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Allanite is a common accessory mineral that generally incorporates considerable amounts of Th, U and light rare Earth elements in its structure, making it a useful mineral for in situ U-Th-Pb geochronology and Sm-Nd isotope measurements. Here, we present in situ U-Th-Pb ages and Sm-Nd isotopic compositions for nine allanite samples considered as potential reference materials (CAPb, Tara, Daibosatsu, LE40010, LE2808, A007, A011, A012 and SQ-51), with ages ranging from ~ 2650 Ma to ~ 12 Ma. Our study indicates that Daibosatsu and LE40010 have relatively homogeneous 147Sm/144Nd and 143Nd/144Nd isotopic compositions (147Sm/144Nd ratio variation is less than 2%) and, thus, can serve as primary reference materials for Sm-Nd microanalysis. In contrast, CAPb, Tara, LE2808, A007, A011 and A012 all show homogeneous calculated initial 143Nd/144Nd isotopic compositions, but with variable 147Sm/144Nd compositions, and thus can be used only as secondary reference materials for Sm-Nd microanalysis. Of these materials, LE40010 allanite can serve as a suitable primary reference material for in situ U-Pb dating, CAPb allanite can serve as a suitable primary reference material for in situ Th-Pb dating, and LE2808, LE40010, A007, A011 and A012 can serve as suitable secondary reference materials for in situ U-Pb geochronology. In addition, Daibosatsu is suitable as a secondary reference material for Cenozoic Th-Pb dating to monitor data reproducibility.

Extensive magmatism in NE China, eastern Central Asian Orogenic Belt, has produced multi-stage granitic plutons and accompanying W mineralization. The Narenwula complex in the southwestern Great Xing’an Range provides important insights into the petrogenesis, geodynamic processes and relationship with W mineralization. The complex comprises granodiorites, monzogranites and granite porphyry. Mafic microgranular enclaves are common in the granodiorites, and have similar zircon U–Pb ages as their host rocks (258.5–253.9 Ma), whereas the W-bearing granitoids yield emplacement ages of 149.8–148.1 Ma. Permian granodiorites are I-type granites that are enriched in large-ion lithophile elements and light rare earth elements, and depleted in high field strength elements and heavy rare earth elements. Both the mafic microgranular enclaves and granodiorites have nearly identical zircon Hf isotopic compositions. The results suggest that the mafic microgranular enclaves and granodiorites formed by the mixing of mafic and felsic magmas. W-bearing granitoids are highly fractionated A-type granites, enriched in Rb, Th, U and Pb, and depleted in Ba, Sr, P, Ti and Eu. They have higher W concentrations and Rb/Sr ratios, and lower Nb/Ta, Zr/Hf and K/Rb ratios than the W-barren granodiorites. These data and negative ϵHf(t) values (–6.0 to –2.1) suggest that they were derived from the partial melting of ancient lower crust and subsequently underwent extreme fractional crystallization. Based on the regional geology, we propose that the granodiorites were generated in a volcanic arc setting related to the subduction of the Palaeo-Asian Ocean, whereas the W-bearing granitoids and associated deposits formed in a post-orogenic extensional setting controlled by the Mongol–Okhotsk Ocean and Palaeo-Pacific Ocean tectonic regimes.

Natural BDL plagioclase as a reference material for the determination of Sr isotopes by means of laser ablation multi-collector inductively coupled plasma mass spectrometry.

Evaluation of the IRMM-524A Fe metal as a primary reference material and natural samples of pyrite and ilmenite as secondary reference materials is presented for the Fe isotopic analysis using femtosecond LA-MC-ICP-MS.

Five-carbon (C5) structural units are the fundamental building blocks of many natural products. An unprecedented palladium-catalyzed three-component dehydrogenative cascade coupling of indoles, 2-methylbut-2-ene, and carboxylic acids has been developed. The approach enables the straightforward introduction of a C3'-bonded five-carbon structural unit with a tertiary alcohol quaternary carbon center into indoles. The protocol employs 2-methylbut-2-ene as the C5 source and is featured by a broad substrate scope, atom and step economies, and high chemo- and regioselectivies.

Abundant arc-type magmatic and metamorphic rocks exist on Earth today, which provide insights into the equilibrium state of the subduction process. However, magmatic samples generated during the initial stage of subduction is largely unknown. This hinders our understanding of the subduction initiation process and by inference, the onset of plate tectonics as well as the history of crustal formation. To address this issue, we carried out a comprehensive geochemical-geochronological study of a suite of Late Triassic to mid-Jurassic plutonic rocks from southern Alaska that potentially represent magmas from the initial to mature stages of arc formation. While all studied samples show typical arc-type geochemical signatures, i.e., enrichment of large ion lithophile elements (LILEs) and depletion of high field strength elements (HFSEs) relative to the heavy rare earth elements (HREEs), the Late Triassic trondhjemites show unique geochemical features such as strongly positive eHf(t) and eNd(t) coupled with lower δ18O (average 4.77‰ ± 0.09‰). These signatures, along with its higher zircon saturation temperatures compared with younger plutonic rocks, are best explained by shallow partial melting of subducting high-temperature hydrothermally altered lower oceanic crust (i.e., gabbro). If true, these surprising findings would open up new ways to study subduction initiation which would have important bearing on future research on the onset of global plate tectonics and the formation of the continental crust.

Lode gold deposits, which are currently the world’s major gold supply, have been shown to be generated mostly by phase separation of metamorphic fluids and/or interaction between these fluids and wall rocks. Here we use garnet oxygen isotopes by secondary ion mass spectrometry to document the crucial role of magmatic hydrothermal fluids and their mixing with meteoric water in the formation of the world-class Dongping gold deposit in the North China Craton. Garnet grains from quartz veins of various paragenetic stages and the mineralized alteration envelope at Dongping have dynamic δ18O variations of 3.8 to −11.0‰, with large intragrain fluctuations up to 5.3‰. These values correspond to calculated δ18O values of 6.1 to −9.1‰ for the hydrothermal fluids from which the garnet formed. The isotope data, notably the cyclic alternation in δ18O within individual garnet grains, are best interpreted to reflect multiple pulses of magmatically derived fluids and subsequent mixing of each pulse with variable amounts of meteoric water. The results presented here allow us to quantify the significant interplay between magmatic hydrothermal fluids and meteoric water that spanned the entire mineralization history and triggered gold deposition of a lode gold deposit. This study highlights the potential use of in situ oxygen isotope analysis of garnet in tracing the origin and evolution of hydrothermal fluids in the Earth’s crust that may have formed other giant ore deposits.

It is generally hypothesized that high-silica (SiO2 > 75 wt%) granite (HSG) originates from crystal fractionation in the shallow crust. Yet, identifying the complementary cumulate residue of HSG within plutons remains difficult. In this work, we examine the genetic links between the porphyritic monzogranite and HSG (including porphyritic granite, monzogranite, and alkali feldspar granite) from the coastal area of southeastern China using detailed zircon U-Pb ages, trace elements, Hf-O isotopes, and whole-rock geochemistry and Nd-Hf isotopic compositions. Zircon U-Pb ages indicate that the porphyritic monzogranite and HSG are coeval (ca. 96–99 Ma). The HSG and porphyritic monzogranite have similar formation ages within analytic error, identical mineral assemblages, similar Nd-Hf isotopic compositions, and consistent variations in their zircon compositions (i.e., Eu/Eu*, Zr/Hf, and Sm/Yb), which suggests that their parental magma came from a common silicic magma reservoir and that the lithological differences are the result of melt extraction processes. The porphyritic monzogranite has relatively high SiO2 (70.0–73.4 wt%), Ba (718–1070 ppm), and Sr (493–657 ppm) contents, low K2O and Rb concentrations and low Rb/Sr ratios (0.1–0.2), and it displays weak Eu anomalies (Eu/Eu* = 0.57–0.90). Together with the petrographic features of the porphyritic monzogranite, these geochemical variations indicate that the porphyritic monzongranite is the residual silicic cumulate of the crystal mush column. The HSG (SiO2 = 75.0–78.4) has variable Rb/Sr ratios (2–490) and very low Sr (1–109 ppm) and Ba (9–323 ppm) contents. Zircon from the HSG and porphyritic monzogranite overlap in Eu/Eu*, Zr/Hf, and Sm/Yb ratios and Hf contents; however, some zircon from the HSG show very low Eu/Eu* (

The North China Craton (NCC) experienced strong destruction (i.e., decratonization) during the Mesozoic, which triggered intensive magmatism, tectonism and thermal events and formed large-scale gold and other metal deposits in the eastern part of the craton. However, how the decratonization controls the formation and distribution of large-scale of gold and other metal deposits is not very clear. Based on a large number of published data and new results, this paper systematically summarizes all the data for the rock assemblages, chronology, geochemistry and petrogenesis of Mesozoic magmatic rocks, as well as for the mineralizing ages of gold and other metal deposits and the evolution of the Mesozoic basins in the eastern NCC. The results are used to restore the extensional rates of Mesozoic to Cenozoic basins and the strike-slip distance of the Tanlu Fault, to ascertain the location of the Paleo-Pacific plate subduction zones during the Mesozoic to Cenozoic, and to reconstruct the temporal and spatial distribution of Mesozoic gold and other metal deposits and magmatic rocks in the eastern NCC. It is obtained that the magmatism and mineralization in the eastern NCC westward migrate from east to west during the Early to Middle Jurassic, but they eastward migrate from west to east during the Early Cretaceous. The metallogenesis of these deposits is genetically related to magmatism, and the magmas provided some ore-forming materials and fluids for the generation of metal deposits. The geodynamic mechanism of decratonization and related magmatism and mineralization is proposed, i.e., the westward low-angle subduction of the Paleo-Pacific slab beneath the NCC formed continental magmatic arc with plenty of porphyry Cu-Mo-Au deposits in the Jurassic, similar to the Andean continental arc in South America. The mantle wedge was metasomatized by the fluids/melts derived from the subducting slab, laying a material foundation for hydrothermal mineralization in the Early Cretaceous. While the rollback of the subducting slab with gradually increasing subduction angle and the retreat of the subduction zones during the Early Cretaceous induced strong destruction of the craton and the formation of extensive magmatic rocks and large-scale gold and other metal deposits.

Highly precise and accurate measurements of Fe isotope ratios for fourteen reference materials from the USGS, MPI-DING and CGSG were successfully carried out using a developed analytical technique by fs LA-MC-ICP-MS. A synthetic standard, i.e., Cr-979S, was produced as a calibration standard for instrumental mass bias and isobaric interference corrections. The results for samples with low Cr concentration (54Cr/54Fe 0.0001), e.g., BHVO-2G, δ56Fe values deviated from reference values when using the standard-sample bracketing method alone. Combining the standard-sample bracketing method with Cr-979S standard corrections and standard sample cone + H skimmer cone, the measured Fe isotopic compositions of GOR128-G and GOR132-G with extremely high Cr concentrations (54Cr/54Fe > 0.01) were identical to reference values within errors (δ56Fe = −0.01 ± 0.13‰, 2SD, n = 18; δ56Fe = 0.00 ± 0.13‰, 2SD, n = 13; respectively). A series of reference materials with varying Cr concentrations, including the USGS reference glasses (BCR-2G, BHVO-2G, BIR-1G, TB-1G, NKT-1G, GSD-1G and GSE-1G), MPI-DING reference glasses (KL2-G, ML3B-G, GOR128-G and GOR132-G) and CGSG reference materials (CGSG-1 and CGSG-4), were used to test our developed method of in situ Fe isotopic measurements using the combined standard-sample bracketing method and Cr-979S standard corrections by fs LA-MC-ICP-MS. All the reference materials yield relatively homogeneous Fe isotopic compositions with δ56Fe values ranging from −0.03‰ to 0.13‰ and δ56Fe reproducibility is below 0.15‰ (2SD), suggesting that the proposed isobaric interference correction and mass bias correction method is a useful tool for providing high-quality in situ Fe isotopic data of geological samples with both low and high Cr concentrations.

Due to their relatively high Hf contents (i.e., several hundreds to thousands of ppm), columbite-group minerals (CGMs) are suitable for Lu–Hf isotope analysis, which can provide new insights into the source of such minerals in combination with the U–Pb age of rare-metal deposits. However, few studies have reported Lu–Hf isotope data for CGMs. Tantalum is a major element in CGMs (12–48 wt% Ta2O5) and has a significant effect on measurements of Hf isotopes using MC-ICP-MS. This effect was first evaluated in this study by analysis of mixed Hf–Ta standard solutions with different Ta/Hf ratios and LA-MC-ICP-MS analysis of various CGMs. This analytical artifact reflects serious tailing of the large 181Ta signal onto the 180Hf and 179Hf masses during analysis. Therefore, in order to obtain accurate Hf isotope data for CGMs by MC-ICP-MS, we present an improved chemical separation procedure for Hf from Ta, and also a novel analytical protocol for LA-MC-ICP-MS analysis of CGMs. Accurate in situ176Hf/177Hf ratios for CGMs can be obtained by normalization to 178Hf/177Hf = 1.4672, rather than 179Hf/177Hf = 0.7325, using the exponential law. This approach was validated by solution and laser ablation MC-ICP-MS analysis of four CGM samples from China and Africa. The Lu–Hf isotopic composition of CGMs provides a new geochemical tracer for rare-metal deposits.

Here we present Si and Zr isotopic data of SA01 and SA02 zircons via multi-technique analytical methods to evaluate the suitability of the two zircon reference materials for in situ Si and Zr isotopic analysis using femtosecond laser ablation multi-collector inductively coupled plasma mass spectrometry (fs-LA-MC-ICP-MS). Precise and accurate Si and Zr isotopic compositions were determined by solution nebulization (SN) MC-ICP-MS. Fifteen SN-MC-ICP-MS Si isotopic measurements on two aliquots of SA01 zircon solutions gave consistent results with an average δ30Si (relative to NBS28) value of −0.29 ± 0.08‰ (2SD), whereas a slight inter-grain offset was detected for the SA02 zircon with an average δ30Si value of −0.25 ± 0.16‰ (2SD, n = 12). The mean δ94/90Zr (relative to IPGP-Zr) values were 0.02 ± 0.03‰ (2SD, n = 9) and 0.02 ± 0.04‰ (2SD, n = 9) for SA01 and SA02 zircons, respectively. Extensive homogeneity test of both Si and Zr isotopic compositions was performed on SA01 and SA02 zircons by spot analysis with fs-LA-MC-ICP-MS. The Si and Zr isotopic results for SA01 zircon showed good agreement with our SN-MC-ICP-MS measurements, as did the Zr isotope results of SA02 zircon. In spite of the inter-grain offset in the Si isotopic composition revealed by SN-MC-ICP-MS, intra-grain homogeneity was confirmed for SA02 zircon by the LA-MC-ICP-MS method. In situ analyses of SA01 and SA02 zircons yielded mean δ30Si values of −0.24 ± 0.10‰ (2SD, n = 143) and −0.26 ± 0.12‰ (2SD, n = 135), and mean δ94/90Zr values of 0.03 ± 0.09‰ (2SD, n = 153) and 0.02 ± 0.09‰ (2SD, n = 153), respectively. Both solution and in situ dataset demonstrated the suitability of SA01 for calibrating in situ zircon Si and Zr isotopic analysis. We suggest that SA02 zircon is also a suitable reference material for micro-beam Zr isotopic analysis as well as a monitor for in situ Si isotopic analysis. Furthermore, an analytical approach using the spot mode of fs-LA is presented in this study. In situ Si and Zr isotopic analysis may benefit from it for improving spatial resolution and precision.

To meet the rapid development of zircon U-Pb geochronology and Hf-O isotope geochemistry, it is imperative to develop well-characterized zircon reference materials for microbeam analysis. Here, zircon KV01 separated from the Kaap Valley pluton, South Africa is introduced as a potential Archean reference material for microbeam U-Pb age and Hf-O isotope determination. SIMS and LA-ICP-MS U-Pb isotopic measurements gave grand mean 207Pb/206Pb ages of 3233±16 Ma (2s, n=90) and 3230±26 Ma (2s, n=52), which are consistent with reported CA-ID-TIMS results. Slight heterogeneity of oxygen isotopes is revealed by SIMS analyses that yielded a relatively large δ18O range of 4.61–6.51‰. Among them, the zircon grains with clear oscillatory zones give a grand mean δ18O value of 6.17±0.33‰ (2s), which is suggested to record the primary O isotopic compositions. The homogeneity in the Hf isotopic compositions of KV01 zircon was checked by the laser ablation and solution MC-ICP-MS methods. They yielded consistent results with a recommended 176Hf/177Hf ratio of 0.280810±0.000013 (2s). The results reported here demonstrate that KV01 zircon could be a reliable reference material for microbeam 207Pb/206Pb age and Hf isotope determinations of ancient zircons, and be suitable as a quality monitor for SIMS oxygen isotopic analysis.

The short-lived 182Hf-182W system has been used to constrain the early Earth’s accretion and differentiation. This paper reports high precision W isotopic compositions and trace element concentrations for Archean (4.0–3.0 Ga) intermediate to felsic rocks from the Slave, North China, and Kaapvaal cratons to discuss early Earth differentiation and mantle mixing processes. The 4.0–3.8 Ga diorite and trondhjemite samples from the Acasta Gneiss Complex (AGC) in the Slave Craton and Anshan Complex in the North China Craton have positive μ182W values ranging from 8.3 ± 3.6 to 14.5 ± 4.0, whereas the 3.36–2.95 Ga TTG rocks from the North China Craton have a uniform modern mantle-like μ182W value of 0.7 ± 3.9 (2 SD, n = 11); with one exception, the 3.32 Ga old sample F28-2, which has a positive μ182W anomaly (7.3 ± 3.9 and 13.0 ± 3.2 for two individual analyses). The Earth’s oldest potassic granites, occurring as conglomerates in the Moodies Group, an intrusive trondhjemite, and an amphibolite with ages of ~3.55 Ga in the Kaapvaal Craton exhibit W isotopic compositions indistinguishable from what is proposed for the modern mantle. The positive 182W anomalies in the 4.0–3.8 Ga rocks could possibly be the result of either early mantle differentiation that occurred within the lifetime of 182Hf or a partial lack of late accreted material. The signature of 182W excess in the 3.32 Ga sample (F28-2) is inherited from earlier crust, presumably similar to the 3.8 Ga TTGs, either by melting or crustal contamination. The transition in μ182W values from positive to near-zero would indicates that a significant event occurred at ∼3.6 Ga which caused efficient mixing of early differentiated mantle and late accreted material, possibly indicating the transition of tectonic regimes from plume to plate tectonics on the Earth.

Lu and Hf content, and Hf isotopic composition of 13 Chinese rock reference materials are reported for the first time. The reference materials span a broad compositional range. Results indicate that they are of comparable quality to the well characterised and widely utilised USGS and GSJ rock reference materials.

It is well known that the destruction of the North China Carton (NCC) is closely related to subduction of the Paleo-Pacific slab, but materials recording such subduction has not been identified at the peak time of decratonization. This paper presents data of whole-rock major and trace elements and Sr-Nd-Hf isotopes and zircon U-Pb ages and Hf-O isotopes for Mesozoic volcanic rocks from the Liaodong-Jinan region in the northeastern NCC, in order to trace the subduction-related materials in their source and origin. The Mesozoic volcanic rocks in the Liaodong-Jinan region are mainly composed of two series of rocks, including alkaline basaltic trachyandesite, trachyandesite and trachyte, and subalkaline trachyandesite and andesite. Zircon U-Pb dating yields eruption ages of 129–124 Ma for these rocks. The Early Cretaceous volcanic rocks are all enriched in LILEs (such as Rb, Sr, Ba and Th) and LREEs, depleted in HFSEs (such as Nb, Ta and Ti), indicating that they were originated from mantle sources that had been modified by subducted crustal materials. However, they have relatively heterogeneous and variable isotopic compositions. The alkaline basaltic trachyandesite, trachyandesite and trachyte have enriched whole-rock Sr-Nd-Hf and zircon Hf isotopic compositions and mantle-like δ 18O values, suggesting that they were derived from low-degree partial melting of an isotopically enriched lithospheric mantle source. In contrast, the subalkaline trachyandesite and andesite have relatively depleted isotopic compositions with zircon e Hf( t ) values up to +5.2 and heavy zircon O isotopic compositions with δ 18O values of +8.1‰ to +9.0‰, indicating that they were originated from a lithospheric mantle source that had been metasomatized by melts/fluids derived from the recycled low-T altered oceanic basalt. All of these geochemical features suggest that the Early Cretaceous volcanic rocks in the Liaodong-Jinan region would result from mixing of mafic magmas with different compositions. Such magmas were originated from the enriched lithospheric mantle and the young metasomatized mantle, respectively, with variable extents of enrichment and depletion in trace elements, radiogenic isotopes and O isotopes. Importantly, the identification of the low-T altered oceanic crust component in the origin of Early Cretaceous volcanic rocks by the zircon Hf-O isotopes provides affirmative isotopic evidence and direct material records for Mesozoic subduction of the Paleo-Pacific slab that induced decratonization of the North China Craton.

We present an analytical protocol for in situ U–Pb isotope dating of wolframite series minerals [(Fe,Mn)WO4], the main ore mineral for tungsten, by LA-SF-ICP-MS. Precision and accuracy of the protocol was intensively assessed using our newly developed well-characterized U–Pb wolframite reference material. The tungsten oxide interference on Hg and Pb was investigated in detail. The matrix effect between ferberite and hübnerite during laser ablation was thoroughly examined for wolframite series minerals with a different Mn/(Mn + Fe) ratio. The closure temperature of wolframite, with respect to the U–Pb system, was evaluated. The application of eleven wolframite samples, with ages from ∼1780 Ma to ∼26 Ma, robustly demonstrated the feasibility of our approach. Most studied wolframite series minerals yielded U–Pb concordant or subconcordant ages. Samples with a relatively high U content and negligible common Pb content typically had a 206Pb/238U age precision of ca. 1%. The new in situ data agree well with published cassiterite or wolframite ages from the same locations. LA-SF-ICP-MS, with the advantages of high sensitivity, rapidity, and relatively low cost, as well as moderate spatial resolution (i.e., 32 or 44 μm) that is sufficiently high to avoid sulfide inclusions, is the method of choice for in situ wolframite U–Pb microanalysis.

In the present work, we describe a sequential U–Pb and Sm–Nd systematics measurement from natural LREE-enriched minerals using Neptune Plus MC-ICP-MS coupled with a 193 nm excimer laser in a single shot. MC-ICP-MS is equipped with an optical zoom lens to bring ion beams into the collector coincidently. The key features allow rapid switching between the U–Pb and Sm–Nd collector configurations, which are applied to simultaneously measure the U–Pb age and Sm–Nd isotope of common natural LREE-enriched minerals. The robustness and usefulness of the present protocol are investigated using a series of well-characterized mineral reference materials (i.e., monazite, titanite, perovskite) with known U–Pb and Sm–Nd isotopic values, which demonstrate its potential and versatility in geochemistry and cosmochemistry for microanalysis.

We present a new procedure for U-Pb dating of vesuvianite using laser ablation sector field inductively coupled plasma mass spectrometry (LA-SF-ICP-MS). Vesuvianite is a common mineral in skarn ore deposits and in metamorphic and metasomatic argillaceous carbonate rocks. The age of vesuvianite growth directly dates the formation of skarn mineralization, possibly also the metamorphism and metasomatism of argillaceous limestones. Vesuvianite U-Pb dating may provide age information for hydrothermal, metamorphic, and metasomatic processes that may be hard to get by zircon U-Pb dating. We analyzed eleven vesuvianite samples. Matrix effects were corrected by using Ti-bearing andradite (schorlomite) of known age as no well-characterized vesuvianite was available as an U-Pb reference material. The robustness of the analytical protocol was assessed by additional U-Pb dating of four vesuvianite samples by ID-TIMS. The U-Pb ages determined by ID-TIMS and LA-SF-ICP-MS agree well within uncertainties. An additional seven vesuvianite samples yielded in situ U-Pb ages that agree with previously published zircon, cassiterite, or wolframite U-Pb ages from the same area. Therefore, U-Pb dating of vesuvianite by LA-SF-ICP-MS represents a fast, relatively low-cost approach with high spatial resolution that may be particularly suited to date skarn mineralization.

The Taihangshan Mountain Belt, in the central North China Craton, represents an important crustal and tectonic boundary. To explore the complex tectonic evolution of this area during the Mesozoic–Cenozoic, we gathered zircon and apatite (U–Th)/He thermochronology data along a vertical transect (elevation of 630−1584 m) of the northern part of the Taihang Mountain Belt. From our data, we observed three separate rapid cooling phases that occurred at 100 Ma, 50−40 Ma and 27 Ma. Combined with previously published geochronological ages, we suggest that the uplift of the Taihang Mountain Belt initiated during the Jurassic and experienced multiphase rapid uplift from the Cretaceous to the Cenozoic. The early Cretaceous rapid cooling/uplifting events are widespread in the North China Craton and are caused by the collision between the Okhotomorsk Block and the East Asian continental margin. The Eocene and Oligocene rapid cooling events correspond to the initial rifting and thermal subsidence of the Bohai Bay Basin, indicating a coupling between the creation of basins and mountains.

The nepheline syenite pegmatite in the Saima alkaline complex in northeastern China is characterized by REE mineralization, mainly rinkite-(Ce) and associated alteration minerals. As the most abundant REE-bearing mineral in the pegmatite, rinkite-(Ce) closely coexists with microcline, nepheline, natrolite, and calcite. Some rinkite-(Ce) grains show compositional sector-zonation, in which the inner core displays relatively high Ti, Ca, and Sr concentrations, but low Zr, REE, and Na contents. Primary rinkite-(Ce) has undergone multiple episodes of fluid interactions, and accordingly, from weak to strong, three different mineral assemblages of hydrothermal alteration can be summarized: (1) rinkite-(Ce) + secondary natrolite ± K-feldspar ± minor fluorbritholite-(Ce); (2) rinkite-(Ce) relics + secondary natrolite + K-feldspar + fluorbritholite-(Ce) + unidentified Ca-Ti silicate mineral + fluorite and calcite; and (3) pseudomorphs after rinkite-(Ce). The pseudomorphs can be divided into two groups characterized by distinct mineral associations: (1) Ca-bearing strontianite + fluorbritholite-(Ce) + natrolite + fluorite + calcite coexisting with silicate minerals; and (2) calcite + fluorite + fluorbritholite-(Ce) + rinkite-(Ce) relics ± Ca-bearing strontianite ± ancylite-(Ce) associated with a calcite matrix. These alteration mineral assemblages are evidence of magmatic-derived alkali metasomatism due to an alkali-CO2-F-rich fluid and Ca-metasomatism due to a different, externally derived Sr- and Ca-rich fluid. The metasomatic events acted as the potential driving force for the rinkite-(Ce) dissolution and pseudomorph-forming process. The high concentration of rinkite-(Ce) in the nepheline syenite pegmatite results from the fractional crystallization of the Saima CO2-rich alkaline silicate magma, and the successive alterations of rinkite-(Ce) attest to the important role played by hydrothermal fluids in controlling the remobilization of REE and the crystallization of secondary rare earth minerals.

The petrogenesis of biotite granites, which may be metaluminous or peraluminous in composition, is a subject of debate. In this study, we present new zircon U-Pb geochronology and O-Hf isotopic, and whole-rock major and trace element, and Sr-Nd isotopic data for biotite granites in the Langla–Laqinpu area of northern Lhasa Terrane, central Tibet. The rocks are distributed along the eastern segment of the Bangong–Nujiang Tethys Ocean suture, and were emplaced during the late Early Cretaceous (ca.119 Ma). The biotite granites are peraluminous, and have high SiO2 (67.5–72.4 wt%) and low MgO (0.57–1.20 wt%) and CaO (2.36–4.38 wt%) contents with variable K2O/Na2O ratios (0.77–1.32), and show geochemical affinity with the upper-continental crust, e.g., enrichment of Rb, Th, U, K and Pb, depletion of Nb, Ta, Ti, P, Eu, and Sr. They are characterized by relatively high initial 87Sr/86Sr ratios ((87Sr/86Sr)i = 0.7098–0.7137) and low eNd(t) values (−8.4 to −10.3), and high zircon δ18O values (8.29–13.47‰) and variable eHf(t) values (−0.02 to −21.36), indicating they were derived through partial melting of a crustal source consisting of metagreywackes with or without minor metaigneous rocks. Taking into account all available regional geological data, we suggest that the Bangong–Nujiang Tethys Ocean may undergo diachronous closure–although the eastern segment may have been closed by the late Early Cretaceous, its western and western–middle segments may still have been at least partially open and active at that time. The Langla–Laqinpu biotite granites were probably generated in post-collisional setting, following slab break-off after closure of the Bangong–Nujiang Tethys Ocean.