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.     

Metallogenic Mechanism and Tectonic Setting of Tungsten Mineralization in the Yangbishan Deposit in Northeastern China

The Yangbishan iron–tungsten deposit in the Shuangyashan area of Heilongjiang Province is located in the center of the Jiamusi Massif in northeastern China. The rare earth element and trace element compositions of the scheelite show that it formed in a reducing environment and inherited the rare earth element features of the ore-forming fluid. The geochemical characteristics of the gneissic granite associated with the tungsten mineralization show that the magma formed in this reducing environment and originated from the partial melting of metamorphosed shale that contained organic carbon and was enriched with tungsten. In addition, in situ Hf isotopic analysis of zircons from the gneissic granite indicates that they probably originated from the partial melting of a predominantly Paleo–Mesoproterozoic crustal source. According to LA-ICP-MS zircon dating, the Yangbishan orerelated gneissic granite has an Early Paleozoic crystallization age of 520.6 ± 2.8 Ma. This study, together with previous data, indicates that the massifs of northeastern China, including Erguna, Xing'an, Songliao, Jiamusi, and Khanka massifs, belonged to an orogenic belt that existed along the southern margin of the Siberian Craton during the late Pan-African period. The significant continental movements of this orogeny resulted in widespread magmatic activity in northeastern China from 530 Ma to 470 Ma under a tectonic setting that transitioned from compressional syn-collision to extensional postcollision.     

Morphological and Phylogenetic Study Based on New Materials of Anchiornis huxleyi (Dinosauria,Theropoda) from Jianchang,Western Liaoning,China

Anchiornis huxleyi, which is a member of the Middle–Late Jurassic Yanliao Biota, is the smallest feathered dinosaur ever known. It has been described as a critical link between feathered dinosaurs and birds. Recent studies, including those of Anchiornis, Xiaotingia, Eosinopteryx and Aurornis, challenged Archaeopteryx as the most basal bird. The new Anchiornis huxleyi specimens that are described in this paper show some minor different characters compared to previously reported Anchiornis specimens, which has revised the character list of Anchiornis and indicates a different phylogenetic point from former opinions.     

Petrology and PGE Abundances of High‐Cr and High‐Al Podiform Chromitites and Peridotites from the Bulqiza Ultramafic Massif,Eastern Mirdita Ophiolite,Albania

The Bulqiza ultramafic massif, which is part of the eastern Mirdita ophiolite of northern Albania, is world renowned for its high-Cr chromitite deposits. High-Cr chromitites hosted in the mantle section are the crystallized products of boninitic melts in a supra-subduction zone (SSZ). However, economically important high-Al chromitites are also present in massive dunite of the mantle-crust transition zone (MTZ). Chromian-spinel in the high-Al chromitites and dunites of the MTZ have much lower Cr# values (100Cr/(Cr+Al)) (47.7–55.1 and 46.5–51.7, respectively) than those in the high-Cr chromitites (78.2–80.4), harzburgites (72.6–77.9) and mantle dunites (79.4–84.3). The chemical differences in these two types of chromitites are reflected in the behaviors of their platinum-group elements (PGE). The high-Cr chromitites are rich in IPGE relative to PPGE with 0.10–0.45 PPGE/IPGE ratios, whereas the high-Al chromitites have relatively higher PPGE/IPGE ratios between 1.20 and 7.80. The calculated melts in equilibrium with the high-Cr chromitites are boninitic-like, and those associated with the high-Al chromitites are MORB-like but with hydrous, oxidized and TiO2-poor features. We propose that the coexistence of both types of chromitites in the Bulqiza ultramafic massif may indicates a change in magma composition from MORB-like to boninitic-like in a proto-forearc setting during subduction initiation.     

Petrological and Os Isotopic Characteristics of Zedong Peridotites in the Eastern Yarlung–Zangbo Suture in Tibet

The Zedong ophiolites in the eastern Yarlung–Zangbo suture zone of Tibet represent a mantle slice of more than 45 km~2. This massif consists mainly of mantle peridotites, with lesser gabbros, diabases and volcanic rocks. The mantle peridotites are mostly harzburgite, lherzolite; a few dike-like bodies of dunite are also present. Mineral structures show that the peridotites experienced plastic deformation and partial melting. Olivine(Fo89.7–91.2), orthopyroxene(En_(88–92)), clinopyroxene(En_(45–49) Wo_(47–51) Fs_(2–4)) and spinel [Mg~#=100×Mg/(Mg+Fe)]=49.1–70.7; Cr~#=(100×Cr/(Cr+Al)=18.8–76.5] are the major minerals. The degree of partial melting of mantle peridotites is 10%–40%, indicating that the Zedong mantle peridotites may experience a multi–stage process. The peridotites are characterized by depleted major element compositions and low REE content(0.08–0.62 ppm). Their "spoon–shaped" primitive–mantle normalized REE patterns with(La/Sm)_N being 0.50–6.00 indicate that the Zedong ultramafic rocks belong to depleted residual mantle rocks. The PGE content of Zedong peridotites(18.19–50.74 ppb) is similar with primary mantle with Pd/Ir being 0.54–0.60 and Pt/Pd being 1.09–1.66. The Zedong peridotites have variable, unradiogenic Os isotopic compositions with ~(187)Os/~(188)Os=0.1228 to 0.1282. A corollary to this interpretation is that the convecting upper mantle is heterogeneous in Os isotopes. All data of the Zedong peridotites suggest that they formed originally at a mid-ocean ridge(MOR) and were later modified in supra–subduction zone(SSZ) environment.     

Metallogeny of the Baiyangping Lead‐Zinc Polymetallic Ore Concentration Area,Northern Lanping Basin of Yunnan Province,China

The Lanping Basin in the Nujiang‐Lancangjiang‐Jinshajiang (the Sanjiang) area of northeastern margin of the Tibetan Plateau is an important part of eastern Tethyan metallogenic domain. This basin hosts a number of large unique sediment‐hosted Pb‐Zn polymetallic deposits or ore districts, such as the Baiyangping ore concentration area which is one of the representative ore district. The Baiyangping ore concentration area can be divided into the east and west ore belts, which were formed in a folded tectogene of the India‐Asia continental collisional setting and was controlled by a large reverse fault. Field observations reveal that the Mesozoic and Cenozoic sedimentary strata were outcropped in the mining area, and that the orebodies are obviously controlled by faults and hosted in sandstone and carbonate rocks. However, the ore‐forming elements in the east ore belt are mainly Pb‐Zn‐Sr‐Ag, while Pb‐Zn‐Ag‐Cu‐Co elements are dominant in the west ore belt. Comparative analysis of the C‐O‐Sr‐S‐Pb isotopic compositions suggest that both ore belts had a homogeneous carbon source, and the carbon in hydrothermal calcite is derived from the dissolution of carbonate rock strata; the ore‐forming fluids were originated from formation water and precipitate water, which belonged to basin brine fluid system; sulfur was from organic thermal chemical sulfate reduction and biological sulfate reduction; the metal mineralization material was from sedimentary strata and basement, but the difference of the material source of the basement and the strata and the superimposed mineralization of the west ore belt resulted in the difference of metallogenic elements between the eastern and western metallogenic belts. The Pb‐Zn mineralization age of both ore belts was contemporary and formed in the same metallogenetic event. Both thrust formed at the same time and occurred at the Early Oligocene, which is consistent with the age constrained by field geological relationship.     

Provenance Study of Fe–Ti Oxide Minerals in the Quaternary Sediments in Yichang Area and Its Implication of Formation Time of the Yangtze Three Gorges, China

The Three Gorges are considered to be critical to understand the formation of Yangtze River. Recent research results suggest that the Yangtze Three Gorges was created during the Quaternary but the exact time is debatable. Fe–Ti oxide minerals are seldom used to study sediment provenance, expecially using scanning electron microscopy(SEM), and energy dispersive spectrometer(EDS). In this study, the provenance of Quaternary sediments in Yichang area, which is located to the east of the Yangtze Three Gorges, was investigated by using SEM and EDS to research Fe–Ti oxides. The Panzhihua vanadium titanomagnetite and Emeishan basalt outcrop are located to the west of the Three Gorges. Further, the materials from them are observed in the Quaternary sediments of Yichang area. Fe–Ti oxide minerals from the Huangling granite are observed in the Yunchi and Shanxiyao Formations, which were formed before 0.75 Ma B.P., whereas Fe–Ti oxide minerals from the Huangling granite, Panzhihua vanadium titanomagnetite, and Emeishan basalt are observed in the riverbed and fifth-terrace sediments of the Yangtze River, which were formed after 0.73 Ma B.P.. Thus, we can infer that the Three Gorges formed after the deposition of the Shanxi Formation and before the fifth-terrace; i.e., 0.75–0.73 Ma B.P..     

Occurrence and Chemical Compositions of Amphiboles in Altered Dioritic Rocks of Laiwu Skarn‐Type Iron Deposit in West Shandong Area,China

The Laiwu Fe deposit is the largest skarn‐type deposit in West Shandong in China, with an estimated reserve of 290 Mt of iron ore. Here, we investigate the occurrence and chemical composition of amphiboles in altered dioritic rocks of this deposit. Three generations of amphibole group minerals were identified in these rocks. The first type (Type 1) is a hornblende with a generally euhedral crystal shape, 150–500 μm in size, and dominantly occurs in the host monzonite. The second type (Type 2) of hornblende occurs as fine grains (<100 μm) or concentric rims, less than 50 μm in thickness, around the Type 1 hornblende. The third type (Type 3) of amphibole is anhedral actinolite occurring along the boundary or the cracks of the Type 1 or 2 hornblende grains. The Type 1 hornblende has higher FeO (12.5–15.6 wt.%) and lower MgO contents (11.2–14.6 wt.%) than the Type 2 hornblende, which has an FeO content ranging from 8.8 to 10.5 wt.% and MgO content ranging from 14.2 to 17.1 wt.%. The Type 3 actinolite shows the lowest FeO (4.6–6.4 wt.%) and highest MgO (19.8–21.2 wt.%) contents. We infer that the Type 2 hornblende formed from Fe‐rich hydrothermal fluids released during rapid upwelling of the crystallizing magma. The fluids were relatively reduced and enriched in Fe. The Type 3 actinolite formed by coupled dissolution and reprecipitation, and its formation is one of the features denoting Fe‐enrichment events. Our study of these types of amphibole provides insights into the ore formation process.     

Automated Extraction of a Five‐Year LA‐ICP‐MS Trace Element Data Set of Ten Common Glass and Carbonate Reference Materials: Long‐Term Data Quality,Optimisation and Laser Cell Homogeneity

LA‐ICP‐MS is increasingly applied to obtain quantitative multi‐element data with minimal sample preparation, usually achieved by calibration using reference materials (RMs). However, some ubiquitous RMs, for example the NIST SRM 61× series glasses, suffer from reported value uncertainties for certain elements. Moreover, no long‐term data set of analyses conducted over a range of ablation and tuning conditions exists. Thus, there has been little rigorous examination of the extent to which offsets between measured and reported values are the result of error in these values rather than analytically induced fractionation. We present new software (‘LA‐MINE’), capable of extracting LA‐ICP‐MS data with no user input, and apply this to our system, yielding over 5 years of data (~ 5700 analyses of ten glass and carbonate RMs). We examine the relative importance of systematic analytical bias and possible error in reported values through a mass‐specific breakdown of fourteen of the most commonly determined elements. Furthermore, these data, obtained under a wide range of different ablation conditions, enable specific recommendations of how data quality may be improved, for example the role of diatomic gas, the effect of differential inter‐glass fractionation factors and choice of transport tubing material. Finally, these data demonstrate that the two‐volume Laurin ablation cell is characterised by no discernible spatial heterogeneity in measured trace element ratios.     

A New Reference Material for Tritium Organic Molecules in Sediment: Results of an International Intercomparison Exercise

Solid matrix ³H reference materials are challenging to prepare given the volatile nature of ³H and are often unrepresentative of the range of ³H forms that may be encountered during routine analysis. As a result, few ³H reference materials are currently available, undermining verification of analytical techniques for environmental ³H measurement. To address this, an International Working Group on Organically‐Bound Tritium Analysis determined to produce a tritium natural matrix reference material (NMRM). The reference material comprises marine sediment blended with sewage sludge contaminated with ³H‐organic species arising from authorised discharges from a radiopharmaceutical manufacturing site. Previous studies have demonstrated that the ³H species have persisted in the environment over three decades providing valuable supporting data to underpin the characterisation of the NMRM. The preparation and characterisation of the NMRM are described along with the subsequent application of the reference material in an international intercomparison exercise involving nineteen laboratories from nine countries. A reference value of 168 ± 22 Bq kg^?1 was derived from the data arising from the proficiency test.