Constraints of C–O–S–Pb isotope compositions and Rb–Sr isotopic age on the origin of the Tianqiao carbonate-hosted Pb–Zn deposit,SW China

The Tianqiao Pb–Zn deposit in the western Yangtze Block, southwest China, is part of the Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province. Ore bodies are hosted in Devonian and Carboniferous carbonate rocks, structurally controlled by a thrust fault and anticline, and carried about 0.38 million tons Pb and Zn metals grading > 15% Pb + Zn. Both massive and disseminated Pb–Zn ores occur either as veinlets or disseminations in dolomitic rocks. They are composed of ore minerals, pyrite, sphalerite and galena, and gangue minerals, calcite and dolomite. δ³⁴S values of sulfide minerals range from + 8.4 to + 14.4‰ and display a decreasing trend from pyrite, sphalerite to galena (δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena). We interpret that reduced sulfur derived from sedimentary sulfate (gypsum and barite) of the host Devonian to Carboniferous carbonate rocks by thermal–chemical sulfate reduction (TSR). δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite range from –5.3 to –3.4‰ and + 14.9 to + 19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid was a mixture origin of mantle, marine carbonate rocks and sedimentary organic matter. Sulfide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.378 to 18.601, ²⁰⁷Pb/²⁰⁴Pb = 15.519 to 15.811 and ²⁰⁸Pb/²⁰⁴Pb = 38.666 to 39.571) that are plotted in the upper crust Pb evolution curve and overlap with that of Devonian to Carboniferous carbonate rocks and Proterozoic basement rocks in the SYG province. Pb isotope compositions suggest derivation of Pb metal from mixed sources. Sulfide minerals have ⁸⁷Sr/⁸⁶Sr ratios ranging from 0.7125 to 0.7167, higher than Sinian to Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than basement rocks. Again, Sr isotope compositions are supportive of a mixture origin of Sr. They have an Rb–Sr isotopic age of 191.9 ± 6.9Ma, possibly reflecting the timing of Pb–Zn mineralization. C–O–S–Pb–Sr isotope compositions of the Tianqiao Pb–Zn deposit indicate a mixed origin of ore-forming fluids, which have Pb–Sr isotope homogenized before the mineralization. The Permian flood basalts acted as an impermeable layer for the Pb–Zn mineralization hosted in the Devonian–Carboniferous carbonate rocks.     

Cadmium and sulfur isotopic compositions of the Tianbaoshan Zn–Pb–Cd deposit,Sichuan Province,China

Although Zn–Pb deposits are one of the most important Cd reservoirs in the earth, few studies have focused on the Cd isotopic fractionation in Zn–Pb hydrothermal systems. This study investigates the causes and consequences of cadmium and sulfur isotope fractionation in a large hydrothermal system at the Tianbaoshan Zn–Pb–Cd deposit from the Sichuan–Yunnan–Guizhou (SYG) metallogenic province, SW China. Moderate variations in Cd and S isotope compositions have been measured in sphalerite cover a distance of about 78 m. Sphalerite has δ^114/110Cd values ranging from 0.01 to 0.57‰, and sulfides (sphalerite, galena and chalcopyrite) have δ³⁴S_CDT values ranging from 0.2 to 5.0‰. Although δ³⁴S_CDT and δ^114/110Cd values in sphalerites have no regular spatial variations, the δ³⁴S_CDT values in galena and calculated ore-forming fluid temperatures decreased from 2.1 to 0.2‰ and from about 290 to 130 °C, respectively, from the bottom to the top of the deposit. Heavy Cd isotopes are enriched in early precipitated sphalerite in contrast to previous studies. We suggest that Cd isotopic compositions in ore-forming fluids are heterogeneous, which result in heavy Cd isotope enrichment in early precipitated sphalerite. In comparison with other Zn–Pb deposits in the SYG area, the Tianbaoshan deposit has moderate Cd contents and small isotope fractionation, suggesting differences in origin to other Zn–Pb deposits in the SYG province.In the Tianbaoshan deposit, the calculated δ³⁴S∑_S-fluids value is 4.2‰, which is not only higher than the mantle-derived magmatic sulfur (0 ± 3‰), but also quite lower than those of Ediacaran marine sulfates (about 30 to 35‰). Thus, we suggest that reduced sulfur of ore-forming fluids in the deposit was mainly derived from the leaching of the basement, which contains large amount of volcanic or intrusive rocks. Based upon a combination of Cd and S isotopic systems, the Tianbaoshan deposit has different geochemical characteristics from typical Zn–Pb deposits (e.g., the Huize deposit) in SYG area, indicating the unique origin of this deposit.     

Geological and isotopic evidence for magmatic-hydrothermal origin of the Ag–Pb–Zn deposits in the Lengshuikeng District,east-central China

The Lengshuikeng ore district in east-central China has an ore reserve of ～43 Mt with an average grade of 204.53 g/t Ag and 4.63 % Pb?+?Zn. Based on contrasting geological characteristics, the mineralization in the Lengshuikeng ore district can be divided into porphyry-hosted and stratabound types. The porphyry-hosted mineralization is distributed in and around the Lengshuikeng granite porphyry and shows a distinct alteration zoning including minor chloritization and sericitization in the proximal zone; sericitization, silicification, and carbonatization in the peripheral zone; and sericitization and carbonatization in the distal zone. The stratabound mineralization occurs in volcano-sedimentary rocks at ～100–400 m depth without obvious zoning of alterations and ore minerals. Porphyry-hosted and stratabound mineralization are both characterized by early-stage pyrite–chalcopyrite–sphalerite, middle-stage acanthite–native silver–galena–sphalerite, and late-stage pyrite–quartz–calcite. The δ³⁴S values of pyrite, sphalerite, and galena in the ores range from ?3.8 to +6.9‰ with an average of +2.0‰. The C–O isotope values of siderite, calcite, and dolomite range from ?7.2 to ?1.5‰ with an average of ?4.4‰ (V-PDB) and from +10.9 to +19.5‰ with an average of +14.8‰ (V-SMOW), respectively. Hydrogen, oxygen, and carbon isotopes indicate that the hydrothermal fluids were derived mainly from meteoric water, with addition of minor amounts of magmatic water. Geochronology employing LA–ICP–MS analyses of zircons from a quartz syenite porphyry yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 136.3?±?0.8 Ma considered as the emplacement age of the porphyry. Rb–Sr dating of sphalerite from the main ore stage yielded an age of 126.9?±?7.1 Ma, marking the time of mineralization. The Lengshuikeng mineralization classifies as an epithermal Ag–Pb–Zn deposit.     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

Geochemical/isotopic evolution of Pb–Zn deposits in the Central and Eastern Taurides,Turkey

The Central and Eastern Taurides contain numerous carbonate-hosted Pb–Zn deposits, mainly in Devonian and Permian dolomitized reefal–stramatolitic limestones, and in massive Jurassic limestones. We present and compare new fluid inclusion and isotopic data from these ore deposits, and propose for the first time a Mississippi Valley-type (MVT) mode of origin for them.

Fluid inclusion studies reveal that the ore fluids were highly saline (13–26% NaCl equiv.), chloride-rich (CaCl₂) brines, and have average homogenization temperatures of 112°C, 174.5°C, and 211°C for the Celal Da?, Delikkaya, and Ayrakl? deposits, respectively. Furthermore, the δ³⁴S values of carbonate-hosted Pb–Zn deposits in the Central and Eastern Taurides vary between –5.4‰ and?+13.70‰. This indicates a possible source of sulphur from both organic compounds and crustal materials. In contrast, stable sulphur isotope data (average δ³⁴S –0.15‰) for the Çad?rkaya deposit, which is related to a late Eocene–Oligocene (?) granodioritic intrusion, indicates a magmatic source. The lead isotope ratios of galena for all investigated deposits are heterogeneous. In particular, with the exception of the Suçat? district, all deposits in the Eastern (Delikkaya, Ayrakl?, Denizovas?, Çad?rkaya) and Central (Katranba??, Küçüksu) Taurides have high radiogenic lead isotope values (²⁰⁶Pb/²⁰⁴Pb between 19.058 and 18.622; ²⁰⁷Pb/²⁰⁴Pb between 16.058 and 15.568; and ²⁰⁸Pb/²⁰⁴Pb between 39.869 and 38.748), typical of the upper continental crust and orogenic belts.

Fluid inclusion, stable sulphur, and radiogenic lead isotope studies indicate that carbonate-hosted metal deposits in the Eastern (except for the Çad?rkaya deposit) and the Central Taurides are similar to MVT Pb–Zn deposits described elsewhere. The primary MVT deposits are associated with the Late Cretaceous–Palaeocene closure of the Tethyan Ocean, and formed during the transition from an extensional to a compressional regime. Palaeogene nappes that typically limit the exposure of ore bodies indicate a pre-Palaeocene age of ore formation. Host rock lithology, ore mineralogy, fluid inclusion, and sulphur?+?lead isotope data indicate that the metals were most probably leached from a crustal source such as clastic rocks or a crystalline massif, and transported by chloride-rich hydrothermal solutions to the site of deposition. Localization of the ore deposits on autochthonous basement highs indicates long-term basinal fluid migration, characteristic of MVT depositional processes. The primary MVT ores were oxidized in the Miocene, resulting in deposition of Zn-carbonate and Pb-sulphate–carbonate during karstification. The ores underwent multiple cycles of oxidation and, in places, were re-deposited to form clastic deposits. Modified deposits resemble the ‘wall-rock replacement’ and the ‘residual and karst fill’ of non-sulphide zinc deposits and are predominantly composed of smithsonite.     

Geological and isotopic constraints on the origin of the Anle carbonate-hosted Zn–Pb deposit in northwestern Yunnan Province,SW China

The Anle Zn–Pb deposit, hosted by Upper Cambrian dolostone, is located in the southern Songpan–Ganzi Block in southwest China. In this deposit, ore bodies occur as stratiform lenses and consist of galena, sphalerite and pyrite as ore minerals, and quartz, dolomite and calcite as gangue minerals. The mineralization shows mainly vein, banded and brecciated structures. Four ore bodies have been found in the Anle deposit, with a combined 2.0 million tonnes (Mt) of sulfide ores at average grades of 1.64 wt.% Pb, 6.64 wt.% Zn and 45 g/t Ag. Brown, brownish-yellow and yellow sphalerite samples have δ⁶⁶Zn values ranging from + 0.08 to + 0.10‰ (average + 0.09‰, n = 3), + 0.12 to + 0.38‰ (average + 0.24‰, n = 8) and + 0.40 to + 0.50‰ (average + 0.46‰, n = 3), respectively. We interpret the progressively heavier Zn isotopes from brown to yellow sphalerite as being led by kinetic Raleigh fractional crystallization. Calcite samples have δ¹³C_PDB and δ¹⁸O_SMOW values ranging from − 4.8 to − 0.2‰ (average − 1.7‰, n = 7) and + 17.9 to + 21.4‰ (average + 19.6‰, n = 7), respectively. Whole-rock δ¹³C_PDB and δ¹⁸O_SMOW values of the Cambrian ore-hosting dolostone range from + 0.1 to + 1.1‰ (average + 0.6‰, n = 3) and + 23.2 to + 24.1‰ (average + 23.6‰, n = 3), respectively. This suggests that carbon in the ore-forming fluids was provided by the host dolostone through carbonate dissolution. δ³⁴S_CDT values of sulfide samples range between − 1.3‰ and + 17.8‰ with an average value of + 6.3‰ (n = 25), lower than evaporites (such as barite + 19.8‰) in the overlaying Lower Ordovician sedimentary strata. The data suggest that sulfur in the hydrothermal fluids were derived from evaporites by thermo-chemical sulfate reduction (TSR). ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios for sulfide minerals range from 17.63 to 17.86, 15.58 to 15.69 and 37.62 to 37.95, respectively. The data are similar to those of the age-corrected Cambrian ore-hosting dolostone (²⁰⁶Pb/²⁰⁴Pb = 17.70–17.98, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.65 and ²⁰⁸Pb/²⁰⁴Pb = 37.67–38.06), but lower than those of age-corrected Ordovician sandstone and slate (²⁰⁶Pb/²⁰⁴Pb = 18.54–19.58, ²⁰⁷Pb/²⁰⁴Pb = 15.73–15.81 and ²⁰⁸Pb/²⁰⁴Pb = 38.44–39.60). This indicates that ore Pb was most likely to be derived from the Cambrian ore-hosting dolostone. Therefore, our new geological and isotopic evidence suggests that the Anle Zn–Pb deposit is best classified to be an epigenetic carbonate-hosted Mississippi Valley-type (MVT) deposit.     

Mineral chemistry and H–O–S–Pb isotopic compositions of skarn type copper deposits in the Jiurui district of the Middle-Lower Yangtze River metallogenic belt,Eastern China

The skarn type copper deposits are widespread in the Jiurui district in the Middle-Lower Yangtze River metallogenic belt. This paper reports a detailed study on mineral chemistry, and H, O, S and Pb isotopic compositions on skarn silicate and sulfide minerals in the three major skarn dominant deposits (Wushan, Dongleiwan and Dengjiashan). The Wushan skarn deposit is characterized with prograde garnet-dominated and clinopyroxene limited skarns with average andradite content of 83% and hedenbergite content of 10%, whereas the Dongleiwan and Dengjiashan deposits are featured with retrograde skarn alteration with abundant hydrous minerals such as epidote and chlorite. The garnet and clinopyroxene compositions show 59% andradite and 15% hedenbergite for the Dongleiwan skarns, and 43% and 22% for the Dengjiashan skarns respectively. The pistacite components (Ps value) defined as Fe^3 +/(Fe^3 ++ Al) and Fe^3 +/Fe^2 + value of epidote are 0.12 and 1.63 for the Wushan skarns, 0.30 and 32.73 for the Dongleiwan skarns, and 0.17 and 42.85 for the Dengjiashan skarns. It is suggested that the prograde skarn mineralization in the three deposits was all formed in a relatively oxidizing environment, with the Wushan showing the highest oxidation potential and the Dengjiashan having the least oxidation potential. However, in the retrograde skarns, the Dongleiwan and Dengjiashan deposits show higher oxidation potential than that of Wushan. The three deposits show similar sulfur isotopic compositions of − 2.9 to + 1.4‰ and similar lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of 17.900 to 18.205, 15.538 to 15.649 and 38.170 to 39.025, respectively. All the three deposits should have similar magmatic origin for the ore-forming materials based on their S and Pb isotopes. The oxygen isotopic compositions of the prograde and retrograde fluids in the three deposits show some differences, with δ¹⁸O_Fluid values of + 8.13‰ and + 7.81‰ for the Wushan, + 6.47‰ and + 2.33‰ for the Dongleiwan, and + 8.27‰ and + 4.43‰ for the Dengjiashan. But the hydrogen isotopic compositions are similar for the prograde (− 65 to − 31‰) and retrograde (− 64 to − 33‰) fluids. Therefore, the fluid origins and evolution may be different in each deposit. The hydrothermal fluids for the prograde skarns in all three deposits were likely derived from magmatic–hydrothermal sources, but the Dongleiwan and Dengjiashan show a higher proportion of meteoric water input in the retrograde stage. Considering the similar average prograde temperatures (574 to 560 °C) as calculated from coexisting garnet–clinopyroxene pairs, and similar retrograde temperatures (281 to 246 °C) as calculated from chlorite chemistry for the three deposits, we suggest that the trigger for deposition of sulfide ores in the Wushan garnet-dominated skarn deposit was mainly caused by system cooling with temperature drop along with magmatic intrusion and crystallization process. The Dongleiwan and Dengjiashan skarn deposits constitute a well developed retrograde skarn system with abundant epidote, chlorite, quartz and calcite, which probably caused by fluid mixing of high-temperature saline magmatic–hydrothermal fluids with cooler, oxidizing and dilute meteoric water.     

The genetic relationship between hydrocarbon systems and Mississippi Valley-type Zn–Pb deposits along the SW margin of Sichuan Basin,China

The Chipu Mississippi Valley-type (MVT) deposit is located on the southwest (SW) margin of the Sichuan Basin. Occurrence of plentiful organic matter (bitumen) at this deposit and abundant hydrocarbon reservoirs in the SW Sichuan Basin implies a link between lead–zinc mineralization and hydrocarbon systems in this area. The high δ³⁴S values of most metal sulphides from the different ore stages suggest that H₂S-bearing gases and/or thermochemical sulphate reduction (TSR) by organic matter could have been the source of reduced sulphur involved in ore formation. Sulphides with small positive to negative δ³⁴S values can be attributed to organically bound sulphur at the Chipu deposit. Carbon and oxygen isotopic compositions from sparry carbonates suggest mixing of organic carbon with seawater-derived carbon in the mineralization process. From the early to the later ore stages, δ¹³C_PDB values of ore-hosting carbonates are increasingly more negative, which indicates strengthening of the TSR role during mineralization. Hydrogen and oxygen isotopes in fluid inclusions in the quartz gangue indicate the provenance of the ore-forming fluids in the hydrocarbons. Moreover, some extremely low hydrogen isotope values suggest the addition of hydrogen from the same source. The low H/C ratios and high non-hydrocarbon component of the bitumen (Zhang et al. 2010 Zhang, C.Q., Yu, J.J., Mao, J.W., Yu, H. and Li, H.M. 2010. Research on the biomarker from Chipu Pb-Zn Deposit, Sichuan. Acta Sedimentologica Sinica, 28: 832–844. v.p.in Chinese with English abstract [Google Scholar]) also suggest that the organic matter may have been involved in TSR and subjected to a strong oxidation by ore-bearing fluids. This study attempts to explain the lead–zinc mineralization process and the role of organic matter in it. As there is a demonstrable relationship between the evolution of the hydrocarbons and regional lead–zinc mineralization along the SW edge of the Sichuan Basin, we propose a possible model in which the MVT mineralization coincided with the degradation of hydrocarbon reservoirs due to the large-scale migration of basinal fluids, most likely driven by the late Indosinian orogeny in response to the closure of the Palaeo-Tethys Ocean.     

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

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

Sediment-hosted Zn–Pb–Cu deposits in the Central African Copperbelt

Stratabound epigenetic sulphide Zn–Pb–Cu ore deposits of the Central African Copperbelt in the Democratic Republic of Congo and Zambia are mostly hosted in deformed shallow marine platform carbonates and associated sedimentary rocks of the Neoproterozoic Katanga Supergroup. Economic orebodies, that also contain variable amounts of minor Cd, Co, Ge, Ag, Re, As, Mo, Ga, and V, occur mainly as irregular pipe-like bodies associated with collapse breccias and faults as well as lenticular bodies subparallel to bedding. Kipushi and Kabwe in the Democratic Republic of the Congo and Zambia, respectively, are the major examples of carbonate-hosted Zn–Pb–Cu mined deposits with important by-products of Ge, Cd, Ag and V in the Lufilian Arc, a major metallogenic province famous for its world-class sediment-hosted stratiform Cu–Co deposits. The carbonate-hosted deposits range in age from Neoproterozoic to early Palaeozoic (680 to 450 Ma). The formation of the relatively older Neoproterozoic deposits is probably related to early collision events during the Lufilian Orogeny, whereas the younger Palaeozoic deposits may be related to post-collisional processes of ore formation. Fluid inclusion and stable isotope data indicate that hydrothermal metal-bearing fluids evolved from formation brines during basin evolution and later tectonogenesis. Ore fluid migration occurred mainly along major thrust zones and other structural discontinuities such as karsts, breccias and faults within the Katangan cover rocks, resulting in ore deposition within favourable structures and reactive carbonates of the Katangan Supergroup.     

Geological and C–O–S–Pb–Sr isotopic constraints on the origin of the Qingshan carbonate-hosted Pb–Zn deposit,Southwest China

Located in the western Yangtze Block, the Qingshan Pb–Zn deposit, part of the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province, contains 0.3 million tonnes of 9.86 wt.% Pb and 22.27 wt.% Zn. Ore bodies are hosted in Carboniferous and Permian carbonate rocks, structurally controlled by the Weining–Shuicheng anticline and its intraformational faults. Ores composed of sphalerite, galena, pyrite, dolomite, and calcite occur as massive, brecciated, veinlets, and disseminations in dolomitic limestones.

The C–O isotope compositions of hydrothermal calcite and S–Pb–Sr isotope compositions of Qingshan sulphide minerals were analysed in order to trace the sources of reduced sulphur and metals for the Pb–Zn deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from –5.0‰ to –3.4‰ and +18.9‰ to +19.6‰, respectively, and fall in the field between mantle and marine carbonate rocks. They display a negative correlation, suggesting that CO₂ in the hydrothermal fluid had a mixed origin of mantle, marine carbonate rocks, and sedimentary organic matter. δ³⁴S values of sulphide minerals range from +10.7‰ to +19.6‰, similar to Devonian-to-Permian seawater sulphate (+20‰ to +35‰) and evaporite rocks (+23‰ to +28‰) in Carboniferous-to-Permian strata, suggesting that the reduced sulphur in hydrothermal fluids was derived from host-strata evaporites. Ores and sulphide minerals have homogeneous and low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.561 to 18.768, ²⁰⁷Pb/²⁰⁴Pb = 15.701 to 15.920, and ²⁰⁸Pb/²⁰⁴Pb = 38.831 to 39.641) that plot in the upper crust Pb evolution curve, and are similar to those of Devonian-to-Permian carbonate rocks. Pb isotope compositions suggest derivation of Pb metal from the host rocks. ⁸⁷Sr/⁸⁶Sr ratios of sphalerite range from 0.7107 to 0.7136 and (⁸⁷Sr/⁸⁶Sr)_200Ma ratios range from 0.7099 to 0.7126, higher than Sinian-to-Permian sedimentary rocks and Permian Emeishan flood basalts, but lower than Proterozoic basement rocks. This indicates that the ore strontium has a mixture source of the older basement rocks and the younger cover sequence. C–O–S–Pb–Sr isotope compositions of the Qingshan Pb–Zn deposit indicate a mixed origin of the ore-forming fluids and metals.     

Rb–Sr dating of sulfides and S–Pb isotopic study of the Bayanbaolege Ag polymetallic deposit,Inner Mongolia,NE China

The large-scale Bayanbaolege Ag polymetallic deposit is situated in the Tuquan–Linxi Fe-Sn-Cu-Pb-Zn-Ag metallogenic sub-belt in eastern slopes of the southern Great Xing’an Range, NE China. The sulfide-quartz vein-type orebodies in the deposit are hosted primarily in the Early Cretaceous granodiorite porphyry and Late Permian strata. Three primary paragenetic stages of veining have been identified: (I) arsenopyrite- pyrite-quartz stage, (II) pyrite-sphalerite-quartz stage, and (III) galena-silver minerals (pyrargyrite, argentite, and pearceite)-calcite stage. The Rb–Sr dating of sulfides yielded an isochron age of 129.9 ± 2.9 Ma (MSWD = 2.1) for the sphalerite, which constrains the mineralization age to the Early Cretaceous. Rb and Sr concentrations in the sulfides ranged from 0.0940 to 1.0294 ppm and 0.0950–3.3818 ppm, respectively. The initial ⁸⁷Sr/⁸⁶Sr value of the sphalerite was 0.70852 ± 0.00018, indicating that the mineralized materials were derived from the mixed crust-mantle source area. S isotope analysis showed that the δ³⁴S values of the sulfide samples varied in a narrow range, from −1.5‰ to +1.3‰ (mean −0.65‰), indicating a magmatic S source. Pb isotopic ratios of the sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.306–18.416, ²⁰⁷Pb/²⁰⁴Pb = 15.524–15.605, ²⁰⁸Pb/²⁰⁴Pb = 38.095–38.479) and the granodiorite porphyry (²⁰⁶Pb/²⁰⁴Pb = 18.341–18.933, ²⁰⁷Pb/²⁰⁴Pb = 15.539–15.600, ²⁰⁸Pb/²⁰⁴Pb = 38.134–38.944) reflect that the ore-forming materials originated from contemporaneous magma with Early Cretaceous granodiorite porphyry. This study of the Bayanbaolege deposit and other hydrothermal deposits in the area provides compelling evidence that the widespread Mesozoic magmatism and mineralization in the southern Great Xing’an Range occurred in an intracontinental extensional tectonic setting, which was associated with the westward subduction of the paleo-Pacific plate.     

Sediment-hosted Pb–Zn deposits in the Tethyan domain from China to Iran: Characteristics,tectonic setting,and ore controls

The Tethyan domain from China to Iran hosts many important sediment-hosted Pb–Zn deposits but most have been poorly documented. This study summarizes the salient features of these deposits and discusses the type of ore, tectonic setting, and important ore controls, on the basis of new geological observations and previous publications. The Tethyan domain is characterized by the young and extensive Himalayan–Tibetan and Zagros orogens that formed through collisions between the India/Arabia and Eurasia continents since the Late Cretaceous or early Cenozoic. Abundant Mississippi Valley-type (MVT) and subordinate clastic-dominated (CD, also known as SEDEX) Pb–Zn deposits occur in this domain, including in central and eastern Himalayan–Tibetan orogen in China, the Indian passive margin in southern Pakistan, and various tectonic units of Iran. Economically important deposits contain 0.1–21 Mt Pb + Zn and have total metal resources of ∼75 Mt with ∼48% being oxidized ores. All major deposits known in this domain are MVTs (i.e., the Jinding, Huoshaoyun, Mehdiabad, and Angouran deposits).Mississippi Valley-type Pb–Zn deposits occur in continental-collision-related fold-and-thrust belts and forelands, where deposits are mostly located on the margin of the Eurasian continent, with some in the Indian and Arabian continental margins. Clastic-dominated Pb–Zn deposits occur in central Iran and southern Pakistan, hosted by deep-water siliciclastic sequences of the early Cambrian rifted continental margin of Gondwana and the Jurassic passive continental margin of India, respectively. The youngest mineralized rocks and ages constrain that some important MVT deposits (e.g., the Jinding, Chaqupacha, and Angouran deposits) were formed after a main phase of regional compression, during a regional, large-scale strike-slip or crustal-extension stage in a continental collision setting. In sense of lithologic structure, important ore controls for MVT deposits include evaporite diapir structure, carbonate/evaporite dissolution–collapse structure, pre-existing barite, and porous dolostone. Much of the primary sulfide ore in this domain has been oxidized by supergene processes. This is particularly pronounced in the newly discovered Huoshaoyun deposit, where almost all sulfides have been oxidized to smithsonite and cerussite. An understanding of tectonic setting, ore controls, and supergene processes is essential in exploring for MVT deposits in this domain.     

Geochemistry,geochronology and Sr–Nd–Pb–Hf isotopic compositions of Middle to Late Jurassic syenite–granodiorites–dacite in South China: Petrogenesis and tectonic implications

In situ zircon U–Pb ages and Hf isotope data, major and trace elements and Sr–Nd–Pb isotopic compositions are reported for coeval syenite–granodiorites–dacite association in South China. The shoshonitic syenites are characterized by high K₂O contents (5.9–6.1 wt.%) and K₂O/Na₂O ratios (1.1–1.2), negative Eu anomalies (Eu/Eu* = 0.65 to 0.77), enrichments of Rb, K, Nb, Ta, Zr and Hf, but depletion of Sr, P and Ti. The adakitic granodiorite and granodiorite porphyry intrusions are characterized by high Al₂O₃ contents (15.0–16.8 wt.%), enrichment in light rare earth elements (LREEs), strongly fractionated LREEs (light rare earth elements) to HREEs (heavy rare earth elements), high Sr (438–629 ppm), Sr/Y (29.2–53.6), and low Y (11.7–16.8 ppm) and HREE contents (e.g., Yb = 1.29–1.64 ppm). The calc-alkaline dacites are characterized by LREE enrichment, absence of negative Eu anomalies, and enrichment of LILEs such as Rb, Ba, Th, U and Pb, and depletion of HFSEs such as Nb, Ta, P and Ti.Geochemical and Sr–Nd–Hf isotopic compositions of the syenites suggest that the shoshonitic magmas were differentiated from parental shoshonitic melts by fractional crystallization of olivine, clinopyroxene and feldspar. The parent magmas may have originated from partial melting of the lithospheric mantle with small amount contribution from crustal materials. The adakitic granodiorite and granodiorite porphyry have Sr–Nd–Pb isotopic compositions that are comparable to that of the mafic lower crust. They have low Mg# and MgO, Ni and Cr contents, abundant inherited zircons, low ε_Nd(t) and ε_Hf(t) values as well as old whole-rock Nd and zircon Hf model ages. These granodiorites were likely generated by partial melting of Triassic underplated mafic lower crust. The Hf isotopic compositions of the dacites are relatively more depleted than the Cathaysia enriched mantle, suggesting those magmas were derived from the partial melting of subduction-modified mantle sources. The coeval shoshonitic, high-K calc-alkaline and calc-alkaline rocks in Middle to Late Jurassic appear to be associated with an Andean-type subduction. This subduction could have resulted in the upwelling of the asthenosphere beneath the Cathaysia Block, which induced partial melting of the mantle as well as the mafic lower crust, and formed an arc regime in the coastal South China during Middle to Late Jurassic.     

Mineralogy and speciation of Zn and As in Fe-oxide-clay aggregates in the mining waste at the MVT Zn–Pb deposits near Olkusz,Poland

Oxidation zones of ore deposits offer valuable insights into the long-term fate of many metals and metalloids. In this work, we have studied a paleo-acid rock drainage (ARD) system – the oxidation zone of Mississippi-valley type Zn–Pb deposits near Olkusz in southern Poland. The ARD systems exhausted their acid-generating capacity and have come almost to the conclusion of the mineral and geochemical transformations. Primary pyrite, marcasite, galena and sphalerite have been decomposed but the acidity was neutralized by the abundant carbonate host rocks. Zinc is stored in smithsonite, hemimorphite, and Zn-rich sheet aluminosilicates. Some of these minerals formed simultaneously with the oxidation zone but some precipitated in the soils in situ, thus documenting the mobility of Zn, Al, and Si in the soils. Iron oxides are represented mostly by goethite, either well-crystalline or nanocrystalline, as determined by a combination of powder X-ray diffraction, micro-X-ray diffraction, and Mössbauer spectroscopy. Iron oxides bind a substantial amount of arsenic, to a lesser extent also zinc, lead, and cadmium, as shown by electron microprobe analyses and sequential extractions. The X-ray absorption spectroscopy data of the local environment of arsenic in goethite suggest the existence of bidentate mononuclear complex, in addition to the more common bidentate binuclear complex. These results suggest that arsenic is incorporated in the crystal structure of goethite, in addition to adsorbed to the surface of the particles or occluded in the voids and pores. Zinc is bound in goethite as a mixture of tetrahedrally and octahedrally coordinated cations. This study shows that the mature system binds the metals from the primary sulfides relatively strongly. Yet, some release of the metals was observed in this study, either in the laboratory (by sequential extractions) and in nature (e.g., neoformed Zn phyllosilicates). The physical conditions in the oxidation zone and on the surface are largely similar but the metals, to a certain extent, are still mobile in the soils. We may speculate that their mobility near the surface, in the mining waste, may be enhanced by a higher water/rock ratio than in the oxidation zone. This result implies that although the studied material is relatively benign, it still has a potential to cause local environmental problems.     

Determination of Hf–Sr–Nd isotopic ratios by MC-ICP-MS using rapid acid digestion after flux-free fusion in geological materials

In this study, we established a rapid acid digestion for determining Hf–Sr–Nd isotopic ratios of geological samples by using MC-ICP-MS. Conditions of 1600 °C for 1 min and 1400 °C for 1 min were adopted for fusing intrusive rocks and extrusive rocks, respectively. The rapid acid digestion technique is superior in digestion time compared with high-pressure PTFE bomb method. The procedural blanks of the method were also lower than that flux fusion. Replicate analyses of international certified reference materials (CRMs) indicate that isotopic ratios of ¹⁷⁶Hf/¹⁷⁷Hf, ⁸⁷Sr/⁸⁶Sr and ¹⁴³Nd/¹⁴⁴Nd agree well with previously published data. The external reproducibility (2SD, n = 5) of ten CRMs are ±0.000030 for ⁸⁷Sr/⁸⁶Sr, ±0.000030 for ¹⁴³Nd/¹⁴⁴Nd, and ±0.000018 for ¹⁷⁶Hf/¹⁷⁷Hf.     

Re–Os dating of molybdenite and in-situ Pb isotopes of sulfides from the Lamo Zn–Cu deposit in the Dachang tin-polymetallic ore field,Guangxi, China

The Dachang tin-polymetallic district, Guangxi, China, is one of the largest tin ore fields in the world. Both cassiterite-sulfide and Zn–Cu skarn mineralization are hosted in the Mid-Upper Devonian carbonate-rich sediments adjacent to the underlying Cretaceous Longxianggai granite (91–97 Ma). The Lamo Zn–Cu deposit is a typical skarn deposit in the district and occurs at the contact zone between the Upper Devonian limestone and the granite. The ore minerals mainly consist of sphalerite, arsenopyrite, pyrrhotite, galena, chalcopyrite, and minor molybdenite. However, the age of mineralization and source of the metals are not well constrained. In this study, we use the molybdenite Re–Os dating method and in-situ Pb isotopes of sulfides from the Lamo deposit for the first time in order to directly determine the age of mineralization and the tracing source of metals. Six molybdenite samples yielded a more accurate Re–Os isochron age of 90.0 ± 1.1 Ma (MSWD = 0.72), which is much younger than the reported garnet Sm–Nd isochron age of 95 ± 11 Ma and quartz fluid inclusions Rb–Sr isochron age of 99 ± 6 Ma. This age is also interpreted as the age of Zn–Cu skarn mineralization in the Dachang district. Further, in this study we found that in-situ Pb isotopes of sulfides from the Lamo deposit and feldspars in the district’s biotite granite and granitic porphyry dikes have a narrow range and an overlap of Pb isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.417–18.594, ²⁰⁷Pb/²⁰⁴Pb = 15.641–15.746, and ²⁰⁸Pb/²⁰⁴Pb = 38.791–39.073), suggesting that the metals were mainly sourced from Cretaceous granitic magma.     

The C-O and Zn isotopic compositions of the Laochang Ag-Pb-Zn ore bodies in the Changning-Menglian suture zone,and its geological implicationsSCIEI北大核心CSCD

老厂矿床是昌宁-孟连缝合带内唯一大型矿床,本文报道了老厂矿床Ag-Pb-Zn矿体中Ⅰ号矿体群下部块状矿体和上部网脉状矿体的方解石C-O同位素组成,以及Ⅰ、Ⅱ、Ⅳ三个矿体群内闪锌矿的Zn同位素组成。Ⅰ号矿体群下部块状矿体和上部网脉状矿体方解石δ¹³C_PDB的范围分别为-6.17‰～2.71‰和-2.18‰～3.87‰,δ¹⁸O_PDB的范围分别为-19.57‰～-17.23‰和-22.10‰～-16.21‰;计算获得对应成矿流体的δ¹³C_CO2为-6.16‰～1.53‰和-2.39‰～6.43‰,δ¹⁸O_H2O分别为1.62‰～7.62‰和4.36‰～16.92‰,通过与岩浆CO₂(δ¹³C=-2‰～-8‰)和围岩灰岩(δ¹³C=-1.6‰～4.0‰)的δ¹³C值相比较,指示块状矿体成矿流体中的碳主要来自岩浆,网脉状矿体成矿流体中...     

Zircon U–Pb ages and Hf isotopic compositions of two types of supracrustal rocks in the Northeastern Sulu UHP terrane: constraints on the surface boundary between South China and North China

ABSTRACT

There are voluminous ultrahigh pressure-related orthogneisses and minor metamorphic supracrustal rocks in the northeastern Sulu UHP terrane (NSL), East China. The tectonic affinities of the supracrustal rocks are crucial for unravelling the deep continental subduction processes and locating the tectonic suture between the South China (SCB) and North China (NCB) blocks. In this contribution, we report new zircon U–Pb ages and Hf isotope data for the supracrustal rocks and metagabbros in the Zeku region of the NSL. In the Zeku region, the supracrustal rocks are spatially associated with granitic gneisses, metagabbros, and eclogites. Detrital zircon U–Pb analyses yield ages between 3.39 and 0.65 Ga that cluster as three major age populations including (1) 2.15–1.68 Ga with two subpeaks at ~1.83 Ga and~1.97 Ga, (2) 2.45–2.15 Ga with a peak at ~2.37 Ga, and (3) 0.79–0.65 Ga. In addition, there is a small age population between 3.39 and 2.61 Ga. The youngest age population of 0.79–0.65 Ga indicates that the Zeku supracrustal rocks must have been deposited after 650 Ma rather than during the Palaeoproterozoic as previously thought. The 210–190 Ma metamorphic ages suggest that the Zeku rocks were affected by Triassic collision–subduction and exhumation. Most of the Archaean-Palaeoproterozoic zircons have negative ε_Hf(t) values and two-stage Hf model ages concentrating at 2.4–3.4 Ga (peak at ~2.9 Ga), indicating that source rocks of these zircons were mainly derived from recycling of ancient crustal material. These ages, together with the Hf isotopic compositions and rock assemblages, indicate that the Zeku supracrustal rocks were mainly derived from the Precambrian basement rocks of the northern Yangzte Block and have a tectonic affinity to the SCB, rather than the NCB. Our results, together with previously published data, suggest that there are two types of supracrustal rocks with different zircon U–Pb ages and tectonic affinities in the NSL. On the basis of new data, we suggest that the surface boundary between the SCB and NCB in the Jiaodong Peninsula is a complicated tectonic mélange zone rather than a single fault.     

Geochemical and Sr–Nd–Pb isotopic compositions of Mesozoic mafic dikes from the Gan-Hang tectonic belt,South China: petrogenesis and geodynamic significance

Mesozoic mafic dikes in the Gan-Hang tectonic belt (GHTB) provide an opportunity to explore both the nature of their mantle source(s) and the secular evolution of the underlying Mesozoic lithospheric mantle in the region. The geochronology and primary geochemical and Sr–Nd–Pb isotopic compositions of Group 1 (middle section of GHTB) and Group 2 (the rest of the section) dolerite dikes spanning the GHTB were investigated. K–Ar ages indicate that dikes of both groups were emplaced during the Cretaceous (131–69 Ma). The dikes are doleritic in composition and are enriched in both large ion lithophile elements (LILEs; e.g. Rb, Ba, and Pb) and light rare earth elements (LREEs), with a wide range of Eu anomalies, but are depleted in high field strength elements (HFSEs; e.g. Nb, Ta, and Ti) and heavy rare earth elements (HREEs). Dikes sampled in the middle section of the GHTB (Group 1) show more pronounced REE differentiation and a greater contribution from crustal material than those from the east and west sections (Group 2) and are similar to GHTB volcanic rocks in exhibiting a slight enrichment in LREEs. The dolerites are further characterized by a wide range in ⁸⁷Sr/⁸⁶Sr _i ?=?0.7041–0.7110, ¹⁴³Nd/¹⁴⁴Nd _i ?=?0.511951–0.512758, ?Nd _t ?=?–10.4 to?+5.6, and Pb isotopic ratios (²⁰⁶Pb/²⁰⁴Pb _i ?=?18.1–18.3, ²⁰⁷Pb/²⁰⁴Pb _i ≈ 15.6, and ²⁰⁸Pb/²⁰⁴Pb _i ?=?38.2–38.7). The dikes have undergone fractional crystallization of olivine, clinopyroxene, plagioclase, and Ti-bearing phases, except for dikes from the Anding area, which possibly experienced fractionation of plagioclase. Geochemically, all the dike samples originated from mantle sources ranging in composition from depleted to enriched that contained a component of foundered lower crust; crustal contamination during the ascent of these magmas was negligible. In the context of the late Mesozoic lithospheric extension across South China, mafic dike magmatism was likely triggered by the reactivation of deep faults, which promoted foundering of the lower crust and subsequent mantle upwelling in the GHTB.