南海北部琼东南盆地浅表层沉积物的地球化学特征及对沉积环境的指示*

南海北部琼东南盆地海底存在着巨型麻坑, 现有研究多认为其形成主要与海底流体渗漏有关。目前对琼东南盆地深海沉积物地球化学特征及麻坑区的生物地球化学过程等尚不清楚。文章选取南海北部琼东南盆地C14、C19两个站位岩心样品, 进行了总硫(TS)、总碳(TC)、总有机碳(TOC)、铬还原性硫化物(CRS)及其δ³⁴S_CRS值测试, 并结合总氮/总碳(TN/TOC)比值和已发表的孔隙水中SO₄^2-浓度等进行了地球化学特征分析。研究表明: C14站位以3.91m bsf (below seafloor)为界, 上下分别存在有机质参与的硫酸盐还原反应(OSR)和甲烷厌氧氧化作用(AOM)驱动的硫酸盐还原反应(SR); 3.91m bsf以上的部位沉积物的TS、TC含量均低于3.91m bsf以下部位, 且沉积物孔隙水中SO₄^2-浓度由3.91m bsf以上的缓慢凹型减少变成3.91m bsf以下的线性减少, 说明该处成为沉积物中地球化学特征分界的明显标志; 在3.91m bsf以下, 受到甲烷渗漏的影响。C19站位沉积物中TS与TC含量由浅到深逐渐增加, 但与TN/TOC比值变化呈现几乎相反趋势, 即整个岩心以OSR为主, 并呈现出有机质早期成岩阶段的沉积现象。C14和C19两个站位柱状沉积物的δ³⁴S_CRS值变化范围分别为-50.2‰~-46.9‰和-50.1‰~-42.0‰ (V-CDT标准), 均显示出了较为偏负的硫同位素值, 表明研究区主要的生物化学过程是在相对开放体系下硫酸盐还原作用的结果, 综合说明该研究区麻坑的甲烷流体已经喷发, 目前可能处于衰退期, 甚至已经不活跃, 该结果与前人的认识基本一致。     

Stream geochemical response to reductions in acid deposition in headwater streams: Chronic versus episodic acidification recovery

In the decades since dramatic reductions in acid emissions and subsequent deposition in North America and Europe, the vast majority of research on aquatic chemical recovery has focused on trends in acid–base concentrations during baseflow conditions. Missing from such assessments is consideration of higher flow periods, when flow paths and chemical concentrations change and episodic acidification may occur. Stream samples collected weekly and bi‐hourly during high‐flow storm events from 1992 to 2015 at three watersheds representing a gradient in response to acid deposition in the south‐eastern United States were used to evaluate temporal trends in acid anions, base cations, acid neutralizing capacity (ANC), and pH for each of five distinct flow exceedance regimes, as well as trends in concentration–discharge (C–Q) relationships. For the most well‐buffered watershed (mean ANC = 220 μeq L^?1), ANC and pH increased at a similar rate for baseflow and storm flow conditions. Decreases in sulfate controlled ANC trends at higher flows, whereas smaller sulfate decreases in combination with base cation increases resulted in similar ANC improvements for low‐flow periods. For the most acid sensitive watershed (mean ANC = 10 μeq L^?1), no trends in ANC or pH were observed for the lowest flows (>90% flow exceedance), whereas reductions in sulfate resulted in significant increases in ANC during higher flow conditions. At all sites, greater rates of sulfate decline during high‐flow, as compared with low‐flow, conditions are likely a result of a reduced capacity of near surface soils to adsorb and retain sulfur in these non‐glaciated watersheds. Overall, consistent increases in pH (~0.01–0.02 pH units year^?1) during higher flow conditions (<10% flow exceedance) in contrast to the variable trends observed during lower flows (>50% flow exceedance) illustrate that episodic acidification is recovering at an equal or greater rate than chronic acidification in these watersheds.     

锂离子正极材料重点技术专利分析

正极材料是制造锂离子电池的关键材料之一，占据电池成本的25%以上，在锂离子电池中占据核心地位。该文对锂离子正极材料进行专利信息的挖掘和数据分析，通过专利申请趋势、布局、企业专利实力对锂离子正极材料的技术专利展开分析，总结了锂离子正极材料技术的发展、企业专利实力与保护情况。同时对主要用于动力型锂离子电池中的锰酸锂正极材料进行了申请态势、竞争格局、实力排查以及技术主题和技术功效的分析，可为相关研发人员及企业开发外围专利或改进专利提供思路。     

老挝MK离子吸附型稀土矿床成矿及其矿化分布特征

稀土是重要的战略性关键金属矿产资源,老挝是“一路一带”沿线的重要国家,境内寻找离子吸附性稀土矿找矿潜力巨大。老挝长山褶皱带呈NW-SE向分布,带内海西期黑云母二长花岗岩发育,以低中山地形地貌为主,近期在带内发现多处花岗岩风化壳有关的离子吸附型稀土矿床。文章通过分析该区花岗岩地球化学特征、风化壳剖面及钻孔样品,研究赋存于花岗岩风化壳的离子吸附型稀土矿床成矿地质特征,探讨其在低中山地区的成矿特征,推断低中山地形地貌与矿体分布的关系。研究表明,区内花岗岩风化壳结构分层特征明显,矿体分布受海拔标高及微地貌控制;稀土元素的分馏不仅在垂向上,在水平方向上也十分明显。通过厘定本区离子吸附型稀土矿床成矿特征,发现在低中山地貌区,高海拔第一阶梯矿化不好,且以轻稀土为主,而相对低的第二阶梯矿化较好,矿化强度高,稀土类型向中重稀土过渡的特征明显。     

地下水中镭的固液分配系数及其测定方法研究

近十多年来天然放射性镭(Ra)同位素在水环境、水资源研究领域越来越受到重视,Ra同位素应用在海底地下水排泄估算、湖泊水均衡计算、地下水年龄研究、地下水地表水污染源解析等方面取得了重要的研究成果,这得益于Ra同位素测试技术的发展和对Ra地球化学性质认识的深化。Ra的固液分配系数(K_d)是影响Ra在土壤和含水层中迁移的关键参数,正确认识K_d是利用Ra同位素精准示踪水文过程特别是地下水循环过程的决定性因素。本研究对前人报道的地下水中Ra的K_d值分布范围进行了综合分析,并探讨K_d值的主要影响因素。发现天然环境下K_d值的变化范围为0.1~1×10⁶ mL·g^-1,最大值和最小值之间相差7个数量级。水的盐度、pH值和沉积物中铁(Fe)的含量等对K_d具有显著影响。总结了Ra的K_d值的确定方法,把不同研究者提出的方法归纳为氡(Rn)平衡法、热动力学吸附平衡计算法、实验法和离子交换法,分析了各种方法的优缺点。 提出建立精准的水溶液中Ra的α离子输入反冲项测定方法,优化分析计算流程,提供准确获得Ra的K_d值的技术思路。本研究成果能够为Ra水文地球化学性质研究及其在水文过程中的应用提供参考和技术支撑。     

Evaluation Methods and Indexes for Ultra-deep Petroleum Reservoir Preservation with Case Studies

Following consideration of the characteristics of high temperature, high pressure and high in-situ stress in ultra-deep sedimentary basins, together with the existence of hydrocarbon phase state transformation, hydrocarbon-water-rock interaction and rock mechanical property transition at those depths, the evaluation index system for hydrocarbon preservation was established. The physical leakage evaluation indexes can be divided into three categories: the dynamic efficiency indexes of micro-sealing, caprock integrity and natural gas diffusion. The chemical loss evaluation indexes can be divided into two categories: the thermochemical sulfate reduction (TSR) index in marine gypsum-bearing carbonate strata and the thermochemical oxidation of hydrocarbons (TOH) index in clastic strata. The slippage angle and overconsolidation ratio (OCR) are the key evaluation indexes in the evaluation of the integrity of shale caprocks. TSR intensity can be quantitatively calculated by use of the ZnPVT state parameter method. The TOH strength can be used to estimate the degree of hydrocarbon chemical loss, based on the TOH-related authigenic calcite cement content or the degree of negative δ13C of authigenic calcite. For the evaluation of ultra-deep preservation in specific areas, key indexes can be selected according to the local geological conditions, instead of all indexes needing to be evaluated for every scenario.     

A new approach for molecular characterisation of sediments with Fourier transform ion cyclotron resonance mass spectrometry: Extraction optimisation

Fourier transform ion cyclotron resonance mass spectrometry (FTICRMS) can begin to tease apart the molecular character of sedimentary organic matter (SOM). We therefore tested five different solvents (aqueous base, CHCl₃, MeOH, pyridine and water) for their ability to extract a representative fraction from two organic rich lacustrine sediments, Mangrove Lake, Bermuda (MLB) and Mud Lake, Florida (MLF). Following comparison using liquid state nuclear magnetic resonance spectroscopy (NMR) and negative ion mode electrospray ionization mass spectrometry (FTICRMS) we found that pyridine was the optimal solvent, extracting a more diverse (10–100× greater integration for carbonyl, amide and amine groups) and a larger number of peaks on average (1375–1450 vs. 380–1450). Comparison of the pyridine extracts between MLB, MLF and two organic poor sediments from the Mississippi River Delta and Bayou Grande (Pensacola, FL) showed that only 4.9% of the molecular formulae were common to all four and that unique formulae made up the highest proportion of the assignments. The use of pyridine for extracting immature (Holocene) SOM for FTICRMS analysis can therefore be widely applied to immature sediments and produce representative spectra.     

Boron Isotope Analysis of Silicate Glass with Very Low Boron Concentrations by Secondary Ion Mass Spectrometry

We present an improved method for the determination of the boron isotopic composition of volcanic glasses with boron concentrations of as low as 0.4–2.5 μg g^?1, as is typical for mid‐ocean ridge basalt glasses. The analyses were completed by secondary ion mass spectrometry using a Cameca 1280 large‐radius ion microprobe. Transmission and stability of the instrument and analytical protocol were optimised, which led to an improvement of precision and reduction in surface contamination and analysis time compared with earlier studies. Accuracy, reproducibility (0.4–2.3‰, 2 RSD), measurement repeatability (2 RSE = 2.5–4.0‰ for a single spot with [B] = 1 μg g^?1), matrix effects (? 0.5‰ among komatiitic, dacitic and rhyolitic glass), machine drift (no internal drift; long‐term drift: ~ 0.1‰ hr^?1), contamination (~ 3–8 ng g^?1) and machine background (0.093 s^?1) were quantified and their influence on samples with low B concentrations was determined. The newly developed set‐up was capable of determining the B isotopic composition of basaltic glass with 1 μg g^?1 B with a precision and accuracy of ± 1.5‰ (2 RSE) by completing 4–5 consecutive spot analyses with a spatial resolution of 30 μm × 30 μm. Samples with slightly higher concentrations (≥ 2.5 μg g^?1) could be analysed with a precision of better than ± 2‰ (internal 2 RSE) with a single spot analysis, which took 32 min.     

A Comprehensive Method for Precise Determination of Re,Os, Ir,Ru, Pt,Pd Concentrations and Os Isotopic Compositions in Geological Samples

A comprehensive method for the precise determination of Re, Os, Ir, Ru, Pt and Pd concentrations as well as Os isotopic compositions in geological samples is presented. Samples were digested by the Carius tube method, and the Os was extracted by conventional CCl₄ method. The Re, Ir, Ru, Pt and Pd were first subgroup separated from the matrix elements into Re‐Ru, Ir‐Pt and Pd by a 2‐ml anion exchange column. Subsequently, the Re‐Ru was further purified by a secondary 0.25 ml anion exchange column or by microdistillation of Ru using CrO₃‐H₂SO₄ as an oxidant followed by a secondary 0.25 ml anion exchange separation of Re. The Pd and Ir‐Pt were further successively purified by an Eichrom‐LN column to completely remove Zr and Hf, respectively. Rhenium, Ir, Ru, Pt and Pd were individually measured by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS), except for Ru after microdistillation purification was analysed by negative‐thermal ionisation mass spectrometry (N‐TIMS). The analytical results for peridotite reference material WPR‐1 agree well with the previously published data. Finally, several mafic rock reference materials including TDB‐1, WGB‐1, BHVO‐2, BCR‐2, BIR‐1a and DNC‐1a were analysed for Re‐Os isotopes and platinum‐group element concentrations to test their suitability for certification.     

Improved Inter‐calibration of Faraday Cup and Ion Counting for In Situ Pb Isotope Measurements Using LA‐MC‐ICP‐MS: Application to the Study of the Origin of the Fangshan Pluton,North China

A laser ablation multi‐collector inductively coupled plasma‐mass spectrometry (LA‐MC‐ICP‐MS) method was developed to obtain precise and accurate Pb isotopic ratio measurements in low‐Pb materials (< 10 μg g^?1) using a combination of Faraday cups and ion counters (FC–IC). The low abundance ²⁰⁴Pb (~ 1.4%) was collected using an IC. A NBS 981 standard solution was used to cross‐calculate the FC–IC gain and to investigate the signal response characteristics of the IC. A significant, continuous and linear decrease in the FC–IC gain was observed within 1 hr, but this drift could be corrected using the calibrator‐sample‐calibrator bracketing method. In addition, a non‐linear response of the IC used in this study was observed and corrected by a non‐linear correction algorithm, which was established by measuring a series of gravimetrically prepared NBS 981 standard solutions (NIST SRM 981). Compared with the conventional arrangement, the use of the newly designed X skimmer cone and Jet sample cone improved the signal intensities from Pb isotopes by a factor of 1.9. Compared with only Faraday cups, using a combination FC–IC array was found to enhance the measurement repeatability (RSD) of ^20xPb/²⁰⁴Pb by approximately one order of magnitude when the ²⁰⁴Pb intensity was < 8 mV. Eight natural glasses and the NIST SRM 612 reference material glass (as a calibration material) were measured to evaluate the new protocol for Pb isotope determination. The analytical results were in agreement with the reference values within 2s measurement uncertainties. For MPI‐DING ATHO‐G (5.67 μg g^?1 total Pb), KL2‐G (2.07 μg g^?1 total Pb) and ML3B‐G (1.38 μg g^?1 total Pb), the typical accuracies of ^20xPb/²⁰⁴Pb were 0.09% of preferred values with precisions of < 0.33% (2RSD). The Pb isotope ratios in feldspars from granodiorite and within mafic microgranular enclaves (MMEs) from the Fangshan pluton, North China, were measured using the present method. The Pb isotopic compositions of feldspars from the whole host granodiorite show that that are radiogenic in the margin zone and gradually become less radiogenic. For the MMEs, the Pb isotopic compositions of feldspars are highly variable and overlap with those of the whole host granodiorite. For single‐grain feldspar, the strong rim‐core‐rim variations of the Pb isotopic compositions and trace elements are interpreted to have been generated via magma mixing. These results suggest that the Fangshan pluton underwent magma mixing of mantle‐derived mafic magmas with felsic magmas, and the proportion of the mafic magma influx decreased over time.