U–Pb and Th–Pb dating of apatite by LA-ICPMS

Apatite is a common U- and Th-bearing accessory mineral in igneous and metamorphic rocks, and a minor but widespread detrital component in clastic sedimentary rocks. U–Pb and Th–Pb dating of apatite has potential application in sedimentary provenance studies, as it likely represents first cycle detritus compared to the polycyclic behavior of zircon. However, low U, Th and radiogenic Pb concentrations, elevated common Pb and the lack of a U–Th–Pb apatite standard remain significant challenges in dating apatite by LA-ICPMS, and consequently in developing the chronometer as a provenance tool.This study has determined U–Pb and Th–Pb ages for seven well known apatite occurrences (Durango, Emerald Lake, Kovdor, Mineville, Mud Tank, Otter Lake and Slyudyanka) by LA-ICPMS. Analytical procedures involved rastering a 10 μm spot over a 40 × 40 μm square to a depth of 10 μm using a Geolas 193 nm ArF excimer laser coupled to a Thermo ElementXR single-collector ICPMS. These raster conditions minimized laser-induced inter-element fractionation, which was corrected for using the back-calculated intercept of the time-resolved signal. A Tl–U–Bi–Np tracer solution was aspirated with the sample into the plasma to correct for instrument mass bias. External standards (Ple?ovice and 91500 zircon, NIST SRM 610 and 612 silicate glasses and STDP5 phosphate glass) along with Kovdor apatite were analyzed to monitor U–Pb, Th–Pb, U–Th and Pb–Pb ratiosCommon Pb correction employed the ²⁰⁷Pb method, and also a ²⁰⁸Pb correction method for samples with low Th/U. The ²⁰⁷Pb and ²⁰⁸Pb corrections employed either the initial Pb isotopic composition or the Stacey and Kramers model and propagated conservative uncertainties in the initial Pb isotopic composition. Common Pb correction using the Stacey and Kramers (1975) model employed an initial Pb isotopic composition calculated from either the estimated U–Pb age of the sample or an iterative approach. The age difference between these two methods is typically less than 2%, suggesting that the iterative approach works well for samples where there are no constraints on the initial Pb composition, such as a detrital sample. No ²⁰⁴Pb correction was undertaken because of low ²⁰⁴Pb counts on single collector instruments and ²⁰⁴Pb interference by ²⁰⁴Hg in the argon gas supply.Age calculations employed between 11 and 33 analyses per sample and used a weighted average of the common Pb-corrected ages, a Tera–Wasserburg Concordia intercept age and a Tera–Wasserburg Concordia intercept age anchored through common Pb. The samples in general yield ages consistent (at the 2σ level) with independent estimates of the U–Pb apatite age, which demonstrates the suitability of the analytical protocol employed. Weighted mean age uncertainties are as low as 1–2% for U- and/or Th-rich Palaeozoic–Neoproterozoic samples; the uncertainty on the youngest sample, the Cenozoic (31.44 Ma) Durango apatite, ranges from 3.7–7.6% according to the common Pb correction method employed. The accurate and relatively precise common Pb-corrected ages demonstrate the U–Pb and Th–Pb apatite chronometers are suitable as sedimentary provenance tools. The Kovdor carbonatite apatite is recommended as a potential U–Pb and Th–Pb apatite standard as it yields precise and reproducible ²⁰⁷Pb-corrected, ²³²Th–²⁰⁸Pb, and common Pb-anchored Tera–Wasserburg Concordia intercept ages.     

Metallogenesis and ore-forming time of the Changtuxili Mn–Ag–Pb–Zn deposit in Inner Mongolia: Evidence from C–O–S isotopes and U–Pb geochronology

This paper reports new geochronological (U–Pb) and isotope (C, O, and S) data to investigate the timing of mineralization and mode of ore genesis for the recently discovered Changtuxili Mn–Ag–Pb–Zn deposit, located on the western slopes of the southern Great Hinggan Range in NE China. The mineralization is hosted by intermediate–acidic lavas and pyroclastic rocks of the Baiyingaolao Formation. Three stages of mineralization are identified: quartz–pyrite (Stage I), galena–sphalerite–tetrahedrite–rhodochrosite (Stage II), and quartz–pyrite (Stage III). δ¹³C and δ¹⁸O values for carbonate from the ore vary from −8.51‰ to −4.96‰ and 3.97‰ to 15.90‰, respectively, which are indicative of a low-temperature alteration environment. δ³⁴S_V-CDT values of sulfides range from −1.77‰ to 4.16‰ and show a trend of equilibrium fractionation (δ³⁴S_Py ​> ​δ³⁴S_Sp ​> ​δ³⁴S_Gn). These features indicate that pyrite, sphalerite, and galena precipitated during the period of mineralization. The alteration mineral assemblage and isotope data indicate that the weakly acidic to weakly alkaline ore-forming fluid was derived largely from meteoric water and the ore-forming elements C and S originated from magma. During the mineralization, a geochemical barrier was formed by changes in the pH of the ore-forming fluid, leading to the precipitation of rhodochrosite. On the basis of the mineralization characteristics, new isotope data, and comparison with adjacent deposits, we propose that the Changtuxili Mn–Ag–Pb–Zn deposit is an intermediate-to low-sulfidation epithermal deposit whose formation was controlled by fractures and variability in the pH of the ore-forming fluid. The surrounding volcanic rocks yield zircon U–Pb ages of 160−146 ​Ma (Late Jurassic), indicating that the mineralization is younger than 146 ​Ma.     

Precise U–Pb and Th–Pb age determination of kimberlitic perovskites by secondary ion mass spectrometry

Perovskite, a common Th- and U-enriched accessory mineral crystallised from kimberlitic magmas, has long been thought to be an important geochronometer for dating the emplacement of kimberlite. However, it also contains variably high levels of common Pb, which makes it difficult to obtain a precise measurement of radiogenic Pb/U and Pb/Th isotopic compositions using microbeam techniques such as SIMS and LA-ICP-MS. We present calibration protocols for in situ U–Pb and Th–Pb age determination of kimberlitic perovskite using the large double-focusing Cameca IMS 1280. Linear relationships are found between ln(²⁰⁶Pb?⁺/U⁺) and ln(UO₂⁺/U⁺), and between ln(²⁰⁸Pb?⁺/Th⁺) and ln(ThO⁺/Th⁺), based on which the inter-element fractionation in unknown samples during SIMS analyses can be precisely calibrated against a perovskite standard. The well-characterized Ice River perovskite is chosen as the U–Pb and Th–Pb age standard in this study. The ²⁰⁴Pb-correction method was used to estimate the fraction of common Pb, which is consistent with the results obtained using the ²⁰⁷Pb-based correction method for the dated perovskites of Phanerozoic age.A Tazheran perovskite with unusually high U but rather low Th yielded a Concordia U–Pb age of 462.8 ± 2.5 Ma and a Th–Pb age of 462 ± 4 Ma. Two perovskite samples from the Iron Mountain kimberlite have identical Concordia U–Pb ages of 410.8 ± 3.4 Ma and 411.0 ± 2.6 Ma, which are consistent within errors with their corresponding Th–Pb ages of 409.2 ± 7.2 Ma and 412.3 ± 3.3 Ma, respectively. Two perovskite samples from the Wesselton Mine of South Africa yielded indistinguishable ²⁰⁶Pb/²³⁸U ages of 91.5 ± 2.2 Ma and 90.3 ± 2.9 Ma, and Th–Pb ages of 90.5 ± 0.8 Ma and 88.4 ± 1.6 Ma, respectively. Accuracy and precision of 1–2% (95% confidence level) for these measurements have been demonstrated by the consistency of their U–Pb and Th–Pb ages with the recommended U–Pb ages of previous works.     

Laser-ICP-MS U–Pb zircon ages and geochemical and Sr–Nd–Pb isotopic compositions of the Niyasar plutonic complex,Iran: constraints on petrogenesis and tectonic evolution

We conducted geochemical and isotopic studies on the Oligocene–Miocene Niyasar plutonic suite in the central Urumieh–Dokhtar magmatic belt, in order better to understand the magma sources and tectonic implications. The Niyasar plutonic suite comprises early Eocene microdiorite, early Oligocene dioritic sills, and middle Miocene tonalite + quartzdiorite and minor diorite assemblages. All samples show a medium-K calc-alkaline, metaluminous affinity and have similar geochemical features, including strong enrichment of large-ion lithophile elements (LILEs, e.g. Rb, Ba, Sr), enrichment of light rare earth elements (LREEs), and depletion in high field strength elements (HFSEs, e.g. Nb, Ta, Ti, P). The chondrite-normalized rare earth element (REE) patterns of microdiorite and dioritic sills are slightly fractionated [(La/Yb)_n = 1.1–4] and display weak Eu anomalies (Eu/Eu* = 0.72–1.1). Isotopic data for these mafic mantle-derived rocks display I_Sr = 0.70604–0.70813, ?_Nd (microdiorite: 50 Ma and dioritic sills: 35 Ma, respectively) = +1.6 and ?0.4, TDM = 1.3 Ga, and lead isotopic ratios are (²⁰⁶Pb/²⁰⁴Pb) = 18.62–18.57, (²⁰⁷Pb/²⁰⁴Pb) = 15.61–15.66, and (²⁰⁸Pb/²⁰⁴Pb) = 38.65–38.69. The middle Miocene granitoids (18 Ma) are also characterized by relatively high REE and minor Eu anomalies (Eu/Eu* = 0.77–0.98) and have uniform initial ⁸⁷Sr/⁸⁶Sr (0.7065–0.7082), a range of initial Nd isotopic ratios [?Nd(T)] varying from ?2.3 to ?3.7, and Pb isotopic composition (²⁰⁶Pb/²⁰⁴Pb) = 18.67–18.94, (²⁰⁷Pb/²⁰⁴Pb) = 15.63–15.71, and (²⁰⁸Pb/²⁰⁴Pb) = 38.73–39.01. Geochemical and isotopic evidence for these Eocene–Ologocene mafic rocks suggests that the magmas originated from lithospheric mantle with a large involvement of EMII component during subduction of the Neotethyan ocean slab beneath the Central Iranian plate, and were significantly affected by crustal contamination. Geochemical and isotopic data of the middle Miocene granitoids rule out a purely crustal-derived magma genesis, and suggest a mixed mantle–crustal [MASH (melting, assimilation, storage, and homogenization)] origin in a post-collision extensional setting. Sr–Nd isotope modelling shows that the generation of these magmas involved ～60% to 70% of a lower crustal-derived melt and ～30% to 40% of subcontinental lithospheric mantle. All Niyasar plutons exhibit transitional geochemical features, indicating that involvement of an EMII component in the subcontinental mantle and also continental crust beneath the Urumieh–Dokhtar magmatic belt increased from early Eocene to middle Miocene time.     

Phanerozoic amalgamation of the Alxa Block and North China Craton: Evidence from Paleozoic granitoids,U–Pb geochronology and Sr–Nd–Pb–Hf–O isotope geochemistry

The North China Craton (NCC) has been considered to be part of the supercontinent Columbia. The nature of the NCC western boundary, however, remains strongly disputed. A key question in this regard is whether or not the Alxa Block is a part of the NCC. It is located in the vicinity of the inferred boundary, and therefore could potentially resolve the issue of the NCC's relationship to the Columbia supercontinent. Some previous studies based on the Alxa Block's geological evolution and detrital zircon ages suggested that it is likely not a part of the NCC. The lack of evidence from key igneous rock units, however, requires further constraints on the tectonic affinity of the western NCC and Alxa Block and on the timing of their amalgamation.In this study, new zircon U–Pb age and Hf–O isotopes and whole-rock geochemical and Sr–Nd–Pb isotopic data for the Paleozoic granitoids in or near the eastern Alxa Block were used to constrain the petrogenesis of these rocks and the relationship between the Alxa Block and NCC. Secondary ion mass spectrometry (SIMS) U–Pb zircon dating indicates that the Bayanbulage, Hetun, Diebusige and South Diebusige granitoids were formed at ca. 423 Ma, 345 Ma, 345 Ma and 337 Ma, respectively. The Late Silurian (Bayanbulage) quartz diorites have variable SiO₂ (58.0–67.9 wt.%), and low Sr/Y (20–24) values, while the Early Carboniferous (Hetun, Diebusige and South Diebusige) monzogranites have high SiO₂ (71.5–76.7 wt.%) and Sr/Y (40–94) values. The Late Silurian quartz diorites display relatively homogeneous and high zircon δ¹⁸O (8.5–9.1‰) and ε_Hf(t) (− 8.6 to − 5.3) values, high whole-rock ε_Nd(t) values (− 9.2 to − 7.6) and highly radiogenic Pb isotopes (²⁰⁶Pb/²⁰⁴Pb = 18.13–18.25), whereas the Early Carboniferous monzogranites exhibit relatively low and variable zircon δ¹⁸O (5.7–7.2‰) and ε_Hf(t) (− 23.1 to − 7.4) values, low whole-rock initial ⁸⁷Sr/⁸⁶Sr (0.7043–0.7070) and ε_Nd(t) (− 19.1 to − 13.5) values and variable Pb isotopes (²⁰⁶Pb/²⁰⁴Pb = 16.06–18.22). The differences in whole rock Nd model ages and Pb isotope compositions of the Paleoproterozoic–Permian rocks in either side of the west fault of the Bayanwulashan–Diebusige complexes suggest that the Alxa Block is not a part of the NCC, and that the western boundary of the NCC is probably located on this fault. Furthermore, the linear distribution of the Early Paleozoic–Early Carboniferous granitoids, the high zircon δ¹⁸O values of the Late Silurian quartz diorites, the Early Devonian metamorphism and the foreland basin system formed during the collision between the Alxa Block and the NCC indicate that a Paleozoic cryptic suture zone likely existed in this area and records the amalgamation of the Alxa Block and North China Craton. Together with detrital zircon data, the initial collision was considered to have possibly occurred in Late Ordovician.     

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.     

Monazite RW-1: a homogenous natural reference material for SIMS U–Pb and Th–Pb isotopic analysis

Mineralogy and Petrology - Well-characterized matrix-matched natural mineral references of known age are an important prerequisite for SIMS (secondary ion mass spectrometry) U–Th–Pb...     

Genesis of the Angeer Yinwula Pb–Zn deposit,Inner Mongolia,China: constraints from fluid inclusions,C–H–O–S–Pb isotope systematics,and zircon U–Pb geochronology

Arabian Journal of Geosciences - Soil toxic metal pollution is one of the most prominent environmental problems in the rapid industrialization of societies because of the considerable harm caused...     

Ore genesis of the Tianbaoshan carbonate-hosted Pb–Zn deposit,Southwest China: geologic and isotopic (C–H–O–S–Pb) evidence

The Tianbaoshan Pb–Zn deposit, part of the Sichuan–Yunnan–Guizhou (SYG) Pb–Zn metallogenic province, is located in the western Yangtze Block and contains 2.6 million tonnes of 10–15 wt.% Pb + Zn metals. Ore bodies occur as vein or tubular types and are hosted in Sinian (late Proterozoic) carbonate rocks and are structurally controlled by the SN-trending Anninghe tectonic belt and NW-trending concealed fractures. The deposits are simple in mineralogy, with sphalerite, galena, pyrite, chalcopyrite, arsenopyrite, freibergite, and pyrargyrite as ore minerals and dolomite, calcite, and quartz as gangue minerals. These phases occur as massive, brecciated, veinlet, and dissemination in dolostone of the upper Sinian Dengying Formation. Hydrogen and oxygen isotope compositions of hydrothermal fluids range from –47.6 to –51.2‰ and –1.7 to +3.7‰, respectively. These data suggest that H₂O in hydrothermal fluids had a mixed origin of metamorphic and meteoric waters. Carbon and oxygen isotope compositions range from –6.5 to –4.9‰ and +19.3 to +20.2‰, respectively. These compositions plot in the field between mantle and marine carbonate rocks with a negative correlation, suggesting that CO₂ in the ore-forming fluids had multiple sources, including the Permian Emeishan flood basalts, Sinian-to-Permian marine carbonate rocks, and organic matters in Cambrian-to-Permian sedimentary rocks. Sulphur isotope compositions range from –0.4 to +9.6‰, significantly lower than Cambrian-to-Permian seawater sulphate (+15 to +35‰) and sulphate (+15 to +28‰) from evaporates in Cambrian-to-Permian strata, implicating that the S was derived from host-strata evaporates by thermal–chemical sulphate reduction. ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb ratios range from 18.110 to 18.596, 15.514 to 15.878, and 38.032 to 39.221, respectively, which plot in field of the upper crust Pb evolution curve, unlike those of Proterozoic basement rocks, Sinian dolostone, Devonian-to-Permian carbonate rocks, and the Permian Emeishan flood basalts, implying complex derivation of Pb metal in the ore-forming fluids. Geological and isotopic studies of the Tianbaoshan Pb–Zn deposit reveal that constituents in the hydrothermal fluids were derived from multiple sources and that fluid mixing was a possible metallogenic mechanism. The studied deposit is not distal magmatic–hydrothermal, sedimentary exhalative (SEDEX), or Mississippi Valley (MVT) types, rather, it represents a unique ore deposit type, named in this article the SYG type.     

Re–Os and U–Pb Geochronology of the Erlihe Pb–Zn Deposit, Qinling Orogenic Belt, Central China, and Constraints on Its Deposit Genesis

The Erlihe Pb–Zn deposit is an important mine of the Pb–Zn metallogenic zone in the South Qinling Orogen. It has been considered a sedimentary exhalative deposit in previous investigations because the ore body occurs concordantly at the transitional location of an upright fold. Re and Os isotopic analyses for paragenetic pyrites with sphalerite and galena from the ore body have been used to determine the timing of mineralization and to trace the source of metallogenic materials. The Re–Os isotopic data of four pyrite samples construct an isochron, yielding a weighted average age of 226±17 Ma (mean square weighted deviation=1.7), which is considered the main mineralization age. A dioritic porphyrite vein sample, showing weaker mineralization, was also dated using the SHRIMP zircon U–Pb isotopic method to constrain the youngest metallogenic age of the ore deposit, because it distributes along a group of tensional joints cutting not only the upright fold in the deposit field, but also the main ore bodies. The dioritic porphyrite sample yields a weighted mean 206Pb/238U age of 221±3 Ma, which is slightly younger than the Re–Os isotopic isochron age of the pyrites, considered as the upper age limit of the mineralization, namely the ending age of the mineralization. The Os isotopic compositions of sulfide minerals distribute within a range between Os isotopic compositions of the crust and the mantle, indicating that the ore deposit can be derived from magma-related fluid, and the metallogenic materials are most likely derived from the mixing source of the crust and the mantle. The Erlihe Pb–Zn deposit and associated dioritic porphyrite vein, important records of Qinling tectonic–magmatism–mineralization activities, were formed during the Triassic collisional orogeny processes.     

Zircon U–Pb geochronology,whole-rock geochemical,and Sr–Nd–Pb isotopic constraints on the timing and origin of Permian and Triassic mafic dykes from eastern North China Craton

Acta Geochimica - This work reports an important episode of extensional, mafic magmatism that impacted the North China Craton (NCC) during the Permo-Triassic and influenced the evolution of this...     

Mantle and crustal sources of Archean anorthosite: a combined in situ isotopic study of Pb–Pb in plagioclase and Lu–Hf in zircon

Isotopic analyses of ancient mantle-derived magmatic rocks are used to trace the geochemical evolution of the Earth’s mantle, but it is often difficult to determine their primary, initial isotope ratios due to the detrimental effects of metamorphism and secondary alteration. We present in situ analyses by LA-MC-ICPMS for the Pb isotopic compositions of igneous plagioclase (An_75–89) megacrysts and the Hf isotopic compositions of BSE-imaged domains of zircon grains from two mantle-derived anorthosite complexes from south West Greenland, Fiskenæsset and Nunataarsuk, which represent two of the best-preserved Archean anorthosites in the world. In situ LA-ICPMS U–Pb geochronology of the zircon grains suggests that the minimum crystallization age of the Fiskenæsset complex is 2,936 ± 13 Ma (2σ, MSWD = 1.5) and the Nunataarsuk complex is 2,914 ± 6.9 Ma (2σ, MSWD = 2.0). Initial Hf isotopic compositions of zircon grains from both anorthosite complexes fall between depleted mantle and a less radiogenic crustal source with a total range up to 5 ε_Hf units. In terms of Pb isotopic compositions of plagioclase, both anorthosite complexes share a depleted mantle end member yet their Pb isotopic compositions diverge in opposite directions from this point: Fiskenæsset toward a high-μ, more radiogenic Pb, crustal composition and Nunataarsuk toward low-μ, less radiogenic Pb, crustal composition. By using Hf isotopes in zircon in conjunction with Pb isotopes in plagioclase, we are able to constrain both the timing of mantle extraction of the crustal end member and its composition. At Fiskenæsset, the depleted mantle melt interacted with an Eoarchean (~3,700 Ma) mafic crust with a maximum ¹⁷⁶Lu/¹⁷⁷Hf ~0.028. At Nunataarsuk, the depleted mantle melt interacted with a Hadean (~4,200 Ma) mafic crust with a maximum ¹⁷⁶Lu/¹⁷⁷Hf ~0.0315. Evidence from both anorthosite complexes provides support for the long-term survival of ancient mafic crusts that, although unidentified at the surface to date, could still be present within the Fiskenæsset and Nunataarsuk regions.     

U–Pb zircon ages,geochemical and Sr–Nd–Pb isotopic constraints on the dating and origin of intrusive complexes in the Sulu orogen,eastern China

TPost-orogenic intrusive complexes from the Sulu belt of eastern China consist of pyroxene monzonites and dioritic porphyrites. We report new U–Pb zircon ages, geochemical data, and Sr–Nd–Pb isotopic data for these rocks. Laser ablation-inductively coupled plasma-mass spectrometry U–Pb zircon analyses yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 127.4 ± 1.2 Ma for dioritic porphyrites, consistent with crystallization ages (126 Ma) of the associated pyroxene monzonites. The intrusive complexes are characterized by enrichment in light rare earth elements and large ion lithophile elements (i.e. Rb, Ba, Pb, and Th) and depletion in heavy rare earth elements and high field strength elements (i.e. Nb, Ta, P, and Ti), high (⁸⁷Sr/⁸⁶Sr)_i ranging from 0.7083 to 0.7093, low ?_Nd(t) values from ?14.6 to ? 19.2, ²⁰⁶Pb/²⁰⁴Pb = 16.65–17.18, ²⁰⁷Pb/²⁰⁴Pb = 15.33–15.54, and ²⁰⁸Pb/²⁰⁴Pb = 36.83–38.29. Results suggest that these intermediate plutons were derived from different sources. The primary magma-derived pyroxene monzonites resulted from partial melting of enriched mantle hybridized by melts of foundered lower crustal eclogitic materials before magma generation. In contrast, the parental magma of the dioritic porphyrites was derived from partial melting of mafic lower crust beneath the Wulian region induced by the underplating of basaltic magmas. The intrusive complexes may have been generated by subsequent fractionation of clinopyroxene, potassium feldspar, plagioclase, biotite, hornblende, ilmenite, and rutile. Neither was affected by crustal contamination. Combined with previous studies, these findings provide evidence that a Neoproterozoic batholith lies beneath the Wulian region.     

Origin of the Yinshan epithermal-porphyry Cu–Au–Pb–Zn–Ag deposit,southeastern China: insights from geochemistry,Sr–Nd and zircon U–Pb–Hf–O isotopes

The Yinshan deposit is a large epithermal-porphyry polymetallic deposit, and the timing and petrogenesis of ore-hosting porphyries have been hotly debated. We present new results from geochemical, whole-rock Sr–Nd and zircon U–Pb–Hf–O isotopic investigations. Zircon U–Pb data demonstrate that the quartz porphyry, dacitic porphyry, and quartz dioritic porphyry formed at ?172.2 ± 0.4 Ma, ?171.7 ± 0.5 Ma, and ?170.9 ± 0.3 Ma, respectively. Inherited zircon cores show significant age spreads from ?730 to ?1390 Ma. Geochemically, they are high-K calc-alkaline or shoshonitic rocks with arc-like trace element patterns. They have similar whole-rock Nd and zircon Hf isotopic compositions, yet an increasing trend in ?_Nd(t) and ?_Hf(t) values typifies the suite. Older (inherited) zircons of the three porphyries display Hf compositions comparable to those of the Jiangnan Orogen basement rocks. In situ zircon oxygen isotopic analyses reveal that they have similar oxygen isotopic compositions, which are close to those of mantle zircons. Moreover, a decreasing trend of δ¹⁸O values is present. We propose that the ore-related porphyries of the Yinshan deposit were emplaced contemporaneously and derived from partial melting of Neoproterozoic arc-derived mafic (or ultra-mafic) rocks. Modelling suggests that the quartz porphyries, dacitic porphyries, and quartz dioritic porphyries experienced ?25%, ?10%, and ?10% crustal contaminations by Shuangqiaoshan rocks. Our study provides important constraints on mantle–crust interaction in the genesis of polymetallic mineralization associated with Mesozoic magmatism in southeastern China.     

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.     

U–Th–Pb monazite dating and the timing of arc–continent collision in East Timor

The Timor Orogen represents one of the youngest arc–continent collisions exposed on the Earth. It has the potential to provide some of the key parameters about how this style of orogeny evolves. However, the metamorphic age of the highest-grade rocks formed in the collision remains controversial. Using U–Th–Pb dating of monazite from amphibolite-grade sillimanite and garnet-bearing schists we show the peak metamorphism occurred at 5.5–4.7 Ma. The young age of the monazite and the presence of significant amounts of common Pb required the development of a new protocol to simultaneously account for the ²³⁰Th disequilibrium and the ²⁰⁷Pb common Pb correction. The new estimate of metamorphic age is consistent with the estimates based on plate reconstructions for the initiation of arc–continent collision in East Timor. The metamorphic event is a result of this collision.     

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.     

The geological significance of Pb–Bi- and Pb–Sb-sulphosalts in the Damajianshan tungsten polymetallic deposit,Yunnan Province,China

The Sanjiang Tethyan domain in SE Asia is one of the most important mineral belts in China. Cu, Pb–Zn, Ag, Au and Sn are the most important resources in this domain, while the tungsten mineralization is poorly reported. In this study, we report on mineralogy in recent discovered Damajianshan (DMJS) tungsten (–Cu–As–Mo–Bi) polymetallic deposit in the southern part of Sanjiang Tethyan domain related to Triassic quartz porphyry. Studies have shown that besides common ore minerals, such as native bismuth, bismuthinite, ikunolite, some specific minerals of Pb–Bi- and Pb–Sb-sulphosalts (e.g. izoklakeite, bournonite, cosalite, and boulangerite) have also been found. Based on paragenetic mineral assemblages, fluid inclusions, and thermodynamic studies, the physicochemical conditions were evaluated for the entire metallogenic process. The sulfur fugacity (logf_S2) ranges from − 9.7 to − 37 with ore-forming temperatures between 190 °C and 330 °C, and the oxygen fugacity (logf_O2) ranges from − 37.5 to − 38.5 when the temperature is 250 °C. The sulfur fugacity and oxygen fugacity show strong fluctuations with broadly negative correlation, indicating that these variations in physicochemical conditions should be responsible for mineral assemblages, and are one of the most significant factors leading to the formation of the DMJS deposit. Our mineralogical studies provide new information for tungsten mineralization and further exploration of tungsten resources in the Sanjiang Tethyan mineralization domain.     

Genesis of the Weiquan Ag–Polymetallic Deposit in East Tianshan, China: Evidence from Zircon U–Pb Geochronology and C–H–O–S–Pb Isotope Systematics

The Weiquan Ag-polymetallic deposit is located on the southern margin of the Central Asian Orogenic Belt and in the western segment of the Aqishan-Yamansu arc belt in East Tianshan,northwestern China. Its orebodies, controlled by faults, occur in the lower Carboniferous volcanosedimentary rocks of the Yamansu Formation as irregular veins and lenses. Four stages of mineralization have been recognized on the basis of mineral assemblages, ore fabrics, and crosscutting relationships among the ore veins. Stage I is the skarn stage(garnet + pyroxene), Stage Ⅱ is the retrograde alteration stage(epidote + chlorite + magnetite ± hematite 士 actinolite ± quartz),Stage Ⅲ is the sulfide stage(Ag and Bi minerals + pyrite + chalcopyrite + galena + sphalerite + quartz ± calcite ± tetrahedrite),and Stage IV is the carbonate stage(quartz + calcite ± pyrite). Skarnization,silicification, carbonatization,epidotization,chloritization, sericitization, and actinolitization are the principal types of hydrothermal alteration. LAICP-MS U-Pb dating yielded ages of 326.5±4.5 and 298.5±1.5 Ma for zircons from the tuff and diorite porphyry, respectively. Given that the tuff is wall rock and that the orebodies are cut by a late diorite porphyry dike, the ages of the tuff and the diorite porphyry provide lower and upper time limits on the age of ore formation. The δ~(13)C values of the calcite samples range from-2.5‰ to 2.3‰, the δ~(18)O_(H2 O) and δD_(VSMOW) values of the sulfide stage(Stage Ⅲ) vary from 1.1‰ to 5.2‰ and-111.7‰ to-66.1‰, respectively,and the δ~(13)C, δ~(18)O_(H2 O) and δD_(V-SMOW) values of calcite in one Stage IV sample are 1.5‰,-0.3‰, and-115.6‰, respectively. Carbon, hydrogen, and oxygen isotopic compositions indicate that the ore-forming fluids evolved gradually from magmatic to meteoric sources. The δ~(34)S_(V-CDT) values of the sulfides have a large range from-6.9‰ to 1.4‰, with an average of-2.2‰, indicating a magmatic source, possibly with sedimentary contributions. The ~(206)Pb/~(204)Pb, ~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of the sulfides are 17.9848-18.2785,15.5188-15.6536, and 37.8125-38.4650, respectively, and one whole-rock sample at Weiquan yields~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of 18.2060, 15.5674, and 38.0511,respectively. Lead isotopic systems suggest that the ore-forming materials of the Weiquan deposit were derived from a mixed source involving mantle and crustal components. Based on geological features, zircon U-Pb dating, and C-H-OS-Pb isotopic data, it can be concluded that the Weiquan polymetallic deposit is a skarn type that formed in a tectonic setting spanning a period from subduction to post-collision. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from host rocks during their ascent, and a gradual mixing with meteoric water took place in the later stages.