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.     

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...     

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.     

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.     

Reconnaissance-style EPMA chemical U–Th–Pb dating of uraninite

EPMA chemical U-Th-Pb uraninite analysis has been used to constrain the age of the granite-related, Rössing South uranium prospect in Namibia and the Kintyre unconformity-related uranium deposit in Western Australia. Uraninite from the Rössing South prospect has an age of 496.1 ± 4.1 Ma, which is similar to the age of other uranium deposits in the region at Rössing and Goanikontes. Uraninite grains analysed from the Kintyre deposit have an age of 837 +35/-31 Ma suggesting that the uranium mineralisation occurred during or after the latest period of sedimentation in the Yeneena Basin during the ca 850 to ca 800 Ma Miles Orogeny.     

LA–ICP–MS U–Pb定年技术相关问题探讨

LA–ICP–MS U–Pb定年技术是地质科学中被广泛应用的重要手段。发展至今，该技术已相对成熟，但在实际工作中仍需要注意一些关键问题。笔者就该技术的样品准备、定年结果的取舍、铅丢失问题、普通铅问题和定年结果投图与解释等5个方面进行简要探讨。研究认为，对于复杂矿物进行U–Pb定年研究建议不分选出单矿物，而是采用矿物识别定位手段和LA–ICP–MS仪器相结合的技术手段，直接在岩石光片或探针片上进行原地原位微区定年分析，但要注意样品准备过程中可能存在的铅污染问题。在碎屑矿物定年结果选择方面，对于大于1.5Ga的定年测点，笔者建议采用₂₀₇Pb/₂₀₆Pb年龄代表该颗粒的结晶年龄，而对于小于1.5 Ga的定年测点则应采用₂₀₆Pb/₂₃₈U年龄。对沉积岩最大沉积年龄的判断和选择主要依靠统计学方法，必要时需要结合地球化学数据和地质背景信息作为辅助判断依据。对于连续分布在谐和线上的年轻样品要提高警惕，需要采用谐和图、加权平均图、CL图像和元素含量等多种手段识别是否存在铅丢失不一致线。针对普通铅校正问题，笔者重...     

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.     

Staurolite as an isotopic U–Pb geochronometer

A new approach is suggested for measuring the real U–Pb and Pb–Pb ages of rock-forming metamorphic staurolite. Previously, two approaches have been used for this purpose: (1) measurement of the lead isotopic compositions, uranium and lead contents in leach substance as a product of the step-leaching technique; age is calculated by plotting the Pb–Pb leaching isochron; and (2) lead and uranium isotopic compositions are measured in completely dissolved mineral material without leaching. In both cases, it is assumed a priori that inclusions, overgrowths, secondary phases, and the host mineral are cogenetic. This assumption may lead to errors in the measured age. The technique suggested in this paper uses various reagents (acids) to purify staurolite from the above-mentioned secondary phases while obtaining a staurolite “pure culture,” its subsequent disolution, introduction of the mixed spike, separation of lead and uranium compounds, and, finally, estimation of a real staurolite age using several samples to plot the monomineralic Pb–Pb isochron or by plotting measured Pb/U ratios in the diagram with concordia. The data can be used then to reconstruct the P–T–t evolution of metamorphism.     

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.     

Origin of epithermal Ag–Au–Cu–Pb–Zn mineralization in Guanajuato, Mexico

The Guanajuato epithermal district is one of the largest silver producers in Mexico. Mineralization occurs along three main vein systems trending dominantly northwest–southeast: the central Veta Madre, the La Luz system to the northwest, and the Sierra system to the east. Mineralization consists dominantly of silver sulfides and sulfosalts, base metal sulfides (mostly chalcopyrite, galena, sphalerite, and pyrite), and electrum. There is a broad zonation of metal distribution, with up to 10 % Cu+Pb+Zn in the deeper mines along the northern and central portions of the Veta Madre. Ore occurs in banded veins and breccias and as stockworks, with gangue composed dominantly of quartz and calcite. Host rocks are Mesozoic sedimentary and intrusive igneous rocks and Tertiary volcanic rocks. Most fluid inclusion homogenization temperatures are between 200 and 300 °C, with salinities below 4 wt.% NaCl equivalent. Fluid temperature and salinity decreased with time, from 290 to 240 °C and from 2.5 to 1.1 wt.% NaCl equivalent. Relatively constant fluid inclusion liquid-to-vapor ratios and a trend of decreasing salinity with decreasing temperature and with increasing time suggest dilution of the hydrothermal solutions. However, evidence of boiling (such as quartz and calcite textures and the presence of adularia) is noted along the Veta Madre, particularly at higher elevations. Fluid inclusion and mineralogical evidence for boiling of metal-bearing solutions is found in gold-rich portions of the eastern Sierra system; this part of the system is interpreted as the least eroded part of the district. Oxygen, carbon, and sulfur isotope analysis of host rocks, ore, and gangue minerals and fluid inclusion contents indicate a hydrothermal fluid, with an initial magmatic component that mixed over time with infiltrating meteoric water and underwent exchange with host rocks. Mineral deposition was a result of decreasing activities of sulfur and oxygen, decreasing temperature, increasing pH, and, in places, boiling.     

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.     

The Jabali nonsulfide Zn–Pb–Ag deposit,western Yemen

The Jabali Zn–Pb–Ag deposit is located about 110 km east of Sana'a, the capital of Yemen, along the western border of the Marib-Al-Jawf/Sab'atayn basin. The economic mineralization at Jabali is a nonsulfide deposit, consisting of 8.7 million tons at an average grade of 9.2% zinc, derived from the oxidation of primary sulfides. The rock hosting both primary and secondary ores is a strongly dolomitized carbonate platform limestone of the Jurassic Shuqra Formation (Amran Group). The primary sulfides consist of sphalerite, galena and pyrite/marcasite. Smithsonite is the most abundant economic mineral in the secondary deposit, and is associated with minor hydrozincite, hemimorphite, acanthite and greenockite. Smithsonite occurs as two main generations: smithsonite 1, which replaces both host dolomite and sphalerite, and smithsonite 2, occurring as concretions and vein fillings in the host rock. At the boundary between smithsonite 1 and host dolomite, the latter is widely replaced by broad, irregular bands of Zn-bearing dolomite, where Zn has substituted for Mg. The secondary mineralization evolved through different stages: 1) alteration of original sulfides (sphalerite, pyrite and galena), and release of metals in acid solutions; 2) alteration of dolomite host rock and formation of Zn-bearing dolomite; 3) partial dissolution of dolomite by metal-carrying acid fluids and replacement of dolomite and Zn-bearing dolomite by a first smithsonite phase (smithsonite 1). To this stage also belong the direct replacement of sphalerite and galena by secondary minerals (smithsonite and cerussite); 4) precipitation of a later smithsonite phase (smithsonite 2) in veins and cavities, together with Ag- and Cd-sulfides.The δ¹⁸O composition of Jabali smithsonite is generally lower than in other known supergene smithsonites, whereas the carbon isotope composition is in the same range of the negative δ¹³C values recorded in most supergene nonsulfide ores. Considering that the groundwaters and paleo-groundwaters in this area of Yemen have negative δ¹⁸O values, it can be assumed that the Jabali smithsonite precipitated in different stages from a combination of fluids, possibly consisting of local groundwaters variably mixed with low-temperature hydrothermal waters. The carbon isotope composition is interpreted as a result of mixing between carbon from host rock carbonates and soil/atmospheric CO₂.The most favorable setting for the development of the Jabali secondary deposit could be placed in the early Miocene (~ 17 Ma), when supergene weathering was favored by major uplift and exhumation resulting from the main phase of Red Sea extension. Low-temperature hydrothermal fluids may have also circulated at the same time, through the magmatically-induced geothermal activity in the area.     

Metallogeny of precious and base metal mineralization in the Murchison Greenstone Belt, South Africa: indications from U–Pb and Pb–Pb geochronology

The 3.09 to 2.97 Ga Murchison Greenstone Belt is an important metallotect in the northern Kaapvaal Craton (South Africa), hosting several precious and base metal deposits. Central to the metallotect is the Antimony Line, striking ENE for over 35?km, which hosts a series of structurally controlled Sb–Au deposits. To the north of the Antimony Line, hosted within felsic volcanic rocks, is the Copper–Zinc Line where a series of small, ca. 2.97 Ga Cu–Zn volcanogenic massive sulfide (VMS)-type deposits occur. New data are provided for the Malati Pump gold mine, located at the eastern end of the Antimony Line. Crystallizations of a granodiorite in the Malati Pump Mine and of the Baderoukwe granodiorite are dated at 2,964?±?7 and 2,970?±?7?Ma, respectively (zircon U–Pb), while pyrite associated with gold mineralization yielded a Pb–Pb age of 2,967?±?48?Ma. Therefore, granodiorite emplacement, sulfide mineral deposition and gold mineralization all happened at ca. 2.97?Ga. It is, thus, suggested that the major styles of orogenic Au–Sb and the Cu–Zn VMS mineralization in the Murchison Greenstone Belt are contemporaneous and that the formation of meso- to epithermal Au–Sb mineralization at fairly shallow levels was accompanied by submarine extrusion of felsic volcanic rocks to form associated Cu–Zn VMS mineralization.     

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 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.     

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.     

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.     

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.     

Some new data on the genesis of the Linghou Cu–Pb–Zn polymetallic deposit—Based on the study of fluid inclusions and C–H–O–S–Pb isotopes

The Linghou deposit, located near Hangzhou City of Zhejiang Province, eastern China, is a medium-sized polymetallic sulfide deposit associated with granitic intrusion. This deposit is structurally and lithologically controlled and commonly characterized by ore veins or irregular ore lenses. In this deposit, two mineralization events were identified, of which the former produced the Cu–Au–Ag orebodies, while the latter formed Pb–Zn–Cu orebodies. Silicification and calc-silicate (skarn type), phyllic, and carbonate alternation are four principal types of hydrothermal alteration. The early Cu–Au–Ag and late Pb–Zn–Cu mineralizations are characterized by quartz ± sericite + pyrite + chalcopyrite + bornite ± Au–Ag minerals ± magnetite ± molybdenite and calcite + dolomite + sphalerite + pyrite + chalcopyrite + galena, respectively. Calcite clusters and calcite ± quartz vein are formed during the late hydrothermal stage.The NaCl–H₂O–CO₂ system fluid, coexisting with NaCl–H₂O system fluid and showing the similar homogenization temperatures (385 °C and 356 °C, respectively) and different salinities (16.89–21.68 wt.% NaCl eqv. and 7.70–15.53 wt.% NaCl eqv.), suggests that fluid immiscibility occurred during the Cu–Au–Ag mineralization stage and might have given rise to the ore-metal precipitation. The ore-forming fluid of the Pb–Zn–Cu mineralization mainly belongs to the NaCl–H₂O–CO₂ system of high temperature (~ 401 °C) and mid-high salinity (10.79 wt.% NaCl eqv.).Fluids trapped in the quartz-chalcopyrite vein, Cu–Au–Ag ores, Pb–Zn–Cu ores and calcite clusters yielded δ¹⁸O_H2O and δD values varying from 5.54‰ to 13.11‰ and from − 71.8‰ to − 105.1‰, respectively, indicating that magmatic fluids may have played an important role in two mineralization events. The δ¹³C_PDB values of the calcite change from − 2.78‰ to − 4.63‰, indicating that the CO₃^2 − or CO₂ in the ore-forming fluid of the Pb–Zn–Cu mineralization was mainly sourced from the magmatic system, although dissolution of minor marine carbonate may have also occurred during the ore-forming processes. The sulfide minerals have homogeneous lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb ranging from 17.958 to 18.587, ²⁰⁷Pb/²⁰⁴Pb ranging from 15.549 to 15.701, and ²⁰⁸Pb/²⁰⁴Pb ranging from 37.976 to 39.052, indicating that metallic elements of the Linghou deposit came from a mixed source involving mantle and crustal components.Based on geological evidence, fluid inclusions, and H–O–C–S–Pb isotopic data, the Linghou polymetallic deposit is interpreted as a high-temperature, skarn-carbonate replacement type. Two types of mineralization are both related to the magmatic–hydrothermal system, with the Cu–Au–Ag mineralization having a close relationship with granodiorite.