Seawater contribution to polymetallic Ni–Mo–PGE–Au mineralization in Early Cambrian black shales of South China: Evidence from Mo isotope,PGE, trace element,and REE geochemistry

The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ^98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ^98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 10⁷ compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.     

A multistage origin for Kupferschiefer mineralization

New Re–Os age determinations on mineralized material from the Polish Kupferschiefer elucidate the timing of mineralization and thus the likely mechanisms of ore deposition. Three mineralization parageneses were analysed: (a) chalcocite as pore space filling in sandstone, (b) disseminated Cu–Mo mineralization in shale, and (c) massive, bedded copper sulphides. The resulting ages fall into two ranges: 245.2 (± 1.6)–264.7 (± 1.8) Ma and 162.3 (± 0.8)–184.3 (± 2.2) Ma. These results substantiate previous age determinations, although no Upper Triassic ages were found in this study. Some of the younger ages for the mineralization could represent alteration and recrystallization of existing sulphides. The results confirm that mineralization took place in several stages, from soon after Kupferschiefer sediment deposition in the Upper Permian and for at least 100 m.y. after, until at least the Cretaceous. The genesis of the mineralization can be explained by the episodic release of hydrothermal fluids from the subsiding adjacent Southern Permian sedimentary basin, although the relative importance of each successive mineralizing ‘event’ for introducing additional metals is as yet unknown.     

Oxygen and carbon isotope and Sr/Ca signatures of high-latitude Permian to Jurassic calcite fossils from New Zealand and New Caledonia

Calcite fossils from New Zealand and New Caledonia provide insight into the Permian to Jurassic climatic history of Southern High Latitudes (southern HL) and Triassic Southern Intermediate Latitudes (southern IL). These results permit comparison with widely studied, coeval sections in Low Latitudes (LL) and IL. Oxygen isotope ratios of well-preserved shell materials indicate a partially pronounced Sea Surface Temperature (SST) gradient in the Permian, whereas for the Triassic no indication of cold climates in the southern HL is found. The Late Jurassic of New Zealand is characterized by a slight warming in the Oxfordian–Kimmeridgian and a subsequent cooling trend in the Tithonian. Systematic variations in the δ¹³C values of southern HL samples are in concert with those from LL sections and confirm the global nature of the carbon isotope signature and changes in the long-term carbon cycle reported earlier.Systematic changes of Sr/Ca ratios in Late Triassic brachiopods, falling from 1.19 mmol/mol in the Oretian (early Norian) to 0.67 mmol/mol in the Warepan (late Norian) and subsequently increasing to 1.10 mmol/mol in the Otapirian (~ Rhaetian), are observed. Also Sr/Ca ratios of Late Jurassic belemnite genera Belemnopsis and Hibolithes show synchronous changes in composition that may be attributed to secular variations in the seawater Sr/Ca ratio. For the two belemnite genera an increase from 1.17 mmol/mol in the Middle Heterian (~ Oxfordian) to 1.78 mmol/mol in the Mangaoran (~ late Middle Tithonian) and a subsequent decrease to 1.51 mmol/mol in the Waikatoan (~ Late Tithonian) is documented.     

Detrital zircon provenance of upper Cambrian-Permian strata and tectonic evolution of the Ellsworth Mountains,West Antarctica

Detrital zircons from the upper Cambrian-Devonian sandstones (Crashsite Group; n = 485) and Carboniferous tillite (Whiteout Conglomerate; n = 81) of the Ellsworth Mountains, Antarctica record a steady supply of Neoproterozoic (“Pan-African”) orogeny (~ 550–600 Ma), Grenville (~ 1000 Ma) and Neoarchean (~ 3000–3500 Ma) zircons into the northern marginal basin of Gondwana. The overlying Permian Glossopteris-bearing Polarstar Formation shales (n = 85) have the same zircon provenance as underlying units but also include a dominance of depositional-age (263 Ma) euhedral zircons which are interpreted to be of local, volcanic arc origin. Modeling of detrital zircon provenance suggests that source areas were present in Pan-African and Laurentian crust throughout the Paleozoic. We also report calcite twinning strain results (12 strain analyses; n = 398 twins) for the Cambrian Minaret Fm. in the Heritage range which is predominantly a layer-parallel shortening strain in the direction (WSW-ENE) of Permian Gondwanide orogen thrust transport. There is a secondary, sub-vertical twinning strain overprint. The initiation of localized lower-middle Cambrian rifting (Heritage Group deposition) in Grenville-aged crust as Gondwana amalgamated and the subsequent Jurassic counterclockwise rotation of the Ellsworth-Whitmore terrane out of the Permian Gondwanide belt into central Antarctica each remain tectonic curiosities.     

The role of evaporites in the formation of magnetite–apatite deposits along the Middle and Lower Yangtze River,China: Evidence from LA-ICP-MS analysis of fluid inclusions

Numerous magnetite–apatite deposits occur in the Ningwu and Luzong sedimentary basins along the Middle and Lower Yangtze River, China. These deposits are located in the contact zone of (gabbro)-dioritic porphyries with surrounding volcanic or sedimentary rocks and are characterized by massive, vein and disseminated magnetite–apatite ± anhydrite mineralization associated with voluminous sodic–calcic alteration. Petrologic and microthermometric studies on multiphase inclusions in pre- to syn-mineralization pyroxene and garnet from the deposits at Meishan (Ningwu basin), Luohe and Nihe (both in Luzong basin) demonstrate that they represent extremely saline brines (~ 90 wt.% NaCl_equiv) that were trapped at temperatures of about 780 °C. Laser ablation ICP-MS analyses and Raman spectroscopic studies on the natural fluid inclusions and synthetic fluid inclusions manufactured at similar P–T conditions reveal that the brines are composed mainly of Na (13–24 wt.%), K (7–11 wt.%), Ca (~ 7 wt.%), Fe (~ 2 wt.%), Cl (19–47 wt.%) and variable amounts of SO₄ (3–39 wt.%). Their Cl/Br, Na/K and Na/B ratios are markedly different from those of seawater evaporation brines and lie between those of magmatic fluids and sedimentary halite, suggesting a significant contribution from halite-bearing evaporites. High S/B and Ca/Na ratios in the fluid inclusions and heavy sulfur isotopic signatures of syn- to post-mineralization anhydrite (δ³⁴S_Anh = + 15.2 to + 16.9‰) and pyrite (δ³⁴S_Py = + 4.6‰ to + 12.1‰) further suggest a significant contribution from sedimentary anhydrite. These interpretations are in line with the presence of evaporite sequences in the lower parts of the sedimentary basins.The combined evidence thus suggests that the magnetite–apatite deposits along the Middle and Lower Yangtze River formed by fluids that exsolved from magmas that assimilated substantial amounts of Triassic evaporites during their ascent. Due to their Fe-oxide dominated mineralogy, their association with large-scale sodic–calcic alteration and their spatial and temporal associations with subvolcanic intrusions we interpret them as a special type of IOCG deposits that is characterized by unusually high contents of Na, Ca, Cl and SO₄ in the ore-forming fluids. Evaporite assimilation apparently led to the production of large amounts of high-salinity brine and thus to an enhanced capacity to extract iron from the (gabbro)-dioritic intrusions and to concentrate it in the form of ore bodies. Hence, we believe that evaporite-bearing sedimentary basins are more prospective for magnetite–apatite deposits than evaporite-free basins.     

Tectonics of the North Qilian orogen,NW China

The Qilian Orogen at the northern margin of the Tibetan Plateau is a type suture zone that recorded a complete history from continental breakup to ocean basin evolution, and to the ultimate continental collision in the time period from the Neoproterozoic to the Paleozoic. The Qilian Ocean, often interpreted as representing the “Proto-Tethyan Ocean”, may actually be an eastern branch of the worldwide “Iapetus Ocean” between the two continents of Baltica and Laurentia, opened at ≥ 710 Ma as a consequence of breakup of supercontinent Rodinia.Initiation of the subduction in the Qilian Ocean probably occurred at ~ 520 Ma with the development of an Andean-type active continental margin represented by infant arc magmatism of ~ 517–490 Ma. In the beginning of Ordovician (~ 490 Ma), part of the active margin was split from the continental Alashan block and the Andean-type active margin had thus evolved to western Pacific-type trench–arc–back-arc system represented by the MORB-like crust (i.e., SSZ-type ophiolite belt) formed in a back-arc basin setting in the time period of ~ 490–445 Ma. During this time, the subducting oceanic lithosphere underwent LT-HP metamorphism along a cold geotherm of ~ 6–7 °C/km.The Qilian Ocean was closed at the end of the Ordovician (~ 445 Ma). Continental blocks started to collide and the northern edge of the Qilian–Qaidam block was underthrust/dragged beneath the Alashan block by the downgoing oceanic lithosphere to depths of ~ 100–200 km at about 435–420 Ma. Intensive orogenic activities occurred in the late Silurian and early Devonian in response to the exhumation of the subducted crustal materials.Briefly, the Qilian Orogen is conceptually a type example of the workings of plate tectonics from continental breakup to the development and evolution of an ocean basin, to the initiation of oceanic subduction and formation of arc and back-arc system, and to the final continental collision/subduction and exhumation.     

Rapid Eocene erosion,sedimentation and burial in the eastern Himalayan syntaxis and its geodynamic significance

The lower Bomi Group of the eastern Himalayan syntaxis comprises a lithological package of sedimentary and igneous rocks that have been metamorphosed to upper amphibolite-facies conditions. The lower Bomi Group is bounded to the south by the Indus–Yarlung Suture and to the north by unmetamorphosed Paleozoic sediments of the Lhasa terrane. We report U–Pb zircon dating, geochemistry and petrography of gneiss, migmatite, mica schist and marble from the lower Bomi Group and explore their geological implications for the tectonic evolution of the eastern Himalaya. Zircons from the lower Bomi Group are composite. The inherited magmatic zircon cores display ²⁰⁶Pb/²³⁸U ages from ~ 74 Ma to ~ 41.5 Ma, indicating a probable source from the Gangdese magmatic arc. The metamorphic overgrowth zircons yielded ²⁰⁶Pb/²³⁸U ages ranging from ~ 38 Ma to ~ 23 Ma, that overlap the anatexis time (~ 37 Ma) recorded in the leucosome of the migmatites. Our data indicate that the lower Bomi Group do not represent Precambrian basement of the Lhasa terrane. Instead, the lower Bomi Group may represent sedimentary and igneous rocks of the residual forearc basin, similar to the Tsojiangding Group in the Xigaze area, derived from denudation of the hanging wall rocks during the India–Asia continental collision. We propose that following the Indian–Asian collision, the forearc basin was subducted, together with Himalayan lithologies from the Indian continental slab. The minimum age of detrital magmatic zircons from the supracrustal rocks is ~ 41.5 Ma and their metamorphism had happened at ~ 37 Ma. The short time interval (< 5 Ma) suggests that the tectonic processes associated with the eastern Himalayan syntaxis, encompassing uplift and erosion of the Gangdese terrane, followed by deposition, imbrication and subduction of the forearc basin, were extremely rapid during the Late Eocene.     

Application of pyrite trace element chemistry to exploration for SEDEX style Zn-Pb deposits: McArthur Basin,Northern Territory,Australia

Sedimentary pyrites in black shales contain abundant trace elements that provide information on the chemistry of the seawater at the time of sedimentation. This study focuses on the Barney Creek Formation (~ 1640 Ma) in the McArthur Basin in the Northern Territory of Australia, which is host to one of the world's largest SEDEX Zn-Pb-Ag deposits, and several smaller deposits. Fine-grained sedimentary pyrite has been sampled from three drill holes through the Barney Creek Formation at various distances from SEDEX mineralisation. Samples were selected through the stratigraphy of each hole and analysed by LA-ICPMS for a suite of 14 trace elements. The data show that sedimentary pyrite at the base of the Barney Creek Formation, closest (within 1 km) to SEDEX mineralisation, is strongly enriched in Zn and Tl by one to two orders of magnitude compared to the global average for sedimentary pyrite. In contrast sedimentary pyrite from the hole furthest from SEDEX mineralisation (~ 60 km) contains mean Zn and Tl values equal to, or less than, the global average. Based on the three drill hole pyrite data sets it is concluded that trace elements that are contributed to the basin during hydrothermal exhalation, and adsorbed into contemporaneous sedimentary pyrite, are principally Zn, Tl, Cu, Pb, Ag and As. In contrast, trace elements that are adsorbed into sedimentary pyrite from background seawater are principally Mo, Ni, Co, Se and As. These differences have enabled the development of a SEDEX fertility diagram for sedimentary basins, based on the composition of sedimentary pyrite, that distinguish high Zn, but barren shales, from high zinc SEDEX-related shales. In parallel with the increase in Zn and Tl in sedimentary pyrite approaching mineralisation there is a decrease in Ni, Co and Mo. This means that the ratios Zn/Ni and Tl/Co are particularly good pyrite vectors to SEDEX mineralisation in the McArthur Basin, varying over 4 to 6 orders of magnitude from barren shales to mineralised shales. It is speculated that the reason for the reverse relationship between Ni, Co and Zn, Tl may be caused by hydrothermal exhalations into the water column that effect the ion-exchange pyrite surface complexation processes that alter the uptake of these elements into sedimentary pyrite.Another important conclusion of this study is that hydrothermal exhalations into a sedimentary basin may affect the redox sensitive trace element chemistry of sedimentary pyrite and therefore the trace element chemistry of pyritic black shales. Nickel, Co and Mo all decrease in proximity to hydrothermal vents that form SEDEX deposits, whereas Zn, Tl and Pb increase. Selenium and bismuth are the only redox sensitive trace elements that appear to be unaffected by hydrothermal activity in the McArthur Basin. This has implications on how trace element concentrations of black shales and pyrite are used to reflect past global ocean chemistry.     

Late-glacial to Holocene transition in northern Spain deduced from land-snail shelly accumulations

Shells of the helicid Cepaea nemoralis were studied using taphonomic, isotopic and morphometric measurements to estimate late glacial–Holocene (~ 12.1–6.3 cal ka BP) environmental conditions in northern Spain. Higher taphonomic alteration among Holocene shells suggests lower sedimentation rates or higher shell-destruction rates than during glacial conditions. Shells preserved the aragonitic composition despite differing degree of skeleton damage. Shell δ¹³C values were ? 10.3 ± 1.1‰, ? 8.2 ± 2.3‰, and ? 7.3 ± 1.6‰ for modern, Holocene and late-glacial individuals, respectively. Higher δ¹³C values during the late-glacial and some Holocene periods imply higher water stress of C₃ plants and/or higher limestone contribution than today. Intrashell δ¹³C values were higher during juvenile stages suggesting higher limestone ingestion to promote shell growth. Shell δ¹⁸O values were ? 1.1 ± 0.7‰, ? 0.9 ± 0.8‰ and ? 0.1 ± 0.7‰ for modern, Holocene and late-glacial specimens, respectively. A snail flux-balance model suggests that during ~ 12.1 ? 10.9 cal ka BP conditions were drier and became wetter at ~ 8.4 ? 6.3 cal ka BP and today. Intrashell δ¹⁸O profiles reveal that glacial individuals experienced more extreme seasonality than interglacial shells, despite possible larger hibernation periods. Shell size correlated positively with δ¹⁸O values, suggesting that growth rates and ultimate adult size of C. nemoralis may respond to climate fluctuation in northern Spain.     

Geology,mineralization, and fluid inclusion characteristics of the Chorukh-Dairon W–Mo–Cu skarn deposit in the Middle Tien Shan,Northern Tajikistan

The Chorukh-Dairon deposit is part of the metallogenic belt of WMo, CuMo, AuW, and Au deposits along the Late Paleozoic active continental margin of the Tien Shan. It is related to the Late Carboniferous multiphase pluton, with successive intrusive phases of early monzogabbro through monzonite-quartz monzonite to monzogranite and leucogranite, and the latest lamprophyre dikes. The deposit is an example of complex W–Mo–Cu magmatic-hydrothermal system related to magnetite-series shoshonitic igneous suite. It contains zones of W–Cu–Mo oxidized prograde and retrograde skarns, with abundant scapolite, plagioclase, K-feldspar, andradite garnet, magnetite, as well as molybdoscheelite and minor chalcopyrite, and molybdenite. Skarns are overprinted by hydrosilicate alteration assemblages, with amphibole, chlorite, epidote, quartz, calcite, scapolite, albite, scheelite, and chalcopyrite, and are cut by quartz-carbonate-barite-fluorite-sulfide veins.The fluid evolution included a release of high temperature (~ 400–500 °C), high pressure (900–1100 to 700–800 bars), high salinity magmatic-hydrothermal aqueous chloride fluid, with its direct separation from crystallizing magma and formation of prograde and retrograde skarns. Fluid enrichment in Ca (up to 15–22 wt.% CaCl₂) at the retrograde skarn stage was possibly related to magmatic differentiation and provided intense molybdoscheelite deposition from a homogenous fluid. In contrast, hydrosilicate alteration assemblages were formed at lower temperatures (~ 350–400 °C) initially from a homogenous and then from a boiling Ca-rich (20–22 wt.% CaCl₂) magmatic-hydrothermal fluid, with the latter contributing to the most intense scheelite deposition. The stable isotope data (δ¹³C_CO2 = − 3.0 ± 0.5‰ and δ¹⁸О_H2O = + 6.5 ± 0.5‰, δ³⁴S = + 7.5 to + 7.7‰) obtained for the hydrosilicate stage minerals suggest significant fluid sourcing from magmatic and meteoric waters as well as from sedimentary rocks enriched in seawater sulfate, possibly evaporites, although a strongly homogenous character of the isotopic composition reveals intense isotope homogenization in a magmatic chamber. Some light sulfur isotope enrichment of sulfides from the quartz-carbonate-barite-fluorite-sulfide veins (δ³⁴S = + 6.0 to + 6.1‰) may be linked to the evolution of the magmatic source toward more mantle-related sulfur species, as these veins were formed after emplacement of the late mafic (lamprophyre) dikes.     

Evidence for SEDEX-style mineralization in the 1.7 Ga Tawallah Group,McArthur Basin,Australia

The Paleoproterozoic McArthur Basin (McArthur Group) of northern Australia hosts world-class sedimentary ‘exhalative’ (SEDEX) McArthur type Zn–Pb deposits, which are largely hosted within a sequence of 1.64 Ga pyritic carbonaceous shales deposited in an extensional rift setting. A well-known example of these is McArthur River (or Here's Your Chance [HYC] Zn–Pb–Ag deposit). The ~ 1.78 Ga McDermott and ~ 1.73 Ga Wollogorang formations (Tawallah Group) both contain carbonaceous shales deposited in similar environments. Our observations suggest the carbonaceous facies of the Wollogorang Formation were deposited under mostly euxinic conditions, with periodically-high concentrations of sedimentary pyrite deposition. The carbonaceous shales in the older McDermott Formation contain considerably less early pyrite, reflecting a mostly sulfide-poor, anoxic depositional environment. Localized fault-bound sub-basins likely facilitated lateral facies variations, which is evident from synsedimentary breccias.The presence of evaporitic oxidized facies within the McDermott and Wollogorang formations, alongside evidence for synsedimentary brecciation in reduced shales are favourable criteria for SEDEX-style base metal deposition. Both formations overlie volcanic units, which could have been sources of base metals. Detailed X-ray petrography, new geochemical data and sulfur isotope data from historical drill cores indicate multiple horizons of stratiform and sediment breccia-hosted base metal sulfide within carbonaceous shale units, with high-grade Zn concentrations. A close association between sphalerite and ferromanganean dolomite alteration draws comparisons with younger SEDEX mineralization at HYC. Additionally, SEDEX alteration indices, used demonstrably as a vector to the younger orebodies, indicate the sedimentary rocks analyzed in this study are marginally below the ore window when compared to the overlying mineralized stratigraphy.Our data imply that localized active circulation of metalliferous brines occurred in the Tawallah Group basin. High-grade sulfide deposition in reduced facies alteration may represent distal expressions of larger SEDEX-style deposits. Furthermore, abundant pyrite and high molybdenum in the Wollogorang Formation suggest the global oceanic sulfate concentration was sufficient by ~ 1.73 Ga to engender intermittent but strong bottom-water euxinia during shale deposition, thus providing a robust chemical trap for base metal sulfide mineralization.     

Magnetostratigraphy of deep drilling core SG-1 in the western Qaidam Basin (NE Tibetan Plateau) and its tectonic implications

The Qaidam Basin is the largest intermontane basin of the northeastern Tibetan Plateau and contains a continuous Cenozoic sequence of lacustrine sediments. A ~ 1000-m-deep drilling (SG-1) with an average core recovery of ~ 95% was carried out in the depocenter of the Chahansilatu playa (sub-depression) in the western Qaidam Basin, aimed to obtain a high-resolution record of the paleoenvironmental evolution and the erosion history. Stepwise alternating field and thermal demagnetization, together with rock magnetic results, revealed a stable remanent magnetization for most samples, carried by magnetite. The polarity sequence consisted of 16 normal and 15 reverse zones which can be correlated with chrons 1n to 2An of the global geomagnetic polarity time scale. Magnetostratigraphic results date the entire core SG-1 at ~ 2.77 Ma to ~ 0.1 Ma and yielded sediment accumulation rate (SAR) ranging from 26.1 cm/ka to 51.5 cm/ka. Maximum SARs occurred within the intervals of ~ 2.6–2.2 Ma and after ~ 0.8 Ma, indicating two episodes of erosion, which we relate to pulse tectonic uplift of the NE Tibetan Plateau with subsequent global cooling.     

Thermo-tectonic history of the Issyk-Kul basement (Kyrgyz Northern Tien Shan,Central Asia)

Lake Issyk-Kul occupies a large Late Mesozoic–Cenozoic intramontane basin between the mountain ranges of the Northern Kyrgyz Tien Shan. These ranges are often composed of granitoid basement that forms part of a complex mosaic assemblage of microcontinents and volcanic arcs. Several granites from the Terskey, Kungey, Trans-Ili and Zhetyzhol Ranges were dated with the zircon U/Pb method (SHRIMP, LA-ICP-MS) and yield concordant Late Ordovician–Silurian (~ 456–420 Ma) emplacement ages. These constrain the “Caledonian” accretion history of the Northern Kyrgyz Tien Shan in the amalgamated Palaeo-Kazakhstan continent. The ancestral Tien Shan orogen assembled in the Early Permian when final closure of the Turkestan Ocean ensued collision of Palaeo-Kazakhstan and Tarim. A Late Palaeozoic structural basement fabric formed and Middle–Late Permian post-collisional magmatism added to crustal growth of the Tien Shan. Permo‐Triassic cooling (~ 300–220 Ma) of the ancestral Tien Shan was unraveled using ⁴⁰Ar/³⁹Ar K-feldspar and titanite fission-track (FT) thermochronology on the Issyk-Kul granitoids. Apatite thermochronology (FT and U–Th–Sm/He) applied to the broader Issyk-Kul region elucidates the Meso-Cenozoic thermo-tectonic evolution and constrains several tectonic reactivation episodes in the Jurassic, Cretaceous and Cenozoic. Exhumation of the studied units occurred during a protracted period of intracontinental orogenesis, linked to far-field effects of Late Jurassic–Cretaceous accretion of peri-Gondwanan blocks from the Tethyan realm to Eurasian. Following a subsequent period of stability and peneplanation, incipient building of the modern Tien Shan orogen in Northern Kyrgyzstan started in the Oligocene according to our data. Intense basement cooling in distinct reactivated and fault-controlled sections of the Trans-Ili and Terskey Ranges finally pinpoint important Miocene–Pliocene (~ 22–5 Ma) exhumation of the Issyk-Kul basement. Late Cenozoic formation of the Tien Shan is associated with ongoing indentation of India into Eurasia and is a quintessential driving force for the reactivation of the entire Central Asian Orogenic Belt.     

3D geological modeling for prediction of subsurface Mo targets in the Luanchuan district,China

Three-dimensional (3D) district-scale geoscience information for the Luanchuan Mo district was integrated for understanding the development of its regional geology and ore-forming processes and for decision-making about potential targets for mineral exploration. The methodology and datasets used were: (1) construction of an initial geological model (25 km × 20 km × 2.5 km) using 1:10,000 scale geological map, nine geological cross-sections and gravity and magnetic data; (2) construction of three large-scale Mo deposits model (5 km × 4 km × 2.5 km) using 1:2000 scale geological and topographic maps, 288 boreholes (total core length of 158,700 m), and 32 1:2000 scale cross-sections; (3) 3D inversion of 1:25,000 scale gravity and magnetic data for identification metallogenic anomaly zones which are associated with Jurassic intrusions; (4) extraction of ore-controlling formation and sequence of the Luanchuan Group using the large-scale 3D models of Mo deposits and results of analysis of lithogeochemical samples from outcrops and borehole cores; (5) identification of ore-forming and ore-controlling faults using the large-scale 3D model of Mo deposits and mineralized Jurassic granite porphyry stocks; (6) boost weights-of-evidence and concentration–volume (C–V) fractal analyses to integrate metallogenic information and to identify and classify potential Mo targets. Four classes of exploration targets were identified using C–V modeling and 3D known orebodies model: the first and second class targets are mainly located in three large magma-skarn type deposit camps, occupying ~ 1.4 km³ with total estimated reserve of ~ 2.3 Mt; the third class targets, which are mainly located in Huangbeiling and Yuku deposit camps comprising concealed magma-skarn type deposits, occupy ~ 2.8 km³ and represent a new target exploration zone in the Luanchuan district; the fourth class targets, which are located in the Huoshenmiao, Majuan, and Daping zones, occupy ~ 15 km³ and represent potential mineral resources with likely similar orebody features as the Yuku deposit.     

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.     

Geology and genesis of the post-collisional porphyry–skarn deposit at Bangpu,Tibet

Bangpu deposit in Tibet is a large but poorly studied Mo-rich (~ 0.089 wt.%), and Cu-poor (~ 0.32 wt.%) porphyry deposit that formed in a post-collisional tectonic setting. The deposit is located in the Gangdese porphyry copper belt (GPCB), and formed at the same time (~ 15.32 Ma) as other deposits within the belt (12 ~ 18 Ma), although it is located further to the north and has a different ore assemblage (Mo–Pb–Zn–Cu) compared to other porphyry deposits (Cu–Mo) in this belt. Two distinct mineralization events have been identified in the Bangpu deposit which are porphyry Mo–(Cu) and skarn Pb–Zn mineralization. Porphyry Mo–(Cu) mineralization in the deposit is generally associated with a mid-Miocene porphyritic monzogranite rock, whereas skarn Pb–Zn mineralization is hosted by lower Permian limestone–clastic sequences. Coprecipitated pyrite and sphalerite from the Bangpu skarn yield a Rb–Sr isochron age of 13.9 ± 0.9 Ma. In addition, the account of garnet decreases and the account of both calcite and other carbonate minerals increases with distance from the porphyritic monzogranite, suggesting that the two distinct phases of mineralization in this deposit are part of the same metallogenic event.Four main magmatic units are associated with the Bangpu deposit, namely a Paleogene biotite monzogranite, and Miocene porphyritic monzogranite, diabase, and fine-grained diorite units. These units have zircon U–Pb ages of 62.24 ± 0.32, 14.63 ± 0.25, 14.46 ± 0.38, and 13.24 ± 0.04 Ma, respectively. Zircons from porphyritic monzogranite yield ε_Hf(t) values of 2.2–8.7, with an average of 5.4, whereas the associated diabase has a similar ε_Hf(t) value averaging at 4.7. The geochemistry of the Miocene intrusions at Bangpu suggests that they were derived from different sources. The porphyritic monzogranite has relatively higher heavy rare earth element (HREE) concentrations than do other ore-bearing porphyries in the GPCB and plots closer to the amphibolite lithofacies field in Y–Zr/Sm and Y–Sm/Yb diagrams. The Bangpu diabase contains high contents of MgO (> 7.92 wt.%), FeOt (> 8.03 wt.%) but low K₂O (< 0.22 wt.%) contents and with little fractionation of the rare earth elements (REEs), yielding shallow slopes on chondrite-normalized variation diagrams. These data indicate that the mineralized porphyritic monzogranite was generated by partial melting of a thickened ancient lower crust with some mantle components, whereas the diabase intrusion was directly derived from melting of upwelling asthenospheric mantle. An ancient lower crustal source for ore-forming porphyritic monzogranite explains why the Bangpu deposit is Mo-rich and Cu-poor rather than the Cu–Mo association in other porphyry deposits in the GPCB because Mo is dominantly from the ancient crust.The Bangpu deposit has alteration zonation, ranging from an inner zone of biotite alteration through silicified and phyllic alteration zones to an outer propylitic alteration zone, similar to typical porphyry deposits. Some distinct differences are also present, for example, K-feldspar alteration at Bangpu is so dispersed that a distinct zone of K-feldspar alteration has not been identified. Hypogene mineralization at Bangpu is characterized by the early-stage precipitation of chalcopyrite during biotite alteration and the late-stage deposition of molybdenite during silicification. Fluid inclusion microthermometry indicates a change in ore-forming fluids from high-temperature (320 °C–550 °C) and high-salinity (17 wt.%–67.2 wt.%) fluids to low-temperature (213 °C–450 °C) and low-salinity (7.3 wt.%–11.6 wt.%) fluids. The deposit has lower δD_V-SMOW (− 107.1‰ to − 185.8‰) values compared with other porphyry deposits in the GPCB, suggesting that the Bangpu deposit formed in a shallower setting and is associated with a more open system than is the case for other deposits in this belt. Sulfides at Bangpu yield δ³⁴S_V-CDT values of − 2.3‰ to 0.3‰, indicative of mantle-derived S implying that coeval mantle-derived mafic magma (e.g., diabase) simultaneously supplied S and Cu to the porphyry system at Bangpu. In comparison, the Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.79–19.28, ²⁰⁷Pb/²⁰⁴Pb = 15.64–15.93, ²⁰⁸Pb/²⁰⁴Pb = 39.16–40.45) of sulfides show that other metals (e.g., Mo, Pb, Zn) were likely derived mainly from an ancient crustal source. Therefore, the formation of the Bangpu deposit can be explained by a two-stage model involving (1) the partial melting of an ancient lower crust triggered by invasion of asthenospheric mantle-derived mafic melts that provide heat and metal Cu and (2) the formation of the Bangpu porphyry Mo–Cu system, formed by magmatic differentiation in the overriding crust in a post-collisional setting.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Sulfur and lead isotopic compositions of massive sulfides from deep-sea hydrothermal systems: Implications for ore genesis and fluid circulation

Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ³⁴S 0.0 to 9.6‰, avg. δ³⁴S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ³⁴S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (²⁰⁶Pb/²⁰⁴Pb 17.541 ± 0.004 to 19.268 ± 0.001, ²⁰⁷Pb/²⁰⁴Pb 15.451 ± 0.001 to 15.684 ± 0.001, ²⁰⁸Pb/²⁰⁴Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ³⁴S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing.     

Geochemical and geochronological constraints on the formation of shear-zone hosted Cu–Au–Bi–Te mineralization in the Stanos area,Chalkidiki, northern Greece

Copper–gold–bismuth–tellurium mineralization in the Stanos area, Chalkidiki Peninsula, Greece, occurs in the Proterozoic- to Silurian-aged Serbomacedonian Massif, which tectonically borders the Mesozoic Circum-Rhodope metamorphic belt to the west and crystalline rocks of the Rhodope Massif to the east. This area contains the Paliomylos, Chalkoma, and Karambogia prospects, which are spatially related to regional NW–SE trending shear zones and hosted by marble, amphibolite gneiss, metagabbro, and various muscovite–biotite–chlorite–actinolite–feldspar–quartz schists of the Silurian Vertiskos Unit. Metallic minerals occur as disseminated to massive aggregates along foliation planes and in boudinaged quartz veins. Iron-bearing sulfides (pyrite, arsenopyrite, and pyrrhotite) formed prior to a copper-bearing stage that contains chalcopyrite along with galena, sphalerite, molybdenite, and various minerals in the system Bi–Cu–Pb–Au–Ag–Te. Fluid inclusion homogenization temperatures of primary aqueous liquid–vapor inclusions in stage I quartz veins range from 170.1 °C to 349.6 °C (peak at ~ 230 °C), with salinities of 4.5 to 13.1 wt.% NaCl equiv. Calculated isochores intersect P–T conditions associated with the upper greenschist facies caused by local overpressures during late-stage tectonic movement along the shear zone in the Eocene, which produced stretching and unroofing of rocks in the region. Values of δ³⁴S for sulfides in the Stanos shear zone range from 2.42 to 10.19‰ and suggest a magmatic sulfur source with a partially reduced seawater contribution. For fluids in equilibrium with quartz, δ¹⁸O at 480 °C varies from 5.76 to 9.21‰ but does not allow for a distinction between a metamorphic and a magmatic fluid.A ¹⁸⁷Re–¹⁸⁷Os isochron of 19.2 ± 2.1 Ma for pyrite in the Paliomylos prospect overlaps ages obtained previously from intrusive rocks spatially-related to the Skouries porphyry Cu–Au, the Asimotrypes Au, and the intrusion-related Palea Kavala Bi–Te–Pb–Sb ± Au deposits in northern Greece, as well as alteration minerals in the carbonate-replacement Madem Lakkos Pb–Zn deposit. Ore-forming components of deposits in the Stanos area were likely derived from magmatic rocks at shallow depth that intruded an extensional shear environment at ~ 19 Ma.     

Carbon and sulfur isotopic fluctuations associated with the end-Guadalupian mass extinction in South China

Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ¹³C_carb, δ¹³C_org), and sulfur isotopic compositions of carbonate associated sulfate (δ³⁴S_sulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ¹³C_carb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ¹³C_carb values, Δ¹³C_carb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ³⁴S_sulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis.