柱撑蒙脱石制备与表征

本文采用多种方法制备keggin离子，并探索出制备稳定keggin离子的适宜酸碱度，用此柱化剂制备出层间距为2．4～2．5nm的柱撑蒙脱石。应用X射线走向衍射技术、红外光谱、差热分析对往撑蒙脱石进行表征，用BET、吡啶吸附考察了其表面物理化学性质。结果表明，用Keggin离子制备出的柱撑蒙脱石其层间距在自然状态下为2．4～2．5nm，350C灼烧，层间距稳℃定在1．8nm，且具有耐热性能好、较大的比表面积和较强的Lewis酸位中心等特点．     

Surface chemical analysis in coal preparation research: complementary information from XPS and ToF-SIMS

The application of X-ray photoelectron spectroscopy (XPS) to coal surface characterisation for preparation research is described. Progress towards the acquisition of complementary surface chemical information by time-of-flight secondary ion mass spectrometry (ToF-SIMS) is also discussed. Surface-based beneficiation techniques such as flotation are assuming greater importance as the proportion of fines in raw coal increases due to the proliferation of high capacity mining methods. A necessary condition for the floatability of a coal particle is adequate hydrophobicity, and the degree of hydrophobicity of the flotation concentrate is one factor influencing the ease with which its dewatering can be affected. The hydrophobicity of a coal is very difficult to measure directly because of microporosity, and it is often necessary to deduce the degree of hydrophobicity from a knowledge of the surface chemistry. XPS is able to provide sufficient analytical data to allow relative levels of hydrophobicity to be estimated. In principle, ToF-SIMS should be able to supply additional information enabling refinement of such estimates; however, there are insufficient data at present to allow the ionic fragments detected to be related to specific functional groups at the coal surface.     

区域采样法测定水中硫酸根离子的研究

在分散度不同的区域内进行区域采样用于水中硫酸根离子的测定，结果令人满意。应用此方法测定硫酸根离子的线性范围为２００．０～３０００ｍｇ／Ｌ；进样频率为１２０次／ｈ；相对标准偏差为１．７０％     

A Reflection on Mg, Cd, Ca, Li and Si Isotopic Measurements and Related Reference Materials

This contribution aims to report the reflections we had with the scientific community during two international workshops on reference materials for stable isotopes in Davos (2002) and Nice (2003). After evaluating the isotopic homogeneity of some existing reference materials, based on either certificates, literature data or specific inter-laboratory rounds, we confirm these as primary reference materials or propose new ones relative to which stable isotope compositions should be reported. We propose DSM-3 for Mg, NIST SRM 915a for Ca, L-SVEC for Li and NBS28 for Si. Cadmium does not yet have a well identified delta zero material, although three commercial mono-elemental Cd solutions have yielded the same isotopic composition relative to one another. In order to scale the linearity of any mass spectrometer, some secondary reference materials are also proposed: Cambridge-1 solution for Mg, the "Münster-Cd" and JEPPIM Cd solutions for Cd and the "Big Batch" silicate for Si. The team from Nancy propose to prepare a mixed spike solution for Li isotopes. Well-characterised natural samples such as ocean or continental waters, diatoms, sponges, rocks and minerals are needed to validate the entire analytical procedure, particularly to take into account the effect of sample mineralisation and of chemical manipulations for elemental separation prior to analysis.     

Sorption Characteristics of Rare Earth Element Eu^3＋ onto Silica-Water Interfaces Studied by Fluorescence Spectroscopy

The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for Ph ranges of 1-8.5 and an initial Eu concentration (Ceu) of 2×10-4 M. The sorption rate of Eu was initially low, but significantly increased at Ph>4. The sorption density of Eu species on a silica surface was ～1.58×10-7 mol/m2 when the dissolved Eu species were completely sorbed onto silica-water interfaces at Ph=～5.8. The sorbed Eu species at Ph<6 is aquo Eu3 , which is sorbed onto silica-water interfaces as an outer-sphere complex at Ph<5, but may be sorbed as an inner-sphere bidentate complex at 5相似文献   

Energetic Particles Observed in the CUSP Region During a Storm Recovery Phase

In this paper we report energetic ion behavior and its composition variations observed by the Cluster/RAPID instrument when the spacecraft was travelling in the high latitude magnetospheric boundary region on the day of the 31 March, 2001, strongest magnetic storm in the past 50 years. The Dst index reached −360 nT at about 09:00 UT. During its early recovery phase, large amounts of oxygen and helium ions were observed; the ratio of oxygen to hydrogen in the RAPID energy range reached as high as 250%, which suggests that the observed energetic particles might be of magnetospheric origin. The observations further show that enhanced energetic electron fluxes are confined in a very narrow region, while protons have occupied a larger region, and heavy ions have been observed in an even larger region. The flux of energetic electrons show a slight enhancement in a region where the magnetic field magnitude is around zero. These observed energetic ions could be quasi-trapped by the current sheet in the stagnation region of the cusp.     

Water soluble components of PM10 Chongqing, China

The concentrations of water soluble ions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, NO₃ ^-, Cl^-, and SO ₄ ^2- ) in PM₁₀ samples collected on cellulose filters by a medium-volume cascade impactor were determined, which were obtained from three kinds of areas in Chongqing: industrial area (Jiulongpo district), commercial and residential area (Jiangbei district) and background area (Jinyun Mountain in the Beibei district). The results showed that except for the background site, the annual average values of PM₁₀ are 23% – 61% higher than the national air quality standard (GradeII) (0.1 mg/m³), even that the value of the control site is still 20% higher than American standard (0.05 mg/m³). This implied that serious pollution of fine particles occurred in Chongqing. Nine kinds of soluble ions in water of PM₁₀ were analyzed by ion chromatography (IC) and the annual average concentrations follow the order of [SO ₄ ^2- ] > [NO³ _-] > [Cl^-] > [F^-], and [Ca²⁺] > [NH₄ ⁺] > [K⁺] > [Na⁺] > [Mg²⁺]. Their values were different in these areas: the industrial area > the commercial and living area > the control area. As for NH_{4 +}, K⁺, Ca²⁺, NO₃ ^- and SO ₄ ^2- , their seasonal average concentrations show a similar variation trend: the values in spring and fall were higher than those in summer and winter. The seasonal average concentrations of [Cl^-], [F^-], [Na⁺] and [Mg²⁺] are much lower than those of other ions. However, the concentrations of [Na⁺] changed more greatly in different seasons than those of the other three ions. Correlation coefficients showed that the three areas have been polluted by coal smoke and dust to different extents, while some local resources of pollution should be taken into consideration as well.     

2010—2020年黄河下游河南典型灌区浅层地下水中砷和氟的演化特征及变化机制

黄河下游典型灌区河南段是豫北平原重要的农业种植区。该地区浅层水质整体较差,因常用于作物灌溉或家畜饮用,会对人体健康产生风险,因此对该地区地下水中砷与氟浓度变化特征和机制的研究将有助于提高对该地区地下水污染的认识水平。本文基于2010年和2020年在灌区范围内采集的327组浅层地下水样品,研究区内地下水砷和氟分布情况,并在此基础上对比研究十年间灌区浅层地下水中砷、氟的演化特征,探索分析砷与氟浓度及空间变化机制。研究结果表明：该地区浅层地下水中存在砷与氟超标问题,2020年浅层地下水中高砷（砷浓度大于10μg/L）和高氟（氟浓度大于1mg/L）的样品数量分别占总数的26.1%和26.06%。高砷水分布在太行山前洼地与黄河冲积平原等泥沙互层结构的沉积环境中,还原性较强,同时地下水径流不畅,较强的阳离子交换作用使得其所处环境中Ca²⁺浓度较高。近十年间砷浓度增加的水样占总数31.8%,砷浓度减少的水样占36.7%。砷浓度的增长（减少）是地下水还原性增强（减弱）使得锰氧化物溶解释放（吸附）导致。近十年间不同地区农业灌溉和水源置换等用水方式导致水位变化是引起砷浓度变化的潜在因素。高氟水主要分布在河南新乡与濮阳的黄河沿线,氟离子浓度受到沉积物中萤石等钙质矿物溶解影响,使得高氟地下水出现在低钙环境中。近十年间研究区中氟离子浓度减少的占总数60.2%,氟离子浓度增加的占32.1%,整体变化趋势向好,但是高氟区中氟离子浓度继续增加。氟浓度的变化同样受到Ca²⁺变化影响,在Ca²⁺浓度降低（升高）时氟浓度进一步升高（降低）。地下水中氟升高地区分布在黄河沿线,因此受到黄河水补给影响较大,地下水径流条件较好,阳离子交换作用减弱,使得Ca²⁺浓度降低,此时地下水中砷浓度受到环境影响而降低,因此研究区氟增加地区中砷与氟的分布和演化呈现反向关系。     

喜马拉雅东段库曲岩体锂、铍和铌钽稀有金属矿物研究及指示意义

稀有金属矿物记录了花岗伟晶岩成岩成矿的重要信息。喜马拉雅是全球著名的淡色花岗岩带,库曲岩体位于喜马拉雅东段的特提斯喜马拉雅岩系中。本文调查了库曲岩体的二云母花岗岩、白云母花岗岩、电气石花岗岩和花岗伟晶岩,其中,花岗伟晶岩涉及花岗岩的伟晶岩相和独立伟晶岩脉。库曲岩体产出的稀有金属矿物包括锂辉石、锂绿泥石、绿柱石、铌铁矿-钽铁矿、钇铀钽烧绿石和细晶石,它们主要赋存于似文象伟晶岩、石英-钠长石-白云母伟晶岩、块体长石-钠质细晶岩、块体长石-电气石钠质细晶岩、锂辉石-块体长石-细晶岩、白云母花岗岩的伟晶岩相以及电气石花岗岩内。显微镜观察、电子探针和LA-ICP-MS测试结果显示锂辉石具有四种产状,包括粗粒锂辉石自形-半自形晶、细粒锂辉石-石英镶嵌晶、中细粒锂辉石-钾长石-钠长石-云母镶嵌晶以及发育锂绿泥石的粗粒锂辉石,揭示了其形成时复杂的熔流体动荡结晶环境。绿柱石背散射电子图像（BSE）下呈均一结构和不均一结构（蚀变边、不规则分带和补丁分带）,元素替代机制包括通道-八面体替代、通道-四面体替代以及通道中碱金属阳离子间的置换。铌铁矿族矿物包括原生、蚀变边和不规则分带结构,部分被钇铀钽烧绿石和细晶石交代。与原生铌铁矿相比,蚀变边和不规则分带铌铁矿族矿物总体上富钽贫锰,显示了结晶分异、过冷却引起的过饱和以及流体作用。根据稀有金属矿物揭示的成因信息,独立伟晶岩脉（似文象伟晶岩）、白云母花岗岩的伟晶岩相和电气石花岗岩在岩浆分异程度、经历的演化过程、以及流体活动方面存在差异,很可能是不同期次岩浆活动的产物。库曲岩体绿柱石的Rb和Zn含量、以及铌铁矿族矿物的Sc₂O₃、SiO₂和PbO含量,与已有指示标志存在相关性,作为潜在指示标志仍需开展更多的研究工作。综合含锂辉石伟晶岩的产出、岩浆分异演化程度、多期花岗质岩浆活动、复杂的流体作用以及所属锂丰度高值区等因素,库曲岩体是喜马拉雅东段找锂的有利地段。     

Inter‐laboratory Characterisation of Apatite Reference Materials for Chlorine Isotope Analysis

Here we report on a set of six apatite reference materials (chlorapatites MGMH#133648, TUBAF#38 and fluorapatites MGMH#128441A, TUBAF#37, 40, 50) which we have characterised for their chlorine isotope ratios; these RMs span a range of Cl mass fractions within the apatite Ca₁₀(PO₄)₆(F,Cl,OH)₂ solid solution series. Numerous apatite specimens, obtained from mineralogical collections, were initially screened for ³⁷Cl/³⁵Cl homogeneity using SIMS followed by δ³⁷Cl characterisation by gas source mass spectrometry using both dual‐inlet and continuous‐flow modes. We also report major and key trace element compositions as determined by EPMA. The repeatability of our SIMS results was better than ± 0.10‰ (1s) for the five samples with > 0.5 % m/m Cl and ± 0.19‰ (1s) for the low Cl abundance material (0.27% m/m). We also observed a small, but significant crystal orientation effect of 0.38‰ between the mean ³⁷Cl/³⁵Cl ratios measured on three oriented apatite fragments. Furthermore, the results of GS‐IRMS analyses show small but systematic offset of δ³⁷Cl_SMOC values between the three laboratories. Nonetheless, all studied samples have comparable chlorine isotope compositions, with mean 10³δ³⁷Cl_SMOC values between +0.09 and +0.42 and in all cases with 1s ≤ ± 0.25.