Initial Pb Isotopic Compositions Research Articles

Post-Imbrium Pb–Pb isochron ages for Apollo basaltic impact melt samples 14078 and 68415

The Apollo 14 and 16 missions returned several samples commonly interpreted as crystalline impact melt, with ages of approximately 3800–3850 Ma. Previous work has suggested that these rocks formed in one or more pre-Imbrium basin forming impact(s). By contrast, recent ages determined for a range of lunar breccias provide compelling evidence that the Imbrium basin was formed at approximately 3920 Ma. Using an approach previously demonstrated in lunar basalts, Pb–Pb isochron ages are determined for two of these proposed impact melt samples (14078: 3848 ± 4 Ma; and 68415: 3834 ± 11 Ma). In the case of 14078, the least radiogenic Pb isotopic compositions measured here are interpreted as representing the initial Pb isotopic composition of the sample. This value indicates derivation from a source (or sources) with high 238 U/ 204 Pb ratios (approx. 2400), similar to those predicted for the Apollo 14 high-Al and very high-K basalts. It was not possible to determine an equivalent initial Pb isotopic composition for 68415, but Pb isotope evolution models indicate that the sample would have been derived from lithologies with lower 238 U/ 204 Pb source ratios (approx. 1000). In both cases, the samples are interpreted as having been formed by impacts local to the Apollo 14 and Apollo 16 landing sites.

Albany K‐Feldspar: A New Pb Isotope Reference Material

Lead isotopes are a powerful and versatile tool to elucidate fundamental geological problems related to the formation and evolution of continental crust. K‐feldspar is a popular target for Pb isotope measurement as it is prevalent in many rock types and tends to capture the initial Pb isotope composition of its parental magma. We present data for a new Pb isotope reference material: Albany K‐feldspar; as well as updated data for Shap K‐feldspar. Results of Pb double‐spike TIMS for Albany K‐feldspar are 206Pb/204Pb = 16.7872 ± 0.0062, 207Pb/204Pb = 15.5640 ± 0.0056, and 208Pb/204Pb = 36.6600 ± 0.0168 (2s). TIMS measurement results for Shap K‐feldspar indicate two isotopically distinct Pb populations. LA‐MC‐ICP‐MS, with a spatial resolution as high as 15 μm, indicates a homogeneous Pb isotopic composition in Albany K‐feldspar. In accord with previous studies, our results show that scatter in the measured Pb isotope ratios, related to the low natural isotopic abundance of 204Pb, along with the effect of isobaric 204Hg‐204Pb interference, increases at lower count rates. However, the mean Pb isotope ratios measured via LA‐MC‐ICP‐MS using a range of spot sizes are in excellent agreement with TIMS results thus highlighting the feasibility of Pb isotope determination via LA‐MC‐ICP‐MS to access geological information preserved in small crystals, including mineral inclusions.

High-precision ID-TIMS U-Pb geochronology of perovskite (CaTiO3) from the Ice River Complex, Southeastern British Columbia

Uranium‑lead perovskite in situ geochronology has become a cornerstone technique for determining the emplacement timing of alkaline, ultrapotassic, and silica-undersaturated igneous rocks, kimberlites, and carbonatites. Accurate in situ dates are dependent on the availability of matrix matched mineral reference materials which themselves are chemically well characterized and dated accurately to the highest possible precision. When dating perovskite to high precision, such as by isotope dilution thermal ionization mass spectrometry (ID-TIMS), appropriately accounting and correcting for the quantity and isotopic composition of Pb incorporated into the crystal upon crystallization (Pbi) is a large source of uncertainty and potential inaccuracy. Unfortunately, although ultra-high precision perovskite dates are attainable with modern mass spectrometry techniques, the accuracy of applied Pbi compositions, which can be a considerable percentage of total Pb in a crystal, has not kept pace, resulting in percent level inaccuracy on precisely measured isotopic ratios.In an effort to characterize the age and initial Pb isotopic composition of a readily available, relatively pure perovskite endmember (93–98%) which will be useful as a matrix matched age reference material for in situ U-Pb geochronology, we date crystals isolated from three samples from the Ice River Complex (samples 81IR6, I90.3, and I92.30) by ID-TIMS and evaluate their suitability as known-age reference materials. We directly determine the isotopic composition of Pbi in each sample by ID-TIMS measurement of cogenetic low 238U/204Pb (μ < 500) phlogopite, apatite, and/or clinopyroxene. Using these initial common Pb isotopic compositions, which are significantly more radiogenic than those predicted by age appropriate Pb evolution models, we obtain ultra-precise weighted-mean 206Pb/238U perovskite dates of 355.83 ± 0.14, 355.04 ± 0.15, and 357.34 ± 0.12 Ma on the three Ice River samples, respectively. These dates are consistent with the relative emplacement ages previously established for units in the Ice River layered ultramafic series based on field relationships. They also demonstrate the feasibility of attaining accurate perovskite dates in instances when maximum precision is critical by utilizing ID-TIMS analysis of cogenetic low uranium phases for direct measurement of Pbi.

Petrogenesis of early cretaceous intermediate to felsic rocks in Shanghai, South China: Magmatic response to Paleo-Pacific plate subduction

Voluminous magmatism and extensional deformation are the prominent late Mesozoic tectonic features in East Asia, which recorded the evolutionary history of the continental marginal lithosphere. Due to the thick covering of Quaternary and Pliocene sediments in the region, the Early Cretaceous magmatism in northeastern South China is not well constrained. In this study, we collected samples from the boreholes in Shanghai, East China and provided geochronological, elemental and isotopic analyses of andesite and granodiorite. Zircon UPb age results indicate that andesites and granodiorites were formed at ca. 135 to 102 Ma. The andesites exhibit moderate MgO contents, slightly radiogenic Sr (87Sr/86Sr(t) = 0.706149 to 0.706170) and variable unradiogenic Nd and Hf isotopic compositions (εNd(t) = −5.32 to −5.12; εHf(t) = −10.8 to −0.6). The granodiorites exhibit arc-like trace-element patterns with high Sr/Y ratios, as well as slightly radiogenic initial Sr (87Sr/86Sr(t) = 0.706754 to 0.706790) and moderately unradiogenic Nd and Hf isotopic compositions (εNd(t) = −6.54 to −6.27; εHf(t) = − 4.0 to −6.7). Both andesites and granodiorites exhibit similar initial Pb isotopic compositions (andesites: 206Pb/204Pb = 18.232–18.259, 207Pb/204Pb = 15.547–15.548, and 208Pb/204Pb = 38.338–38.350; granodiorites: 206Pb/204Pb = 17.930–17.946, 207Pb/204Pb = 15.542–15.543, and 208Pb/204Pb (38.256–38.293). The results recommend that the ca.130 Ma andesites were produced by the partial melting of an enriched lithospheric mantle, which was previously metasomatized with sediments in the source region in a continental arc setting of the Paleo-Pacific subduction. The ca.102 Ma adakitic granodiorites probably originated from partial melting of the lower crust with the addition of mantle-derived magmas. With the consolidation of previous studies, we argue that the flat slab subduction of the paleo-Pacific Plate led to the formation of these intermediate to felsic magmatism.

Isotopic and trace element data of Tissint indicate a homogeneous strewn field, mobilization of Sr, REE, and Pb during shock metamorphism, and limits on the incorporation of martian surficial materials in impact melt glass

The Tissint strewn field has produced over 16 kg of material that has minimal terrestrial weathering and/or contamination. Tissint, along with 16 other incompatible trace element (ITE)-depleted shergottite specimens with igneous crystallization ages spanning 327–2403 Ma, were ejected together from Mars 1.1 m.y. ago. Despite the geochemical similarities of fragments from the Tissint strewn field, there are reported discrepancies in age determinations from different fragments that raise the possibility that the strewn field may be heterogenous. There are also questions about whether the shock ejection event incorporated martian soil components into impact glass, and the sources of radiogenic Sr and Pb that have been measured from leachate fractions in previous studies. An impact melt-rich fragment of Tissint was analyzed by LA-ICPMS for rare-earth element (REE) and highly siderophile element (HSE) concentrations and Pb isotopic compositions. Leachate and residues from 8 specimens representing separate individual fragments collected from the strewn field were analyzed for Rb-Sr. Unleached fractions of the 8 specimens were also analyzed for Sm-Nd and Lu-Hf.The measured REE and HSE concentrations of impact melt glass and associated sulfide measured by LA-ICPMS are consistent with bulk rock compositions of Tissint and show no evidence for incorporation of more ITE-enriched martian surface components. Measured Pb isotopic compositions confirm that the impact melt glass and associated sulfide contain no evidence for incorporation of more radiogenic materials than the Pb compositions inherited from the primary magma. In situ Pb isotopic data from sulfide likely represents the most robust method for constraining initial Pb isotopic compositions of shergottites whereas approaches that rely on leaching and digestion may not remove all mineral and/or crack surface contaminants.Rubidium-strontium analyses of the 8 Tissint specimens indicate that labile components hosting HCl-soluble Rb and Sr are not in isotopic equilibrium with the igneous assemblage and that the washed residues are in isotopic equilibrium with the igneous assemblage. The Sr isotopic compositions of the leachate are within the range of ‘more ITE-enriched’ depleted shergottites, perhaps indicating sources from the igneous pile on Mars. The radiogenic Sr component could represent crack and mineral surface coatings of volatilized materials derived from nearby depleted shergottite rock units during the impact ejection process but are not radiogenic enough to represent ITE-enriched crust or mantle components.The Lu-Hf isotopic data from the specimens indicate no evidence of contamination or element mobility, whereas the Rb-Sr and Sm-Nd isotopic systems show evidence for element mobility and potential mixing with an isotopic component not in equilibrium with the igneous phases. The calculated ages using data compiled from Brennecka et al. (2014), and Grosshans (2013) for Lu-Hf, Rb-Sr, and Sm-Nd are 571 ± 84 Ma, 590 ± 49 Ma and 559 ± 39 Ma, respectively. These data indicate that the specimens analyzed here are cogenetic and the Tissint strewn field appears to be homogeneous.

Calibrating volatile loss from the Moon using the U-Pb system

Previous isotope studies of lunar samples have demonstrated that volatile loss was an important part of the early history of the Moon. The radiogenic U-Pb system, where Pb has a significantly lower T50% condensation temperature than U, has the capacity to both recognize and calibrate the extent of volatile loss but this approach has been hindered by terrestrial Pb contamination of samples. We employ a novel method that integrates analyses of individual samples by Ion Microprobe and Thermal Ionization mass spectrometry to correct for ubiquitous common Pb contamination, a method that results in significantly higher estimates for µ-values (238U/204Pb) than previously reported. Using this method, six of seven samples of low-Ti basaltic meteorites return µ-values between 1900 and 9600, values that are consistent with a re-evaluation of published results that return µ-values of 510–2900 for both low- and high-Ti basalts. While some degree of fractionation during partial melting may increase µ-values, we infer that the source region(s) for the basalts must also have had elevated µ-values by the time the lunar magma ocean solidified. Models to account for the available initial Pb isotopic compositions of lunar basalts in light of timing constraints from thermal modelling imply that their source regions had a µ-value of at least 280, consistent with the elevated µ-values of lunar basalts and that inferred for their sources. Such high µ-values are attributed to the preferential loss of more than 99% of the Pb over U relative to a precursor with a Mars-like composition in the aftermath of the giant impact. Such an extensive loss of Pb is consistent with previously reported losses of other elements with comparable volatility, namely Zn, Rb, Ga and CrO2. Finally, our modelling of highly-radiogenic lunar Pb isotopes assuming crystallization of the lunar magma ocean over 10′s of millions of years shows that the elevated µ-values allows for, but does not require, a young Moon formation age.

U-Pb ID-TIMS reference ages and initial Pb isotope compositions for Durango and Wilberforce apatites

We present new Isotope Dilution Thermal Ionisation Mass Spectrometry (ID-TIMS) U-Pb reference ages for apatites from type locations Durango, Cerro de Mercado, Mexico and Wilberforce, Ontario, Canada. A weighted mean 206Pb/238U obtained from 14 Durango apatite fragments yields an age of 32.716 ± 0.061/0.063/0.072 Ma (2σ analytical uncertainty; analytical and tracer uncertainty combined; analytical, tracer, and decay constant uncertainties combined; MSWD = 0.81). Correction of excess 206Pb from Th-disequilibrium in Durango apatite, using a Th/Umelt of 3.5 ± 1, yields a weighted mean 206Pb/238U age of 32.29 ± 0.12/0.12/0.12 Ma. A concordia-constrained linear 3-D isochron yields an age of 32.683 ± 0.050 Ma for Durango apatites (ratio + error (%) + correlation coefficients; MSWD = 7.6; no propagation of decay constant and Pbc composition uncertainty, isoplot v. 4.15). A weighted mean 206Pb/238U obtained from 9 Wilberforce apatite fragments yield an age of 930.9 ± 8.0/8.0/8.1 Ma (MSWD = 0.65). Excess 206Pb correction for Wilberforce is negligible (<100kyr) relative to the uncertainty. A concordia-constrained linear 3-D isochron yields an age of 923 ± 14 Ma (ratio + error (%) + correlation coefficients; MSWD = 367; no propagation of decay constant and Pbc composition uncertainty, isoplot v. 4.15) for Wilberforce apatites. Initial Pb isotope compositions for these apatites were obtained by regression of the U-Pb data (3-D linear regression) and yielded a 206Pb/204Pb of 18.19 ± 0.12 and 207Pb/204Pb of 15.67 ± 0.10 for the Durango apatite reference material, and a 206Pb/204Pb of 17.06 ± 0.37 and 207Pb/204Pb of 15.33 ± 0.29 for the Wilberforce apatite reference material. Varying the assumed initial Pb composition can have significant effects on the calculated U-Pb age of apatites, which is highlighted with synthetic apatite data based on the composition of the Durango apatite reference material. For Durango apatites, the frequently used estimates of common Pb from two-stage Pb evolution models can artificially shift the U-Pb data and yield inaccurate dates, relative to the use of 3-D isochrons constructed using data obtained from Durango apatite. The use of 3-D isochrons to extract initial Pb isotope data should be restricted to samples/material with single U-Pb date population (closed system) and where estimates from Pb-bearing-U-free co-genetic mineral phases is unavailable and evaluated on a case-by-case basis.

Use of high-U hydrothermal apatite containing excess 206Pb to constrain the age of uranium mineralization at the Coles Hill deposit, Virginia, USA

High-U hydrothermal apatite with complex UPb systematics is closely spatially associated with mineralization at the Coles Hill deposit, the largest unmined uranium deposit known in the United States. The deposit is hosted in metasomatized rocks of the 450- to 430-Ma-old Martinsville Intrusive Complex in south-central Virginia. Direct dating of metamict uranium-ore minerals, mostly coffinite, is not possible due to open-system radon loss. Instead, UPb isotopes in cogenetic apatite were investigated as a means of evaluating the age of mineralization. Here we report in situ electron probe microanalyses (EPMA) of coffinite, isotope-dilution thermal-ionization mass spectrometry (ID-TIMS) UPb data for mineralized whole rock samples, and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) UPb isotope data for apatite in both unmineralized and U-mineralized host rocks.Massive deficits in radiogenic Pb preclude reliable UPb “chemical ages” calculated from EPMA data obtained from coffinite. In contrast, LA-ICPMS data for secondary apatite in unmineralized rocks indicate low-U concentrations (100–102 ppm), “normal” (consistent with models of terrestrial Pb isotopic evolution) initial Pb isotope compositions, and UPb age estimates of ~330 Ma, which is consistent with dates previously proposed for the regional Paleozoic shear zone that hosts the deposit. Ore-stage apatite associated with coffinite has high-U concentrations (typically 102–103 ppm but up to 2.4 wt% U) and large excesses of 206Pb (207Pb/206Pb < 0.01) unsupported by in situ U decay. Data show that initial Pb had variable isotopic compositions including both “normal” Pb derived from host rocks and 206Pb-enriched Pb introduced by secondary metasomatic fluids. Evaluation of the complex evolution and mixing of Pb sources has broader implications for UPb dating of hydrothermal apatite.Excess 206Pb in apatite is derived from decay products of 222Rn lost from coffinite and mobilized by Na-, P-, and U-enriched metasomatic fluids during the main mineralizing event at ~230 Ma. Ore-stage alteration did not uniformly reset the UPb systematics in host rocks precluding a well-constrained whole-rock isochron age. However, whole-rock isotope data imply U mobility at ~200–220 Ma and support a Triassic age for the final stages of mineralization. Results also indicate that apatite with up to several weight percent uranium is able to retain U and its decay products for hundreds of millions of years; an important consideration when assessing this mineral as a potential matrix for long-term storage of radioactive waste.

Geochemistry and Sr–Nd–Hf–Pb isotope systematics of late Carboniferous sanukitoids in northern West Junggar, NW China: Implications for initiation of ridge-subduction

The study of Carboniferous magmatism in northern West Junggar plays an important role in understanding the tectonic evolution of that part of the Central Asian Orogenic Belt. In this study, we present petrology, zircon U–Pb geochronology, mineral and whole-rock geochemistry, and the Sr–Nd–Hf–Pb isotope compositions of volcanic rocks from the Hamutusi area of northern West Junggar. LA–ICP–MS zircon U–Pb analysis of a representative andesite yielded an early to late Carboniferous age of 324.4 ± 6.9 Ma. The volcanic rocks are calc-alkaline, with high SiO2 (54.2–57.8 wt%), MgO (5.97–8.33 wt%), Mg# (60–69), Cr (147–448 ppm), and Ni (29.1–120 ppm) contents, and are enriched in large ion lithophile elements (LILE) and light rare earth elements (LREE), but depleted in high field strength elements (HFSE), these characteristics are similar to those of typical sanukitoids within the Setouchi volcanic belt in Japan. All samples have radiogenic initial Sr and Pb isotopic compositions, and low εNd(t) and εHf(t) values, indicating the sanukitoids were generated by partial melting of subducting sediments in which the melts interacted with the mantle. Geochemical modeling calculations indicate a proportion of 3–10% sediment melt and slab-derived fluids were mixed with the depleted mantle to produce the bulk of the Hamutusi rocks. We conclude that the studied rocks from north West Junggar record the initiation of ridge subduction related to a transition from normal subduction to subduction of young and hot oceanic lithosphere between the early and late Carboniferous.

U-Pb systematics of uranium-rich apatite from Adirondacks: Inferences about regional geological and geochemical evolution, and evaluation of apatite reference materials for in situ dating

High‑uranium apatite samples from iron oxide-apatite (IOA) deposits of the eastern Adirondack Mountains, New York, are evaluated as potential standards for in situ U-Pb dating of high-U apatite. Age data for these minerals also have implications for better understanding the geological evolution in the region. Secondary ion mass spectrometry (SIMS), and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analyses of these samples show that they have high and variable uranium contents of 5–485 ppm. High-precision isotope-dilution thermal ionization mass spectrometry (ID-TIMS) dating yielded U–Pb errorchron ages of 907 ± 14 Ma (MSWD = 20) and 924 ± 13 Ma (MSWD = 547), showed disturbance in the U–Pb systems, and revealed radiogenic compositions of initial Pb (206Pb/204Pb ratios of 339 ± 48 and 162 ± 39). Nominal age calculations using assumed initial Pb isotopic compositions close to average terrestrial crustal Pb yield biased and older ages despite the radiogenic Pb isotopic composition of the apatites (206Pb/204Pb from 1300 to >4000). The apatite ages calculated using the measured initial Pb isotopic compositions are younger than the U–Pb ages of 1008.0 ± 3.2 Ma and 992.4 ± 7.7 Ma determined by SIMS for zircon cores and rims, respectively, separated from one of these ore samples. It indicates protracted fluid activity in the deposit that lasted for ~100 Ma after the ore formation, or later disturbance of the apatite. The time of U enrichment that we inferred from radiogenic composition of initial Pb is within uncertainties with primary ore crystallization, indicating that high 206Pb/204Pb ratios of initial Pb were caused by dissolution-reprecipitation of primary apatite.Despite the variability in U contents and disturbance of the U–Pb system in the apatites, our SIMS and LA-ICPMS analyses show that these samples can be used, with due caution, as reference materials (RMs) for dating apatite with similarly high-U concentration. They potentially provide more precise and accurate results compared to the usage of better behaved but lower-U apatite RMs due to improved counting statistics and reduced matrix effects, especially important for LA-ICPMS with less sensitive quadrupole mass analysers.The McClure Mountain apatite, a widely used reference for in situ dating, was used in the present study as a matrix-matched reference material for in situ LA-ICPMS analyses. We also analysed it by ID-TIMS and obtained more radiogenic Pb-isotopic data and more precise ages that are in agreement within uncertainties with the previously published result (Schoene and Bowring, 2006); combined data yielded a U-Pb errorchron age of 525.3 ± 1.7 Ma (MSWD = 70). The data corrected for initial Pb using the total U/Pb isochron yield the single Concordia age of 525.10 ± 0.75 Ma (MSWD = 1.1). Two independent ID-TIMS U–Pb studies support the use of this apatite as a primary RM for dating of low-U apatite with a normal composition of initial Pb. However, its small grain size and low U concentration (11–29 ppm) can cause elevated uncertainty in LA-ICPMS age determinations for unknowns. Better precision in our LA-ICPMS analyses was achieved using Madagascar (MAD1 and MAD2) apatite RM with U contents in the range of 28–58 ppm.

Paleozoic Alkaline-Mafic Intrusions of the Kuznetsk Alatau, Their Sources and Conditions for Magma Generation

Cambrian, Devonian and Permian differentiated intrusions made up of subalkaline and alkaline gabbro, foidolite, nepheline and alkaline syenites, and rare carbonatites compose an area in the northern part of the Kuznetsk Alatau alkaline igneous province. Primary melts of the intrusions were moderately fractionated ((La/Yb)N up to 7–12) and could be derived by 1–10% partial melting of mantle spinel lherzolite. The LILE and HFSE distribution in the mafic rocks (Rb 6–58, Ba 111–2499, Sr 175–1555, REE 28–208, Zr 40–315, Nb 1.5–52, Th 0.3–12, U 0.2–7.4, ppm) indicates the involvement of OIB- and IAB-type oceanic and marginal-continental lithosphere materials in magma generation. A source of the parental melt was heterogeneous and consisted of a mixture of depleted (PREMA and E-MORB) and enriched (EM-type) mantle magmas with an intermediate isotopic ratio eNd(Т) ~ 3–9. Apparent heterogeneity of the source is reflected in the initial Pb isotopic composition of rocks and minerals: 208Pb/204Pb = 37.49–38.12, 207Pb/204Pb = 15.53–15.71, 206Pb/204Pb = 17.92–20.65. The subsequent upper crustal contamination of the melts led to a simultaneous increase in the isotopic ratios (87Sr/86Sr)Т ~ 0.7042–0.7074; δ18ОV-SMOW ~ 6.3–15.5‰, as well as to the enrichment of rocks in 207Pb. Geochemical data suggest that primary melts were formed by impact of a mantle plume (OIB-type hot spot) on accretion-collisional complexes of the former active continental margin. Such geodynamic setting provides the generation of heterogeneous magma sources even within a small igneous province.

Tourmaline as a Tracer of Late-Magmatic to Hydrothermal Fluid Evolution: The World-Class San Rafael Tin (-Copper) Deposit, Peru

Abstract The world-class San Rafael tin (-copper) deposit (central Andean tin belt, southeast Peru) is an exceptionally large and rich (&amp;gt;1 million metric tons Sn; grades typically &amp;gt;2% Sn) cassiterite-bearing hydrothermal vein system hosted by a late Oligocene (ca. 24 Ma) peraluminous K-feldspar-megacrystic granitic complex and surrounding Ordovician shales affected by deformation and low-grade metamorphism. The mineralization consists of NW-trending, quartz-cassiterite-sulfide veins and fault-controlled breccia bodies (&amp;gt;1.4 km in vertical and horizontal extension). They show volumetrically important tourmaline alteration that principally formed prior to the main ore stage, similar to other granite-related Sn deposits worldwide. We present here a detailed textural and geochemical study of tourmaline, aiming to trace fluid evolution of the San Rafael magmatic-hydrothermal system that led to the deposition of tin mineralization. Based on previous works and new petrographic observations, three main generations of tourmaline of both magmatic and hydrothermal origin were distinguished and were analyzed in situ for their major, minor, and trace element composition by electron microprobe analyzer and laser ablation-inductively coupled plasma-mass spectrometry, as well as for their bulk Sr, Nd, and Pb isotope compositions by multicollector-inductively coupled plasma-mass spectrometry. A first late-magmatic tourmaline generation (Tur 1) occurs in peraluminous granitic rocks as nodules and disseminations, which do not show evidence of alteration. This early Tur 1 is texturally and compositionally homogeneous; it has a dravitic composition, with Fe/(Fe + Mg) = 0.36 to 0.52, close to the schorl-dravite limit, and relatively high contents (10s to 100s ppm) of Li, K, Mn, light rare earth elements, and Zn. The second generation (Tur 2)—the most important volumetrically—is pre-ore, high-temperature (&amp;gt;500°C), hydrothermal tourmaline occurring as phenocryst replacement (Tur 2a) and open-space fillings in veins and breccias (Tur 2b) and microbreccias (Tur 2c) emplaced in the host granites and shales. Pre-ore Tur 2 typically shows oscillatory zoning, possibly reflecting rapid changes in the hydrothermal system, and has a large compositional range that spans the schorl to dravite fields, with Fe/(Fe + Mg) = 0.02 to 0.83. Trace element contents of Tur 2 are similar to those of Tur 1. Compositional variations within Tur 2 may be explained by the different degree of interaction of the magmatic-hydrothermal fluid with the host rocks (granites and shales), in part because of the effect of replacement versus open-space filling. The third generation is syn-ore hydrothermal tourmaline (Tur 3). It forms microscopic veinlets and overgrowths, partly cutting previous tourmaline generations, and is locally intergrown with cassiterite, chlorite, quartz, and minor pyrrhotite and arsenopyrite from the main ore assemblage. Syn-ore Tur 3 has schorl-foititic compositions, with Fe/(Fe + Mg) = 0.48 to 0.94, that partly differ from those of late-magmatic Tur 1 and pre-ore hydrothermal Tur 2. Relative to Tur 1 and Tur 2, syn-ore Tur 3 has higher contents of Sr and heavy rare earth elements (10s to 100s ppm) and unusually high contents of Sn (up to &amp;gt;1,000 ppm). Existence of these three main tourmaline generations, each having specific textural and compositional characteristics, reflects a boron-rich protracted magmatic-hydrothermal system with repeated episodes of hydrofracturing and fluid-assisted reopening, generating veins and breccias. Most trace elements in the San Rafael tourmaline do not correlate with Fe/(Fe + Mg) ratios, suggesting that their incorporation was likely controlled by the melt/fluid composition and local fluid-rock interactions. The initial radiogenic Sr and Nd isotope compositions of the three aforementioned tourmaline generations (0.7160–0.7276 for 87Sr/86Sr(i) and 0.5119–0.5124 for 143Nd/144Nd(i)) mostly overlap those of the San Rafael granites (87Sr/86Sr(i) = 0.7131–0.7202 and 143Nd/144Nd(i) = 0.5121–0.5122) and support a dominantly magmatic origin of the hydrothermal fluids. These compositions also overlap the initial Nd isotope values of Bolivian tin porphyries. The initial Pb isotope compositions of tourmaline show larger variations, with 206Pb/204Pb(i), 207Pb/204Pb(i), and 208Pb/204Pb(i) ratios mostly falling in the range of 18.6 to 19.3, 15.6 to 16.0, and 38.6 to 39.7, respectively. These compositions partly overlap the initial Pb isotope values of the San Rafael granites (206Pb/204Pb(i) = 18.6–18.8, 207Pb/204Pb(i) = 15.6–15.7, and 208Pb/204Pb(i) = 38.9–39.0) and are also similar to those of other Oligocene to Miocene Sn-W ± Cu-Zn-Pb-Ag deposits in southeast Peru. Rare earth element patterns of tourmaline are characterized, from Tur 1 to Tur 3, by decreasing (Eu/Eu*)N ratios (from 20 to 2) that correlate with increasing Sn contents (from 10s to &amp;gt;1,000 ppm). These variations are interpreted to reflect evolution of the hydrothermal system from reducing toward relatively more oxidizing conditions, still in a low-sulfidation environment, as indicated by the pyrrhotite-arsenopyrite assemblage. The changing textural and compositional features of Tur 1 to Tur 3 reflect the evolution of the San Rafael magmatic-hydrothermal system and support the model of fluid mixing between reduced, Sn-rich magmatic fluids and cooler, oxidizing meteoric waters as the main process that caused cassiterite precipitation.

Petrogenesis and Tectonic Setting of the Highly Fractionated Junye Granitic Intrusion in the Yiliu Tungsten Polymetallic Deposit, Guangdong Province, South China: Constraints from Geochemistry and Sr-Nd-Pb-Hf Isotopes

The Yiliu tungsten polymetallic deposit, located in the south central portion of the Nanling nonferrous metal metallogenic province in South China, is an area with common Yanshanian tectonothermal events. Early Yanshanian magmatism leads to the emplacement of voluminous tungsten-bearing granite intrusions, such as the Baoshan, Benggangling and Junye plutons, which are considered temporally and spatially associated with W-polymetallic mineralization in the Yiliu region. Here, we investigate the basic geological and petrological characteristics of the Junye granites, and present major and trace element geochemical data and bulk-rock Sr-Nd-Pb-Hf isotopic data to gain insight into the petrogenesis and tectonic setting of granitic intrusions in the region. The Junye granites are high-K calc-alkaline and metaluminous to weakly peraluminous [A/CNK = molar ratios of Al2O3/(CaO + Na2O + K2O) = 0.97–1.02] with enrichment in SiO2 (75.68–76.44 wt.%), relatively high total alkalis (K2O + Na2O = 8.06–8.45 wt.%) with K2O/Na2O ratios ranging from 1.12 to 1.42, and moderate Al2O3 (12.62–13.00 wt.%), but low in P2O5 (&lt;0.01 wt.%), MgO (0.02–0.04 wt.%), CaO (0.78–0.95 wt.%) and Fe2O3T (0.93–1.07 wt.%). They show spectacular tetrad effect REE (rare earth element) patterns with low ΣREE content (53.2–145.3 ppm), negative Eu anomalies (δEu = 0.09–0.17) and slight enrichment of LREEs (light rare earth elements) relative to HREEs (heavy rare earth elements). The granites are enriched in Rb (481–860 ppm), Th (16.2–46.1 ppm) and U (25.4–40.8 ppm) but depleted in Ba (1.0–5.8 ppm), Sr (11.1–23.4 ppm), P (9.5–26.7 ppm) and Ti (241–393 ppm). All geochemical features lead us to interpret the Junye granites as highly fractionated I-type granites. These granites underwent intense interaction between highly evolved magma and volatile-rich hydrothermal fluids during the late stage of formation, and accompanied fractional crystallization of biotite, plagioclase and accessory minerals, such as apatite, monazite and allanite. Additionally, the granites show uniform Nd isotopic ratios with calculated εNd (152 Ma) values of −8.28 to −8.91 and Nd model age (TDM2) of 1645 to 1698 Ma, stable age-corrected initial Pb isotopic compositions with (206Pb/204Pb)i of 18.646–19.010, (207Pb/204Pb)i of 15.767–15.786 and (208Pb/204Pb)i of 39.113–39.159, respectively, and homogeneous Hf isotopic values yielding εHf (152 Ma) values from −6.9 to −9.5 with TDM2 ages of 1680 to 2214 Ma, collectively suggesting that the granitic magma was probably derived from the remelting of ancient infracrustal materials in the basement of the Nanling region. Consequently, we consider that the Junye granites are the products of partial melting of Paleoproterozoic infracrustal medium- to high-K metamorphic basaltic rocks in the Cathaysia Block, which was caused by the underplating of coeval mantle basaltic magmas that provided abundant heat energy for melting in a tectonic setting, with lithospheric extension and thinning during the late Jurassic period.

Evaporative loss of moderately volatile metals from the superheated 1849 Ma Sudbury impact melt sheet inferred from stable Zn isotopes

The retention of moderately volatile elements on the growing Earth remains a major uncertainty in models of terrestrial accretion. Large impactors were the main carriers of accreted material but their mutual energetic collisions and impacts onto the Earth also caused chemical fractionation for which limited experimental data exist. The objective of this work was to study several moderately volatile elements in the third-largest impact basin preserved on Earth at Sudbury, Ontario. We conducted a new chemostratigraphic transect (n=41) of Zn isotope ratios and concentrations by analysing melt sheet and basin fill samples. The data were compared to common Pb, Cs, Cd and Sb concentration systematics. Within the crystallised melt sheet there are strong trends in the extent of moderately volatile element deficits, Zn isotope composition (δ66/64ZnJMC-L from 0.18 to 0.47‰) and initial Pb isotope composition. The combined evidence suggests that these trends reflect footwall contamination of a melt sheet that had experienced evaporative Zn-loss of up to 75–80%. Accounting for plausible isotopic signatures of target rocks, the maximum mass-dependent Zn isotope fractionation ε was 0.29 ± 0.04‰ (1 s.d.), which translates to modest fractionation factors α=0.99986 to 0.99975. This is comparable to melt fallout-glass and fused sands from nuclear detonation sites. We attribute the observed Zn loss and isotope fractionation to the formation of the impact melt. The rapid formation of a solid lid of breccias upon seawater ingress may have prevented stronger evaporative loss and isotope fractionation. Within the crater fill, there is an up-stratigraphy increase in Zn isotope variability (δ66/64ZnJMC-L from 0.29 to 1.05‰). Combined with evidence for biogenic reduced C, this suggests sedimentation of authigenic particulates within an enclosed crater sea.In the melt sheet, the Zn-Pb and Rb-Cs pairs experienced different extents of maximum evaporative loss (Pb up to 98.4% vs. Zn 78%; and Cs ∼90% vs. Rb ∼30%). The relative loss pattern could reflect evaporation from superheated silicate melt at ∼1,450°C and 1 atm. Loss from super-liquidus melts formed by bolide impacts could have been a significant process shaping the Earth's volatile and moderately volatile inventory.

Sr-Nd-Pb isotopic systematic and geochronology of ultramafic alkaline magmatism of the southwestern margin of the Siberian Craton: Metasomatism of the sub-continental lithospheric mantle related to subduction and plume events

To provide new insights into the origin and evolution of ultramafic lamprophyres (UMLs) and their mantle source, we examined two UML (aillikite and damtjernite) occurrences of different ages in the western portion of the Siberian Craton (Ilbokich and Chadobets). New age, mineral and rock geochemistry, along with Sr–Nd–Pb–C–O isotope data was obtained. Our new 206Pb/238U perovskite age (399 ± 4 Ma) confirms the previously published Early Devonian age of the Ilbokich aillikite. RbSr isochron and 40Ar/39Ar dating yielded a Middle Triassic age (243 ± 3 Ma and 241 ± 1 Ma, respectively) for the Chadobets aillikites, indicating post-Trap emplacement of these rocks.Both UMLs are characterized by incompatible elements, including light rare earth element (LREE) enrichments (La is up to ×200 chondrite concentration), and strong fractionation of REEs ((La/Yb)n: 33–84). Despite the close geochemical affinity of both UMLs, the Nd isotopic compositions of aillikites, as well as the Pb isotopic composition of Chadobets and Ilbokich UMLs, do not overlap and are distinctly different from each other. The initial Sr and Nd isotopic compositions of the Ilbokich UMLs fall in within a narrow 87Sr/86Sr0 range (0.7032–0.7042) and εNd(T) (4.03–3.97). Chadobets UMLs have a similar Sr isotopic signature (87Sr/86Sr0: 0.7031–0.7043) and a more depleted Nd isotopic signature (εNd(T) 4.09–5.08). The initial Pb isotope compositions of the Chadobets UMLs are moderately radiogenic, ranging between 206Pb/204Pb = 18.4–19.0, 208Pb/204Pb = 38.3–38.8, and are characterized by a narrow 207Pb/204Pb ratio between 15.5 and 15.6. The Ilbokich Pb isotope compositions are less variable and range between 206Pb/204Pb = 18.0–18.4, 208Pb/204Pb = 37.8–38.4 and 207Pb/204Pb ratios between 15.5 and 15.6. The oxygen isotopic composition of carbonate from both UMLs is characterized by highly variable δ18O values from +12.1 and up to +20.5‰ (SMOW). The isotopic composition of δ13C values range from −1.3‰ to −7.1.Based on the minor impact of crustal contamination in both aillikites, it is inferred that their radiogenic isotope composition reflects a mantle source signature. The mantle source of the Chadobets aillikites is likely to include carbonatitic magma as a metasomatic agent. In contrast, phlogopite-rich metasomes within the lithospheric mantle could have contributed more significantly to the Ilbokich aillikites. These metasomes could be formed during the Caledonian orogeny, which did not only affect the southwestern boundary of the Siberian Craton, but also expanded to the craton interior. This study provides additional support for the evolution of the south-western portion of the Siberian SCLM, ranging from mantle containing phlogopite enrichment domains during the Early Devonian to hydrous-phase reduced mantle in the Triassic due to the thermal impact of the Siberian Traps.

Geochemical and Sr–Nd–Pb isotopic constraints on the origin and petrogenesis of Paleozoic lamproites in the southern Yangtze Block, South China

Lamproites and kimberlites are natural probes of the subcontinental lithospheric mantle providing insights into the Earth’s continental lithosphere. Whole-rock major-, trace-element and Sr–Nd–Pb isotopic compositions of the Paleozoic (~ 253 Ma) lamproite dikes from the Baifen zone of the Zhenyuan area in southeastern Guizhou Province (in the southern Yangtze Block, South China) are presented. The Baifen lamproites are characterized by high MgO (7.84–14.1 wt%), K2O (3.94–5.07 wt%) and TiO2 (2.69–3.23 wt%) contents, low SiO2 (41.3–45.7 wt%), Na2O (0.21–0.28 wt%) and Al2O3 (6.10–7.20 wt%) contents. All lamproites have elevated Cr (452–599 ppm) and Ni (485–549 ppm) abundances, as well as high Ba (1884–3589 ppm), La (160–186 ppm), Sr (898–1152 ppm) and Zr (532–632 ppm) concentrations. They show uniform REE distribution patterns that are strongly enriched in light REEs relative to heavy REEs [(La/Yb)N = 71.1–87.6], and exhibit OIB-like geochemical features with obvious enrichment of both LILEs and HFSEs in the primitive mantle-normalized multi-element distribution diagram. Moderately radiogenic Sr (87Sr/86Sri = 0.706336–0.707439), unradiogenic Nd (143Nd/144Ndi = 0.511687–0.511704 and eNd(t) = − 12.2 to − 11.9), and low initial Pb (206Pb/204Pbi = 16.80–16.90, 207Pb/204Pbi = 15.34–15.35 and 208Pb/204Pbi = 37.43–37.70) isotopic compositions are obtained from the rocks. They yield old model ages of TDM(Nd) = 1.48–1.54 Ga. These signatures suggest that the Baifen lamproite magmas are alkaline, ultrapotassic and ultramafic in character and mainly represent mantle-derived primary melts, which have undergone insignificant crustal contamination and negligible fractional crystallization. The Baifen lamproites originated from a veined metasomatized lithospheric mantle source. We envisage that they were derived by partial melting of old, mineralogically complex metasomatic vein assemblages in the subcontinental lithospheric mantle beneath the southern Yangtze Block. The source region experienced ancient mantle metasomatism with complex modification by enriched fluids and melts. The metasomatic agents are most likely to originate from pre-existing slab subduction beneath the southeastern margin of the Yangtze Block. Tectonically, the Baifen lamproites were emplaced at the southern margin of the Yangtze Block, and they formed in an intraplate extensional setting, showing an anorogenic affinity. In terms of time and space, the genesis of Baifen lamproites is presumably related to the Emeishan large igneous province. The Emeishan mantle plume is suggested as an effective mechanism for rapid extension and thinning of the lithosphere, followed by decompression melting of the subcontinental lithospheric mantle. Combined with the thermal perturbation from asthenospheric upwelling induced by the Emeishan mantle plume, the lamproite magmas, representing small volume and limited partial melts of ancient enriched mantle lithosphere, arose. We propose that the generation of the Baifen lamproite dikes probably was a consequence of the far-field effects of the Emeishan mantle plume.

Geochemically heterogeneous Martian mantle inferred from Pb isotope systematics of depleted shergottites

Radiogenic isotopic compositions of shergottite meteorites suggest that early planetary differentiation processes, which are related to the crystallization of the Martian Magma Ocean (MMO), resulted in the geochemically heterogeneous Martian mantle. In order to understand the early geochemical evolution of Mars, we investigated the Pb isotope systematics in the depleted Martian mantle on the basis of the analyses of two geochemically depleted shergottites, Dar al Gani (DaG) 476 and Yamato 980459 (Y-980459). Their initial Pb isotopic compositions were estimated from geochemical analyses of highly leached acid residues and age-correction calculations using reference crystallization ages. This yielded μ-values (238U/204Pb) for the DaG 476 and Y-980459 source reservoirs of 2.33 ± 0.07 and 2.32 ± 0.06, respectively. These μ-values are distinct from those of other depleted shergottite source reservoirs (e.g., 1.4 ± 0.1 for the Tissint meteorite) and show a negative correlation with corresponding 147Sm/144Nd, 176Lu/177Hf, ɛ182W, and ε142Nd compositions. Such correlations between long- and short-lived isotopic signatures suggest that a geochemically heterogeneous depleted shergottite source mantle was formed on the early Mars. This geochemical heterogeneity would have been formed by variable mixing of depleted and enriched end-member components that originally formed by fractional crystallization in the MMO. Local remelting in the geochemically depleted Martian mantle after the crystallization of the MMO is another possible explanation for the formation of a geochemically heterogeneous depleted shergottite source mantle.

The Pb isotope evolution of Bulk Silicate Earth: Constraints from its accretion and early differentiation history

Constraining the evolution of Pb isotopes in the bulk silicate Earth (BSE) is hampered due to the lack of a direct determination of Earth’s U/Pb and initial Pb isotope composition. All estimates of these parameters are strongly model dependent and most Pb evolution models start with a meteoritic source, i.e., the primordial Pb composition determined in troilite from the Canyon Diablo iron meteorite. During the condensation of the elements in the solar nebula, accretion of the Earth, and its subsequent chemical evolution, the U/Pb was modified. Different models make different assumptions about the timing and extent of this U-Pb fractionation during Earth’s chemical evolution that cannot always be related to known global geological processes at the time of this modification. This study explores geochemical constraints that can be related to known geological processes to derive an internally consistent model for the evolution of the U-Th-Pb systematics of the silicate Earth.Lead is chalcophile, moderately volatile, and as a result strongly depleted in the BSE compared to primitive meteorites. Any process affecting the abundance and isotope composition of Pb in Earth throughout its early history has to be consistent with the abundance of elements with similar chemical and physical properties in the same reservoir. The abundances of refractory to moderately and highly volatile elements in the BSE imply that the proto Earth was highly depleted in volatile elements, and therefore evolved with a very high U/Pb (238U/204Pb = µ ≥ 100) prior to collision with the Moon-forming giant impactor. This impactor had close to chondritic abundances of moderately to highly volatile elements and delivered most of Earth’s volatile elements, including the Pb budget. Addition of this volatile-rich component caused oxidation of Earth’s mantle and allowed effective transfer of Pb into the core via sulfide melt segregation. Sequestration of Pb into the core therefore accounts for the high µBSE, which has affected ca. 53% of Earth’s Pb budget. In order to account for the present-day Pb isotope composition of BSE, the giant impact must have occurred at 69 ± 10 Myr after the beginning of the solar system. Using this point in time, a model-derived µ-value and the corresponding initial Pb isotope composition of BSE, a single stage Pb isotope evolution curve can be deduced. The result is a model evolution curve for BSE in 208Pb-207Pb-206Pb-204Pb-isotope space that is fully consistent with geochemical constraints on Earth’s accretionary sequence and differentiation history. This Pb-evolution model may act as a reference frame to trace the silicate Earth’s differentiation into crust and mantle reservoirs, similar to the CHUR reference line used for other radio-isotope systems. It also highlights the long-standing Th/U paradox of the ancient Earth.

An advanced stepwise leaching technique for derivation of initial lead isotope ratios in ancient mafic rocks: A case study of Mesoproterozoic intrusions from the Udzha paleo-rift, Siberian Craton

Lead isotope systematics is a powerful tool for the interpretation of magma sources. However, a significant problem in the study of Pb and U is their high mobility during weathering and secondary alteration of igneous rocks. Therefore, recalculations of the time-integrated lead isotopic ratios back to their initial values in ancient rocks should be approached with caution. A standard procedure for deriving initial lead isotopic ratios includes the analyses of minerals which have low U/Pb elemental ratios (e.g., potassium feldspar and/or sulfides). However, these minerals may not always be present in the sample of interest, too small and/or intergrown with other minerals, and thereby mechanically inseparable and/or altered. To circumvent the effects of secondary alteration, a conventional approach is the preliminary treatment of minerals by strong acids (e.g., concentrated HNO3 or Aqua Regia) as well as whole-rock samples in order to remove altered components. The residual phases are then analyzed for initial lead isotopic ratios. However, this procedure does not always yield satisfactory results.In this study, we developed an advanced stepwise leaching technique in which the rock powder was first treated by 2.2 N HCl, then by more concentrated HCl, and finally by concentrated HNO3. This procedure allows for the chemical separation of sulfides, which are dissolved by concentrated HNO3, but unaffected by HCl. At least three leaching steps and two isotopic analyses per sample should be performed. We applied this stepwise leaching procedure to mafic intrusions of a known age (1386 ± 30 Ma) from the Mesoproterozoic Udzha paleo-rift in the northern part of the Siberian Craton. The Pb isotope results for the whole-rock and final leachate fractions are presented for three samples as well as their U, Th and Pb whole-rock data, which revealed completely closed U-Th-Pb isotopic behavior despite moderate alteration of the samples, thereby supporting the 1.38 Ga age of the magmatic event. The obtained initial Pb isotope composition of the mafic intrusion clearly indicates an origin from a long-lived enriched source.

The timing of basaltic volcanism at the Apollo landing sites

Precise crystallisation ages have been determined for a range of Apollo basalts from Pb-Pb isochrons generated using Secondary Ion Mass Spectrometry (SIMS) analyses of multiple accessory phases including K-feldspar, K-rich glass and phosphates. The samples analysed in this study include five Apollo 11 high-Ti basalts, one Apollo 14 high-Al basalt, seven Apollo 15 low-Ti basalts, and five Apollo 17 high-Ti basalts. Together with the samples analysed in two previous similar studies, Pb-Pb isochron ages have been determined for all of the major basaltic suites sampled during the Apollo missions. The accuracy of these ages has been assessed as part of a thorough review of existing age determinations for Apollo basalts, which reveals a good agreement with previous studies of the same samples, as well as with average ages that have been calculated for the emplacement of the different basaltic suites at the Apollo landing sites. Furthermore, the precision of the new age determinations helps to resolve distinctions between the ages of different basaltic suites in more detail than was previously possible. The proposed ages for the basaltic surface flows at the Apollo landing sites have been reviewed in light of these new sample ages. Finally, the data presented here have also been used to constrain the initial Pb isotopic compositions of the mare basalts, which indicate a significant degree of heterogeneity in the lunar mantle source regions, even among the basalts collected at individual landing sites.