of values, 38–126 ppm. At the same time, the water content in the studied eclogite xenoliths is much higher and varies widely, 391–1112 ppm.     

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.     

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.     

Genesis of Si-rich carbonatites in Huanglongpu Mo deposit,Lesser Qinling orogen,China and significance for Mo mineralization

The Huanglongpu carbonatite-related Mo ore field is located in the Lesser Qinling Orogenic belt in the southern margin of the North China block. The ore field is composed of six deposits, Yuantou, Wengongling, Dashigou, Shijiawan, Taoyuan and Erdaohe, all of which are genetically related to carbonatite dykes except for the Shijiawan deposit which is associated with a granitic porphyry. The Yuantou carbonatite dykes intruded into Archean gneiss and other carbonatites emplaced into Mesoproterozoic volcanic and sediment rocks. The carbonatites are mainly composed of calcite and variable amounts of quartz and K-feldspar and minor molybdenite. Re–Os dating of molybdenite from the Yuantou carbonatite yields a weighted average age of 225.0 ± 7.6 Ma, consistent with the molybdenite age (221 Ma) from the Dashigou deposit. The rocks are characterized by high heavy REE (HREE) contents and consistent flat REE distribution patterns with La/Yb_cn ~ 1. Quartz in the carbonatites from Yuantou and Dashigou deposits shows consistent O isotopes (8.1–10.2‰) similar to the associated calcite (7.2–9.5‰). The quartz and associated K-feldspar contain lower Zr, Hf and higher HREE abundances and negligible Eu anomaly relative to those from the granite porphyry in Shijiawan. Both minerals are primary products in the carbonatitic liquid, and not captured from the wall-rocks or crustal-derived silicate magmas, or a hydrothermal origin. Thus, the Huanglongpu carbonatitic liquids were enriched in Si and Mo, which may be produced by intensely fractional crystallization of non-silicate minerals.     

Metallogeny of the Northern Norrbotten Ore Province,northern Fennoscandian Shield with emphasis on IOCG and apatite-iron ore deposits

The Northern Norrbotten Ore Province in northernmost Sweden includes the type localities for Kiruna-type apatite iron deposits and has been the focus for intense exploration and research related to Fe oxide-Cu-Au mineralisation during the last decades. Several different types of Fe-oxide and Cu-Au ± Fe oxide mineralisation occur in the region and include: stratiform Cu ± Zn ± Pb ± Fe oxide type, iron formations (including BIF's), Kiruna-type apatite iron ore, and epigenetic Cu ± Au ± Fe oxide type which may be further subdivided into different styles of mineralisation, some of them with typical IOCG (Iron Oxide-Copper-Gold) characteristics. Generally, the formation of Fe oxide ± Cu ± Au mineralisation is directly or indirectly dated between ~ 2.1 and 1.75 Ga, thus spanning about 350 m.y. of geological evolution.The current paper will present in more detail the characteristics of certain key deposits, and aims to put the global concepts of Fe-oxide Cu-Au mineralisations into a regional context. The focus will be on iron deposits and various types of deposits containing Fe-oxides and Cu-sulphides in different proportions which generally have some characteristics in common with the IOCG style. In particular, ore fluid characteristics (magmatic versus non-magmatic) and new geochronological data are used to link the ore-forming processes with the overall crustal evolution to generate a metallogenetic model.Rift bounded shallow marine basins developed at ~ 2.1–2.0 Ga following a long period of extensional tectonics within the Greenstone-dominated, 2.5–2.0 Ga Karelian craton. The ~ 1.9–1.8 Ga Svecofennian Orogen is characterised by subduction and accretion from the southwest. An initial emplacement of calc-alkaline magmas into ~ 1.9 Ga continental arcs led to the formation of the Haparanda Suite and the Porphyrite Group volcanic rocks. Following this early stage of magmatic activity, and separated from it by the earliest deformation and metamorphism, more alkali-rich magmas of the Perthite Monzonite Suite and the Kiirunavaara Group volcanic rocks were formed at ~ 1.88 Ga. Subsequently, partial melting of the middle crust produced large volumes of ~ 1.85 and 1.8 Ga S-type granites in conjunction with subduction related A −/I-type magmatism and associated deformation and metamorphism.In our metallogenetic model the ore formation is considered to relate to the geological evolution as follows. Iron formations and a few stratiform sulphide deposits were deposited in relation to exhalative processes in rift bounded marine basins. The iron formations may be sub-divided into BIF- (banded iron formations) and Mg-rich types, and at several locations these types grade into each other. There is no direct age evidence to constrain the deposition of iron formations, but stable isotope data and stratigraphic correlations suggest a formation within the 2.1–2.0 Ga age range. The major Kiruna-type ores formed from an iron-rich magma (generally with a hydrothermal over-print) and are restricted to areas occupied by volcanic rocks of the Kiirunavaara Group. It is suggested here that 1.89–1.88 Ga tholeiitic magmas underwent magma liquid immiscibility reactions during fractionation and interaction with crustal rocks, including metaevaporites, generating more felsic magmatic rocks and Kiruna-type iron deposits. A second generation of this ore type, with a minor economic importance, appears to have been formed about 100 Ma later. The epigenetic Cu-Au ± Fe oxide mineralisation formed during two stages of the Svecofennian evolution in association with magmatic and metamorphic events and crustal-scale shear zones. During the first stage of mineralisation, from 1.89–1.88 Ga, intrusion-related (porphyry-style) mineralisation and Cu-Au deposits of IOCG affinity formed from magmatic-hydrothermal systems, whereas vein-style and shear zone deposits largely formed at c. 1.78 Ga.The large range of different Fe oxide and Cu-Au ± Fe oxide deposits in Northern Norrbotten is associated with various alteration systems, involving e.g. scapolite, albite, K feldspar, biotite, carbonates, tourmaline and sericite. However, among the apatite iron ores and the epigenetic Cu-Au ± Fe oxide deposits the character of mineralisation, type of ore- and alteration minerals and metal associations are partly controlled by stratigraphic position (i.e. depth of emplacement). Highly saline, NaCl + CaCl₂ dominated fluids, commonly also including a CO₂-rich population, appear to be a common characteristic feature irrespective of type and age of deposits. Thus, fluids with similar characteristics appear to have been active during quite different stages of the geological evolution. Ore fluids related to epigenetic Cu-Au ± Fe oxides display a trend with decreasing salinity, which probably was caused by mixing with meteoric water. Tentatively, this can be linked to different CuAu ore paragenesis, including an initial (magnetite)-pyrite-chalcopyrite stage, a main chalcopyrite stage, and a late bornite stage.Based on the anion composition and the Br/Cl ratio of ore related fluids bittern brines and metaevaporites (including scapolite) seem to be important sources to the high salinity hydrothermal systems generating most of the deposits in Norrbotten. Depending on local conditions and position in the crust these fluids generated a variety of Cu-Au deposits. These include typical IOCG-deposits (Fe-oxides and Cu-Au are part of the same process), IOCG of iron stone type (pre-existing Fe-oxide deposit with later addition of Cu-Au), IOCG of reduced type (lacking Fe-oxides due to local reducing conditions) and vein-style Cu-Au deposits. From a strict genetic point of view, IOCG deposits that formed from fluids of a mainly magmatic origin should be considered to be a different type than those deposits associated with mainly non-magmatic fluids. The former tend to overlap with porphyry systems, whereas those of a mainly non-magmatic origin overlap with sediment hosted Cu-deposits with respect to their origin and character of the ore fluids.     

Hydrothermal altered serpentinized zone and a study of Ni-magnesioferrite–magnetite–awaruite occurrences in Wadi Hibi,Northern Oman Mountain: Discrimination through ASTER mapping

Economic important minerals and ore deposits are common in hydrothermal altered serpentinized zone. Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) satellite sensor is capable of discrimination of such hydrothermal mineralized zone and detection of hydrothermal altered minerals. In the present study, the hydrothermal altered serpentinized harzburgites of Wadi Hibi area of Northern Oman Mountains have been discriminated by using ASTER VNIR–SWIR spectral bands by image processing methods and the occurrences of Ni-magnesioferrite–magnetite–awaruite in the rocks are studied. The color composite RGB image developed using ASTER spectral bands 8, 4 and 1, mapped well the occurrence of weathered peridotites by pale green to dark blue in colors and discriminated the hydrothermally altered serpentinized rocks by pale brown to dark blue colors due to the strong absorption of OH and Mg–OH molecules that occurred in the serpentine minerals of the rocks in the study area. The ASTER band ratios 4/7, 4/1, and 2/3 × 4/3 RGB images studied are capable of discrimination of hydrothermal mineralized areas more clear by pale blue to purple colors due to the strong absorption of such hydroxyl bearing serpentine minerals. The studied image processing methods are evaluated by applying to the region of Wadi Sarami situated in the Semail ophiolite (Oman). In addition to that, the occurrence of serpentine minerals namely, lizardite and antigorite in the hydrothermally altered serpentinized region are detected qualitatively and quantitatively using Spectral Angle Mapper (SAM) supervised classification image processing method and studied.The interpreted images are verified in the field and checked for the occurrences of minerals including Ni-magnesioferrite, magnetite, pentlandite and awaruite and are confirmed through laboratory studies. Petrographic study of serpentinized harzburgites shows that the rocks consist predominantly of antigorite and lizardite serpentines, olivine and have the opaque minerals assemblage of Ni-magnesioferrite + magnetite + awaruite + pentlandite developed during serpentinization of the rock. The occurrences of such minerals are confirmed by XRD, electron microprobe analyses and spectral measurements in the laboratory.ASTER sensor proved its capability in discriminating the hydrothermal altered serpentinized zone and detecting the mineral occurrences and thus the study recommends the technique to the exploration geologists, scientists and mining geologists for mapping of such rocks and minerals in the similar arid region.     

Effects of acid-sulfate weathering and cyanide-containing gold tailings on the transport and fate of mercury and other metals in Gossan Creek: Murray Brook mine,New Brunswick,Canada

Gossan Creek, a headwater stream in the SE Upsalquitch River watershed in New Brunswick, Canada, contains elevated concentrations of total Hg (Hg_T up to 60 μg/L). Aqueous geochemical investigations of the shallow groundwater at the headwaters of the creek confirm that the source of Hg is a contaminated groundwater plume (neutral pH with Hg and Cl concentrations up to 150 μg/L and 20 mg/L, respectively), originating from the Murray Brook mine tailings, that discharges at the headwaters of the creek. The discharge area of the contaminant plume was partially delineated based on elevated pH and Cl concentrations in the groundwater. The local groundwater outside of the plume contains much lower concentrations of Hg and Cl (<0.1 μg/L and 3.8 mg/L, respectively) and displays the chemical characteristics of an acid-sulfate weathering system, with low pH (4.1–5.5) and elevated concentrations of Cu, Zn, Pb and SO₄ (up to 5400 μg Cu/L, 8700 μg Zn/L, 70 μg Pb/L and 330 mg SO₄/L), derived from oxidation of sulfide minerals in the Murray Brook volcanogenic massive sulfide deposit and surrounding bedrock. The Hg_T mass loads measured at various hydrologic control points along the stream system indicate that 95–99% of the dissolved Hg_T is attenuated in the first 3–4 km from the source. Analyses of creek bed sediments for Au, Ag, Cu, Zn, Pb and Hg indicate that these metals have partitioned strongly to the sediments. Mineralogical investigations of the contaminated sediments using analytical scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), reveal discrete particles (<1–2 μm) of metacinnabar (HgS), mixed Au–Ag–Hg amalgam, Cu sulfide and Ag sulfide.     

Timing of skarn deposit formation of the Tonglushan ore district,southeastern Hubei Province,Middle–Lower Yangtze River Valley metallogenic belt and its implications

The Tonglushan ore district in the Middle–Lower Yangtze River Valley metallogenic belt includes the Tonglushan Cu–Fe, the Jiguanzui Au–Cu, and the Taohuazui Au–Cu skarn deposits. They are characterized by NE-striking ore bodies and hosted at the contact of Triassic carbonate rocks and Late Mesozoic granitoid deposits. New Sensitive High-Resolution Ion Microprobe (SHRIMP) and Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA–ICP-MS) zircon U–Pb, molybdenite Re–Os, and phlogopite ⁴⁰Ar–³⁹Ar ages indicate that these skarn deposits formed between 140.3 ± 1.1 and 137.3 ± 2.4 Ma. These dates are identical to the zircon U–Pb ages for host quartz diorites ranging from 140 ± 2 to 139 ± 1 Ma. These results confirm that both skarn mineralization and related intrusions were initiated during the Early Cretaceous. The high rhenium contents (261.4–1152 μg/g) of molybdenites indicate that a metasomatic mantle fluid was involved in the ore-forming process of these skarn ore systems. This conclusion is consistent with previously published constraints from sulfur, deuterium, and oxygen isotope compositions, and the geochemical signatures, and Sr–Nd isotopic data of the mineralization-hosting intrusions. Geological and geochronological evidence demonstrates that there were two igneous events in the Tonglushan ore district. The first resulted in the emplacement of quartz diorite during the Early Cretaceous (140 ± 2 to 139 ± 1 Ma), and the second is characterized by the eruption of volcanic rocks during the mid-Early Cretaceous (130 ± 2 to 124 ± 2 Ma). The former is spatially, temporally and genetically associated with skarn gold-bearing mineralization (140.3 ± 1.1 to 137.3 ± 2.4 Ma). The recognition of these two igneous events invalidates previous models that proposed continuous magmatism and associated mineral deposits in the Middle–Lower Yangtze River Valley metallogenic belt.     

Geological and geochemical constraints on the genesis of the Xiangquan Tl-only deposit,eastern China

The Xiangquan Tl deposit, located in the northern part of the Middle–Lower Yangtze Valley metallogenic belt, eastern China, is the only known Tl-only deposit. It is hosted in micritic limestone, marl and mudstone of the Lower Ordovician Lunshan Formation. The orebodies are controlled by the Xiao–Xiaolongwang–Dalongwang anticline and two reverse faults, and are generally stratabound and lenticular. Tl is only ore metal contained in disseminated, massive, brecciated and banded ores. The ore is composed of Tl-bearing pyrite, and gangue minerals quartz, fluorite, barite and carbonate. Alteration minerals include fluorite, barite, fine grained quartz and carbonate. Tl occurs isomorphously replacing iron in the lattice of pyrite, and less commonly as tiny independent Tl-bearing minerals which may be lafossaite (TlAsS₂) or lorandite (TlCl) appearing as 0.1–1 μm-sized cubic crystals. Xiangquan is a submarine sedimentary deposit and demonstrates that Tl, as a normally dispersed element, can form not only part of poly-metallic deposits but also as independent Tl deposits.