Molybdenum Mass Fractions and Isotopic Compositions of International Geological Reference Materials

The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ^98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ^98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g^?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.     

Copper Speciation in a Collection of Geochemical Reference Materials Using Sequential Extraction and Evaluation of the Validity Using XANES Spectroscopy

Copper speciation in a collection of Japanese geochemical reference materials (JSO‐1, JLk‐1, JSd‐1, ‐2, ‐3 and ‐4, JMs‐1 and JMs‐2) was achieved by sequential extraction and characterised using X‐ray absorption near‐edge structure spectroscopy. In the first step of the extraction, referred to as the acid fraction, between 1% and 20% total Cu within the reference materials was extracted. Such a result is typically accounted for by absorption of Cu onto clay minerals. However, the presence of Cu sulfate (an oxidation product of chalcopyrite) was observed in some of the stream sediments affected by mining activity (JSd‐2 and JSd‐3) instead. Copper was extracted in the reducible fraction (targeting Fe hydroxide and Mn oxide) (2–49% total Cu). Between 2% and 51% Cu was extracted in the oxidised fraction (targeting sulfides and organic matter). X‐ray absorption near‐edge structure spectroscopy clarified that the reducible fraction consisted of Cu bound to Fe hydroxide, whereas the oxidised fraction was a mixture of Cu bound to humic acid (HA) and Cu sulfide. In the oxidisable fraction, chalcopyrite was the predominant species identified in JSd‐2, and Cu bound to HA was the major species identified in JSO‐1 (a soil sample).     

Identification of Uranyl Minerals Using Oxygen K‐Edge X‐Ray Absorption Spectroscopy

Although most of the world's uranium exists as pitchblende or uraninite, this mineral can be weathered to a great variety of secondary uranium minerals, most containing the uranyl cation. Anthropogenic uranium compounds can also react in the environment, leading to spatial–chemical alterations that could be useful for nuclear forensics analyses. Soft X‐ray absorption spectroscopy (XAS) has the advantages of being non‐destructive, element‐specific and sensitive to electronic and physical structure. The soft X‐ray probe can also be focused to a spot size on the order of tens of nanometres, providing chemical information with high spatial resolution. However, before XAS can be applied at high spatial resolution, it is necessary to find spectroscopic signatures for a variety of uranium compounds in the soft X‐ray spectral region. To that end, we collected the near edge X‐ray absorption fine structure (NEXAFS) spectra of a variety of common uranyl‐bearing minerals, including uranyl carbonates, oxyhydroxides, phosphates and silicates. We find that uranyl compounds can be distinguished by class (carbonate, oxyhydroxide, phosphate or silicate) based on their oxygen K‐edge absorption spectra. This work establishes a database of reference spectra for future spatially resolved analyses. We proceed to show scanning X‐ray transmission microscopy (STXM) data from a schoepite particle in the presence of an unknown contaminant.     

High Precision Sr‐Nd‐Hf‐Pb Isotopic Compositions of USGS Reference Material BCR‐2

The Lamont‐Doherty Earth Observatory radiogenic isotope group has been systematically measuring Sr‐Nd‐Pb‐Hf isotopes of USGS reference material BCR‐2 (Columbia River Basalt 2), as a chemical processing and instrumental quality control monitor for isotopic measurements. BCR‐2 is now a widely used geochemical inter‐laboratory reference material (RM), with its predecessor BCR‐1 no longer available. Recognising that precise and accurate data on RMs is important for ensuring analytical quality and for comparing data between different laboratories, we present a compilation of multiple digestions and analyses made on BCR‐2 during the first author's dissertation research. The best estimates of Sr, Nd and Hf isotope ratios and measurement reproducibilities, after filtering at the 2s level for outliers, were ⁸⁷Sr/⁸⁶Sr = 0.705000 ± 11 (2s, 16 ppm, n = 21, sixteen digestions, one outlier), ¹⁴³Nd/¹⁴⁴Nd = 0.512637 ± 13 (2s, 25 ppm, n = 27, thirteen digestions, one outlier) and ¹⁷⁶Hf/¹⁷⁷Hf = 0.282866 ± 11 (2s, 39 ppm, n = 25, thirteen digestions, no outliers). Mean Nd and Hf values were within error of those reported by Weis et al. (2006, 2007) in their studies of RMs; mean Sr values were just outside the 2s uncertainty range of both laboratories. Moreover, a survey of published Sr‐Nd‐Hf data shows that our results fall within the range of reported values, but with a smaller variability. Our Pb isotope results on acid leached BCR‐2 aliquots (n = 26, twelve digestions, two outliers) were ²⁰⁶Pb/²⁰⁴Pb = 18.8029 ± 10 (2s, 55 ppm), ²⁰⁷Pb/²⁰⁴Pb = 15.6239 ± 8 (2s, 52 ppm), ²⁰⁸Pb/²⁰⁴Pb = 38.8287 ± 25 (2s, 63 ppm). We confirm that unleached BCR‐2 powder is contaminated with Pb, and that sufficient leaching prior to digestion is required to achieve accurate values for the uncontaminated Pb isotopic compositions.     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.     

Production and Certification of Synthetic Selenium Isotopic Reference Materials

Due to intensive research into selenium isotopes in recent years, the increasing requirement for reliable and comparable measurement results has created a strong demand for selenium isotopic certified reference materials (iCRM) that were previously not available. To address this, eleven selenium iCRMs were developed, including ten synthetic iCRMs (GBW 04447–GBW 04456) and one natural iCRM (GBW 04457). The synthetic iCRMs were prepared with ⁷⁶Se, ⁷⁸Se, ⁸⁰Se and ⁸²Se solutions and a natural selenium solution; the natural iCRM was prepared with highly pure selenium material. The property values of isotope ratios in these iCRMs were certified by calibrated mass spectrometry with a collision cell multi‐collector ICP‐MS. The mass discrimination effect of the instrument was corrected with corresponding ⁷⁸Se/⁷⁶Se isotope mixtures and ⁸²Se/⁷⁶Se isotope mixtures, which were gravimetrically prepared with purified, isotopically enriched selenium materials. Homogeneity and stability tests were performed, and no significant influences were found. The uncertainty of the property values of the iCRMs was evaluated according to the Guide to the Expression of Uncertainty in Measurement (GUM) of ISO/BIPM and ISO Guide 35. The δ^82/76Se value of GBW 04457 relative to NIST SRM 3149 was also calculated. These iCRMs are intended for use in calibration of instruments and evaluation of methods for the determination of selenium isotope ratios.     

Statistical analyses of Global U-Pb Database 2017

The method of obtaining zircon samples affects estimation of the global U-Pb age distribution.Researchers typically collect zircons via convenience sampling and cluster sampling.When using these techniques,weight adjustments proportional to the areas of the sampled regions improve upon unweighted estimates.Here,grid-area and modern sediment methods are used to weight the samples from a new database of 418,967 U-Pb ages.Preliminary tests involve two age models.Model-1 uses the most precise U-Pb ages as the best ages.Model-2 uses the~(206)Pb/~(238)U age as the best age if it is less than a1000 Ma cutoff,otherwise it uses the~(207)Pb/~(206)Pb age as the best age.A correlation analysis between the Model-1 and Model-2 ages indicates nearly identical distributions for both models.However,after applying acceptance criteria to include only the most precise analyses with minimal discordance,a histogram of the rejected samples shows excessive rejection of the Model-2 analyses around the1000 Ma cutoff point.Because of the excessive rejection rate for Model-2,we select Model-1 as the preferred model.After eliminating all rejected samples,the remaining analyses use only Model-1 ages for five rock-type subsets of the database:igneous,meta-igneous,sedimentary,meta-sedimentary,and modern sediments.Next,time-series plots,cross-correlation analyses,and spectral analyses determine the degree of alignment among the time-series and their periodicity.For all rock types,the U-Pb age distributions are similar for ages older than 500 Ma,but align poorly for ages younger than 500 Ma.The similarities(500 Ma)and differences(500 Ma)highlight how reductionism from a detailed database enhances understanding of time-dependent sequences,such as erosion,detrital transport mechanisms,lithification,and metamorphism.Time-series analyses and spectral analyses of the age distributions predominantly indicate a synchronous period-tripling sequence of~91-Myr,~273-Myr,and~819-Myr among the various rock types.     

Middle Jurassic–Early Cretaceous tectonic evolution of the Bayanhushuo area,southern Great Xing’an Range,NE China: constraints from zircon U–Pb geochronological and geochemical data of volcanic and subvolcanic rocks

This study presents new zircon U–Pb geochronology, geochemistry, and zircon Hf isotopic data of volcanic and subvolcanic rocks that crop out in the Bayanhushuo area of the southern Great Xing’an Range (GXR) of NE China. These data provide insights into the tectonic evolution of this area during the late Mesozoic and constrain the evolution of the Mongol–Okhotsk Ocean. Combining these new ages with previously published data suggests that the late Mesozoic volcanism occurred in two distinct episodes: Early–Middle Jurassic (176–173 Ma) and Late Jurassic–Early Cretaceous (151–138 Ma). The Early–Middle Jurassic dacite porphyry belongs to high-K calc-alkaline series, showing the features of I-type igneous rock. This unit has zircon ε_Hf(t) values from +4.06 to +11.62 that yield two-stage model ages (T_DM2) from 959 to 481 Ma. The geochemistry of the dacite porphyry is indicative of formation in a volcanic arc tectonic setting, and it is derived from a primary magma generated by the partial melting of juvenile mafic crustal material. The Late Jurassic–Early Cretaceous volcanic rocks belong to high-K calc-alkaline or shoshonite series and have A₂-type affinities. These volcanics have ε_Hf(t) and T_DM2 values from +5.00 to +8.93 and from 879 to 627 Ma, respectively. The geochemistry of these Late Jurassic–Early Cretaceous volcanic rocks is indicative of formation in a post-collisional extensional environment, and they formed from primary magmas generated by the partial melting of juvenile mafic lower crust. The discovery of late Mesozoic volcanic and subvolcanic rocks within the southern GXR indicates that this region was in volcanic arc and extensional tectonic settings during the Early–Middle Jurassic and the Late Jurassic–Early Cretaceous, respectively. This indicates that the Mongol–Okhotsk oceanic plate was undergoing subduction during the Early–Middle Jurassic, and this ocean adjacent to the GXR may have closed by the Late Middle Jurassic–Early Late Jurassic.     

The terrestrial fauna of the Late Triassic Pant-y-ffynnon Quarry fissures,South Wales,UK and a new species of Clevosaurus (Lepidosauria: Rhynchocephalia)

Pant-y-ffynnon Quarry in South Wales yielded a rich cache of fossils in the early 1950s, including articulated specimens of new species (the small sauropodomorph dinosaur Pantydraco caducus and the crocodylomorph Terrestrisuchus gracilis), but no substantial study of the wider fauna of the Pant-y-ffynnon fissure systems has been published. Here, our overview of existing specimens, a few described but mostly undescribed, as well as freshly processed material, provides a comprehensive picture of the Pant-y-ffynnon palaeo-island of the Late Triassic. This was an island with a relatively impoverished fauna dominated by small clevosaurs (rhynchocephalians), including a new species, Clevosaurus cambrica, described here from a partially articulated specimen and isolated bones. The new species has a dental morphology that is intermediate between the Late Triassic Clevosaurus hudsoni, from Cromhall Quarry to the east, and the younger C. convallis from Pant Quarry to the west, suggesting adaptive radiation of clevosaurs in the palaeo-archipelago. The larger reptiles on the palaeo-island do not exceed 1.5?m in length, including a small carnivorous crocodylomorph, Terrestrisuchus, and a possible example of insular dwarfism in the basal dinosaur Pantydraco.     

华北地台北缘集宁地区古元古代片麻状石榴花岗岩的深熔成因及地质意义

本文对华北克拉通北缘集宁地区空间上密切共生的片麻状石榴花岗岩和孔兹岩系富铝片麻岩的岩相学、地球化学及年代学特征进行了对比研究。SHRIMP锆石U-Pb定年方面,在富铝片麻岩中获得了1910±10Ma和1839±13Ma变质锆石年龄,在片麻状石榴花岗岩中获得了1919±17Ma的变质重结晶锆石年龄。在石榴花岗岩的石榴石包裹体中识别出与富铝片麻岩相对应的进变质阶段(M1)和峰期阶段(M2)的矿物组合,由此确认富铝片麻岩的变质作用和导致石榴花岗岩形成的深熔作用是同一构造热事件的产物。通过对二者变质作用演化及特征变质矿物的对比,认为深熔作用主要发生在峰期后等温降压阶段(M3),石榴花岗岩中的石榴石为深熔作用过程中的残留矿物相或转熔矿物相,而石榴花岗岩则是混合有大量残留矿物相的熔体结晶的产物。对片麻状石榴花岗岩和富铝片麻岩的地球化学组成特征进行了对比分析,片麻状石榴花岗岩既有一定的继承性,又有十分明显的变异性。变异性表现为:1)石榴花岗岩主量和微量元素含量分布极不均匀,微量元素含量普遍低于源岩(Cs、Rb、Th、U、Nb、Ta、Zr、Hf等);2)大离子亲石元素Cs和生热元素U、Th亏损明显,Sr相对富集;3)高场强元素Nb、Ta、P、Ti的明显亏损;4)铕异常变化大,存在铕富集型、铕平坦型和铕亏损型共存的稀土配分曲线的岩石,这是深熔成因石榴花岗岩最突出的表现,也可能是原地-半原地深熔花岗岩的主要地球化学标志。综合区域上的地质资料,认为深熔作用与碰撞后伸展构造背景下基性岩浆底侵事件有关。