In Situ U‐Th‐Pb Dating and Sr‐Nd Isotope Analysis of Bastnäsite by LA‐(MC)‐ICP‐MS

Bastnäsite is the end member of a large group of carbonate–fluoride minerals with the common formula (REE) CO₃F·CaCO₃. This group is generally widespread and, despite never occurring in large quantities, represents the major economic light rare earth element (LREE) mineral in deposits related to carbonatite and alkaline intrusions. Since bastnäsite is easily altered and commonly contains inclusions of earlier‐crystallised minerals, in situ analysis is considered the most suitable method to measure its U‐Th‐Pb and Sr‐Nd isotopic compositions. Electron probe microanalysis and laser ablation (multi‐collector) inductively coupled plasma‐mass spectrometry of forty‐six bastnäsite samples from LREE deposits in China, Pakistan, Sweden, Mongolia, USA, Malawi and Madagascar indicate that this mineral typically has high Th and LREE and moderate U and Sr contents. Analysis of an in‐house bastnäsite reference material (K‐9) demonstrated that precise and accurate U‐Th‐Pb ages could be obtained after common Pb correction. Moreover, the Th‐Pb age with its high precision is preferable to the U‐Pb age because most bastnäsites have relatively high Th rather than U contents. These results will have significant implications for understanding the genesis of endogenous ore deposits and formation processes related to metallogenic geochronology research.     

Ore Genesis and Tectonic Significance of the Xiaojiashan Tungsten Deposit,Eastern Tianshan,Xinjiang, China: Evidence from Geology,Fluid Inclusions,and Stable Isotope Geochemistry

The Xiaojiashan tungsten deposit is located about 200 km northwest of Hami City, the Eastern Tianshan orogenic belt, Xinjiang, northwestern China, and is a quartz vein‐type tungsten deposit. Combined fluid inclusion microthermometry, host rock geochemistry, and H–O isotopic compositions are used to constrain the ore genesis and tectonic setting of the Xiaojiashan tungsten deposit. The orebodies occur in granite intrusions adjacent to the metamorphic crystal tuff, which consists of the second lithological section of the first Sub‐Formation of the Dananhu Formation (D₂d ₁²). Biotite granite is the most widely distributed intrusive bodies in the Xiaojiashan tungsten deposit. Altered diorite and metamorphic crystal tuff are the main surrounding rocks. The granite belongs to peraluminous A‐type granite with high potassic calc‐alkaline series, and all rocks show light Rare Earth Element (REE)‐enriched patterns. The trace element characters suggest that crystallization differentiation might even occur in the diagenetic process. The granite belongs to postcollisional extension granite, and the rocks formed in an extensional tectonic environment, which might result from magma activity in such an extensional tectonic environment. Tungsten‐bearing quartz veins are divided into gray quartz vein and white quartz veins. Based on petrography observation, fluid inclusions in both kinds of vein quartz are mainly aqueous inclusions. Microthermometry shows that gray quartz veins have 143–354°C of T_h, and white quartz veins have 154–312°C of T_h. The laser‐Raman test shows that CO₂ is found in fluid inclusions of the tungsten‐bearing quartz veins. Quadrupole mass spectrometry reveals that fluid inclusions contain major vapor‐phase contents of CO₂, H₂O. Meanwhile, fluid inclusions contain major liquid‐phase contents of Cl^?, Na⁺. It can be speculated that the ore‐forming fluid of the Xiaojiashan tungsten deposit is characterized by an H₂O–CO₂, low salinity, and H₂O–CO₂–NaCl system. The range of hydrogen and oxygen isotope compositions indicated that the ore‐forming fluids of the tungsten deposit were mainly magmatic water. The ore‐forming age of the Xiaojiashan deposit should to be ~227 Ma. During the ore‐forming process, the magmatic water had separated from magmatic intrusions, and the ore‐bearing complex was taken to a portion where tungsten‐bearing ores could be mineralized. The magmatic fluid was mixed by meteoric water in the late stage.     

Geochemical Characteristics and Genetic Significance of Datangpo‐Type Manganese Ore Deposits during the Cryogenian Period

The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al₂O₃ and TiO₂, SiO₂, K₂O, and Na₂O, and strong negative correlations between Al₂O₃ and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K₂O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ¹³C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO₃^? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.     

From a river valley to a ria: Evolution of an incised valley (Ría de Ferrol,north‐west Spain) since the Last Glacial Maximum

The evolution of incised valleys is an important area of research due to the invaluable data it provides on sea‐level variations and depositional environments. In this article the sedimentary evolution of the Ría de Ferrol (north‐west Spain) from the Last Glacial Maximum to the present is reconstructed using a multidisciplinary approach, combining seismic and sedimentary facies, and supported by radiocarbon data and geochemical proxies to distinguish the elements of sedimentary architecture within the ria infill. The main objectives are: (i) to analyse the ria environment as a type of incised valley to evaluate the response of the system to the different drivers; (ii) to investigate the major controlling factors; and (iii) to explore the differentiation between rias and estuaries. As a consequence of the sea‐level rise subsequent to the Last Glacial Maximum (ca 20 kyr bp ), an extensive basin, drained by a braided palaeoriver, evolved into a tide‐dominated estuary and finally into a ria environment. Late Pleistocene and Holocene high‐frequency sea‐level variations were major factors that modulated the type of depositional environments and their evolution. Another major modulating factor was the antecedent morphology of the ria, with a rock‐incised narrow channel in the middle of the basin (the Ferrol Strait), which influenced the evolution of the ria as it became flooded during Holocene transgression. The strait acted as a rock‐bounded ‘tidal inlet’ enhancing the tidal erosion and deposition at both ends, i.e. with an ebb‐tidal delta in the outer sector and tidal sandbanks in the inner sector. The final step in the evolution of the incised valley into the modern‐defined ria system was driven by the last relative sea‐level rise (after 4 kyr bp ) when the river mouths retreated landward and a single palaeoriver was converted into minor rivers and streams with scattered mouths in an extensive coastal area.     

Topographical controls on small‐volume pyroclastic flows

Emplacement of small‐volume (<0·1 km³) pyroclastic flows is significantly influenced by topography. The Arico ignimbrite on Tenerife (Canary Islands) is a characteristic small‐volume pyroclastic flow deposit emplaced on high relief topography. The pyroclastic flow flowed down pre‐existing valleys on the southern slopes of the island. In proximal areas deep (up to 100 m) valleys acted as efficient conduits for the pyroclastic flow, which was mostly channelled; in this particular area the ignimbrite corresponds to a homogeneous, moderately welded deposit, consisting of flattened pumices in an abundant ashy matrix with a relatively low lithic fragment content. In intermediate zones significant changes occur in the steepness of the slope and, although still channelled, here the pyroclastic flow was influenced by hydraulic jumps. In this area, two different units can be clearly distinguished in the ignimbrite: the lower unit is composed of a lithic‐rich ground‐layer deposit that formed at the turbulent, highly concentrated head of the flow; the upper unit consists of a well welded pumice‐rich deposit that occasionally reveals a basal layer formed by shearing with the lower part. This division into two units is maintained as far as distal areas near the present‐day coastline, where the slope is very gentle or null and the ignimbrite is not channelled. The ground layer is not found in distal areas. The ignimbrite here only consists of the upper unit, which is occasionally repeated due to a surging process provoked by the lower flow speed, as the pyroclastic flow spread out of the channelled zone. A theoretical model on how topography controlled the deposition of the Arico ignimbrite is derived by interpreting the observed lithological and sedimentological variations in terms of changes in topography and bedrock morphology. This new model is of general applicability and will help to explain other deposits of similar characteristics.     

施工顺序对软土地坪复合地基的影响探讨

场地回填土与搅拌桩施工顺序将直接影响软土地坪复合地基的处理效果,其中沉降控制是影响地坪安全运行的关键。以近海软土地区工业厂房水泥土搅拌桩复合地基工程为例,探讨了复合地基水泥土搅拌桩、回填土两种不同施工顺序的影响因素及相应处理效果;通过数值模拟试验,计算分析了不同填土厚度下两种工况的地基固结总沉降、施工沉降、工后沉降。结果表明,采用“先土后桩”的施工顺序的施工期沉降大于“先桩后土”,但工后沉降大大减小,提高了软土地坪地基处理效果,有利于处理后地坪的安全运行,验证了前述分析结论,为合理设计方案的确定提供了重要的参考依据。     

基于三维激光扫描技术的岩质边坡泥化夹层空间分布和几何形态

为了定量研究泥化夹层的空间分布和几何形态,以云南省玉溪市生活垃圾焚烧发电厂高边坡局部开挖剖面为对象,利用徕卡ScanStation C10三维激光扫描仪和瑞典ROMER RA-7520-2六轴关节臂三维测量仪进行扫描,得到了开挖剖面和泥化夹层的原始点云数据;然后采用Cyclone和Geomagic Wrap软件对点云数据进行一系列处理,分析了泥化夹层的三维空间分布、层面产状、间距、层面粗糙度和几何形态。结果表明：大部分泥化夹层横向分布于整个扫描剖面,少数呈局部分布;泥化夹层的平均倾向为196.41°±5.51°,平均倾角为22.27°±2.23°,间距在3.7~49.1 cm之间,平均值为（20.4±12.0）cm;不同层位及同一层位不同横向位置的泥化夹层厚度都不等,最厚约20 mm,最薄小于1 mm;泥化夹层顶面局部典型区域的平面拟合偏差在-22.4~32.5 mm之间,沿夹层倾向的粗糙度系数在5.67~16.77之间,平均值为10.11±3.25;泥化夹层的表面积与体积之比在5.14~5.86 cm^-1之间。运用三维激光扫描技术研究泥化夹层的空间分布和几何形态是可行的。玉溪市生活垃圾焚烧发电厂高边坡的泥化夹层具有宏观整体上相对平直、相互近似平行、非等距分布、间距小、层数多、厚度薄,细观上顶面粗糙底面相对光滑、三维形态复杂的特点。     

不排水不可压缩条件下两相介质的两重网格算法

对于不排水、不可压缩饱和软土地基的固结问题的有限元分析,可以用Biot固结方程来考虑土体颗粒与孔隙水间的相互作用。由于受Babuska-Brezzi稳定条件的限制,用常规的等插值u-p混合有限元法求解将导致孔隙压力出现紊乱的结果。提出了基于位移和压力线性等插值函数的两重网格,但位移独立变量总数大于独立压力变量总数的计算方法,可以满足Babuska-Brezzi稳定条件,使得位移场和压力场单元插值阶数保持一致。通过几个简单算例验证了提出方法的正确性。     

Chemical Procedures for Rhenium Extraction from Geological Samples: Optimising the Anion Resin Bead Clean‐up Step

Rhenium–osmium geochronometry for samples with low Re and complex matrices requires improved Re extraction methods. Here, we investigate plausible controls on efficiency and efficacy of Re extraction during our anion resin bead purification. Four different protocols are compared, each isolating a single variable to test. Rhenium concentrations for solutions at each step of each protocol document differences in chemical recovery/yield. The negative‐thermal ionisation mass spectrometry (N‐TIMS) signal intensity serves as a proxy for Re yield and purity. These data document correlations between the N‐TIMS signal intensity and (a) the duration of anion resin bead conditioning prior to loading with Re‐bearing solution, and (b) both duration and strength of nitric acid used during rinsing of the Re‐loaded anion resin bead. The optimal protocol improved Re signal intensity around fourteen times compared with our current Re extraction protocol, an aggregate of 2.4 times improvement in chemical recovery (yield) and 5.8 times improvement in emission efficiency (purity). Repeated N‐TIMS isotopic measurements on our in‐house Re standard solution (1407) verify that our optimal protocol‐3 does not fractionate Re isotopes. The improved anion resin bead method considerably lowers the Re detection limit and allows Re‐Os isotopic analysis of picogram‐level Re hosted in geological samples with complex matrices.     

Development and Re‐Evaluation of Tourmaline Reference Materials for In Situ Measurement of Boron δ Values by Secondary Ion Mass Spectrometry

Six tourmaline samples were investigated as potential reference materials (RMs) for boron isotope measurement by secondary ion mass spectrometry (SIMS). The tourmaline samples are chemically homogeneous and cover a compositional range of tourmaline supergroup minerals (primarily Fe, Mg and Li end‐members). Additionally, they have homogeneous boron delta values with intermediate precision values during SIMS analyses of less than 0.6‰ (2s). These samples were compared with four established tourmaline RMs, that is, schorl IAEA‐B‐4 and three Harvard tourmalines (schorl HS#112566, dravite HS#108796 and elbaite HS#98144). They were re‐evaluated for their major element and boron delta values using the same measurement procedure as the new tourmaline samples investigated. A discrepancy of about 1.5‰ in δ¹¹B was found between the previously published reference values for established RMs and the values determined in this study. Significant instrumental mass fractionation (IMF) of up to 8‰ in δ¹¹B was observed for schorl–dravite–elbaite solid solutions during SIMS analysis. Using the new reference values determined in this study, the IMF of the ten tourmaline samples can be modelled by a linear combination of the chemical parameters FeO + MnO, SiO₂ and F. The new tourmaline RMs, together with the four established RMs, extend the boron isotope analysis of tourmaline towards the Mg‐ and Al‐rich compositional range. Consequently, the in situ boron isotope ratio of many natural tourmalines can now be determined with an uncertainty of less than 0.8‰ (2s).