27Al核磁共振波谱法测定环境生物样品中铝研究进展

近二十年来,高分辨率²⁷Al核磁共振(²⁷Al NMR)广泛应用于研究Al(Ⅲ)离子水解过程,Al(Ⅲ)与环境生物配体的配位化学,环境与生物样品中铝含量测定和形态分析,监测铝在植物、动物、酵母菌等微生物中的转运过程,具有快速、直接、非破坏性等优点。²⁷Al NMR不仅适用于高浓度的溶液,也可应用于低浓度(10^-6mol·L^-1)的实际环境、生物样品。应用²⁷Al MASNMR可直接对固态样品中铝的存在状态和含量进行表征和测量。本文中对²⁷Al NMR的应用进展作一评述,并总结了近二十年来文献发表的²⁷Al化学位移数据。引用文献70余篇。     

植物样品中单宁的微波溶出快速测定法研究

研究了利用微波代替一般的沸水浴处理试样的方法。对不同植物样品中单宁的浸提测定，与常规方法做了对照，并讨论了微波功率、时间、酸度等因素对测定结果的影响。研究表明，此法可大大地缩短测定时间，提高测定效率，节省人力、物力，不污染环境，便于大批量样品的测定，相对标准偏差≤１．４％，测定结果较为满意。为植物样品中单宁的测定，提供了一个快速、简便、准确的分析方法，并可借鉴于其它样品的测定。     

填充吸附剂微萃取技术及其在微小体积样品萃取应用中的研究进展

微萃取技术是分析化学领域发展迅速,且已经得到广泛应用的样品前处理技术。填充吸附剂微萃取(MEPS)是一种微量固相萃取技术,使用微量的吸附剂填充于微量注射器,通过反复抽推方式使样品多次流经吸附剂以完成样品吸附萃取过程,萃取后的样品可直接用于色谱分析。典型的MEPS萃取设备包括MEPS注射器和MEPS吸附床(BIN)。MEPS优化的主要因素为MEPS处理过程的参数,包括样品流速、样品量与样品萃取循环次数,吸附剂及淋洗、洗脱溶剂的种类和体积,还需要考虑样品基质对MEPS性能的影响和样品残留和重复使用问题。MEPS中最重要的部分是吸附剂,主要有商品化的MEPS吸附剂,包括硅基的Silica、C18、C8等,碳材料的Hypercarb和聚苯乙烯聚合物类的SDVB、HDVB吸附剂等。研究用的吸附剂包括分子印迹材料、限进分子印迹材料、碳基材料、导电聚合物类材料、改性硅基材料及共价-有机骨架材料等。MEPS结合多种分析仪器已经成功应用于从不同基质中提取单一或多种分析物,所涵盖基质包括生物样品(尿液、唾液、血浆或血液)、河流水体或生活污水以及几种食品和饮料。MEPS处理复杂生物基质样品时,通常需要稀释样品、除蛋白质等预处理。MEPS具有需要样品体积小、操作快速等特点,在生物基质样品分析中有望得到更广泛的使用。在环境样品中,该技术可与现场便携仪器联用,未来将有望在现场进行快速检测,并于易分解样品等方面发挥作用。     

生物样品中微量硒测定方法的进展

概述了近年来硒含量测定方法如荧光法、原子吸收光谱法、原子荧光法、等离子体发射光谱法、分光光度法、气相色谱法、高效液相色谱法等的研究进展,阐述了各种方法在实际研究中的优势与不足,引用文献63篇。     

NEWS

纳米金材料( Au NPs)的广泛应用使其以多种渠道进入环境体系,从而对生物体的健康构成潜在威胁。因此,检测环境样品特别是水体环境中的微量纳米金对于环境监测和纳米粒子的生物安全性研究具有重要意义。然而在实际样品分析中,由于样品基质复杂,纳米粒子的浓度极低且存在易团聚等问题,在仪器分析之前必须辅以合适的样品前处理技术。目前用于纳米粒子分离富集的样品前处理技术较少,且存在操作繁琐、耗时长等问题。武汉大学化学与分子科学学院胡斌教授课题组近期提出了聚合物整体柱毛细管微萃取与等离子体质谱( ICP-MS)在线联用新方法,实现了环境水样中羧基功能基修饰Au NPs的测定,该方法具有灵敏度高、选择性好、样品通量大、试样消耗量少、操作简单、无需消解等特点。     

环境样品分析

本文是“分析试验室”定期评述“环境试样分析”的第７篇评述。它全面评述了１９９８年１对１９９９年１２月间我国环境分析的进展,内容包括：概述,大气样品分析,水样品分析,土壤和沉积物样品分析,生物样品分析,放射性监测,标准、质量控制和质量保证,展望。     

螯合树脂分离富集痕量稀土及生物样品中痕量稀土的测定

采用大孔螯合型丙烯酸系氨羧基离子交换树脂,在pH4.5、0.10mol/1α-羟基异丁酸介质中富集痕量稀土,以0.1mol/l盐酸为淋洗剂,可定量洗脱稀土并与钙、镁、铁、铜分离。方法可用于人发、结石、花生、葡萄、草莓、黄瓜、猪肝等生物样品中痕量稀土的测定。     

粉末样品制备方法对扫描电子显微镜成像质量的影响

纳米粉末材料是化学化工领域常见的样品,在其扫描电子显微镜表征中,通常会遇到以下几个问题：二次电子产率低,粉末聚集结块从而导致无法观察纳米形貌,以及荷电效应等.以二氧化硅小球粉末、ZSM-5分子筛纳米片以及聚苯乙烯小球粉末为研究对象,在不镀金属膜的前提下,分别采用粉末直接涂抹在导电碳胶或银胶上和溶液分散后滴涂在不同基底上的方法进行样品制备,比较了直接涂抹和分散后滴涂在基底上两种方法对扫描电子显微镜成像的影响.结果表明,样品经过溶液分散能够有效的减小粉末的团聚,其中,滴涂在硅片基底上可以减小荷电效应和背景影响,清晰观察到粉末的纳米级形貌.     

微波在样品消解中的应用

介绍微波消解样品的基本原理、特点、应用及注意事项。用微波消解样品，效率高、速度快、易于控制、对环境无污染，应用于矿石、金属、食品、化工产品、医药及环境样品等样品化学分析的预处理，是传统加热消解样品的理想替代方法。     

扫描电子显微镜对样品的要求及样品的制备

扫描电子显微镜对样品的要求很严,要求样品必须是固体,且做到五无:无毒、无放射性、无污染、无磁、无水分,成分稳定,块状样品大小要适中,粉末样品要进行特殊处理,对不导电和导电性能差的样品要进行镀膜,且要选择适当的镀膜仪,方能达到理想的分析效果.     

Capabilities of elemental analysis by EDXRF for geochemistry

Elemental analyses of 10 geological samples from Morocco and some Standard Reference Materials were performed by Energy Dispersion X-Rays Fluorescence, Wavelength Dispersion X-Rays Fluorescence and Neutron Activation Analysis techniques in order to assess the accuracy and sensitivity of the concentrations determined with regard to requirements in geochemical exploration. The possibilities of utilization of EDXRF as an appropriate and economic technique for the analysis of various elements which are important in interpretation of geochemical data were evaluated.     

Sample Preparation with the Use of Oxidative Fluoride Decomposition and Sulfation Exemplified by the Determination of Noble Metals in Geological Standard Reference Materials

A sample preparation procedure was proposed for the reliable determination of noble metals at Clarke values in geological and geochemical materials. The procedure is based on the oxidative fluoride decomposition of a sample followed by the sulfation of the fusion or cake.     

The NIMROC samples as reference materials for neutron activation analysis

The NIMROC reference materials NIM-D, NIM-G, NIM-L, NIM-N, NIM-P, and NIM-S and the precious metal ore PTO-1 have been analysed using thermal and epithermal methods of instrumental neutron activation. The abundances of 40 major, minor and trace elements are reported. The usefulness of the NIMROC reference materials is assessed in terms of the requirements of neutron activation techniques. Of the seven reference materials, NIM-L is the most useful geochemical material for activation analysis. It contains suitably high concentrations of most elements that can be determined. Inhomogeneity problems encountered in PTO-1 for some elements give emphasis to the difficulty of selecting suitable geological material for ultra-trace elements where small quantities of sample are used.     

The future demand for geological reference materials

Geological RMs (G-1 and W-1) were introduced in 1951 for the purpose of validating the accuracy of silicate rock analysis by dc arc spectrography. Since then the introduction of an array of other spectrographic methods has greatly enhanced research into geological processes. The range of elements that could be determined was expanded, and the detection limits for measurement was lowered repeatedly through the years. The development and use of reference materials was critically important in supporting this rapid expansion of geological research. Essentially, all RMs are of importance to the geosciences community since G-1 and W-1 have been prepared and distributed by national geological institutions, first by the USGS or the CRPG, rather than by national metrology institutions. These geological institutions are not yet certifying their RMs according to ISO Guides. The International Association of Geoanalysts (IAG) is seeking to meet this higher metrological requirement. Since the inception of the IAG certification program in 2003, five powdered silicate rock materials have been issued to meet the demand with respect to calibration, method validation, traceability, etc. for whole rock major and trace element analysis. The introduction of microanalytical techniques nearly decades ago and the more recent advent of MC-ICP-MS have become new driving forces in geochemical research. The first opened the possibility of performing in situ elemental composition studies at the ??m scale. The second led to the discovery of small isotope composition variations of mass- and non-mass-dependent processes in ??non-traditional?? stable isotopes (e.g., Fe, Cu, Zn, Mo, W, and Hg) through cosmo- and geochemical processes. Coupling the two techniques expands in situ analysis to isotopic studies. These developments have created great demand for (certified) RMs for both isotope ratio and microanalytical measurements for the geochemical community that is not yet being met. Homogeneity at a ??m scale and unmatched matrices of the natural minerals or synthetic doped glasses hamper the progress in certification of RMs for the microanalytical measurement community. A challenge for the production of isotope RMs is to prepare an RM solution with an isotopic composition similar to the natural systems under investigation. Refined cadmium and nickel metals, for example, have fractionated isotopic compositions far above the range observed in natural systems of interest. Yet, the calibration RM cannot fulfill its purpose when the uncertainty of its isotopic composition exceeds that of the unknowns being measured against it. In this regard, the IAG has recently certified a calibration solution for the determination of Os isotopic ratios. It is also working through member organizations, USGS, and MPI for Geochemistry (Mainz) to develop appropriate microanalytical standards. In addition to these current and future challenges, establishing metrological traceability of geological reference materials in the absence of starting points developed by national metrology institutions is a major issue that needs attention in all future certifications.     

Rare earth element determination in silicate rocks using neutron activation analysis and mass spectrometry

A pre-irradiation group separation procedure for the quantification of 11 to 13 rare earth elements (REE) in geological materials by neutron activation analysis, with yield determination by mass spectrometry isotope dilution analysis of Sm and Nd, is described. Utilization of the shorterlived isotopes of the REE allow sufficient data for most geochemical studies to be obtained within one day of irradiation, although where necessary additional information may be obtained following a decay period of three to four weeks. Analysis of selected USGS rock standards shows the method to be both accurate and precise.     

Certified reference materials of geological and environmental objects: Problems and solutions

A review of publications on the creation and application of certified reference materials for the chemical analysis of geological materials and environmental objects with the aim to ensure the uniformity of measurements is presented.     

土壤地球化学在广南斗月金矿中的应用

对现已发现的超大型金矿和国内金矿资源进行统计,结果表明,大型、超大型矿床中与微细浸染型金矿相对应的金矿成因类型(如渗滤热液型金矿、含碳浅变质碎屑岩型金矿等)占有很大比例。因此开展对微细浸染型金矿的研究和找矿具有重要的实际意义。在广南斗月金矿开展1∶10000土壤地球化学测量(简称化探),了解测区以Au为主的As、Sb、Hg、Ag土壤地球化学背景,确定化探异常下限,圈定Au、As、Sb、Hg、Ag化探(次生晕)异常,根据各异常面积的大小、浓度的高低以及五个元素异常套合(组合)情况等综合因素,对化探综合异常进行评序和分级,结合地质简测等地质资料的综合研究分析,判别具有潜在找矿价值的异常区,为进一步地质勘探工作提供靶区。     

Determination of platinum group elements and gold in geological materials: a review of recent magnetic sector and laser ablation applications

Inductively coupled plasma mass spectrometry (ICP-MS) has been used extensively as a rapid and accurate instrumental technique for determinations of platinum group elements (PGEs) and gold. Methods based upon ICP-MS have been important in analyses of many types of samples, and especially of geological materials containing very low concentrations of these elements. Recently, analytical methods based upon ICP-MS have been improved and widened in scope by the introduction of new magnetic sector (or high resolution) spectrometers, and laser ablation (LA) sampling. Detection limits attainable for PGEs and Au using magnetic sector instruments in analytical procedures cited here are as low as 0.01-0.02 pg g⁻¹; instruments have a dynamic range of up to nine orders of magnitude. This review describes applications of the techniques to analyses of PGEs and gold in minerals, nodules, meteorites, ice, sediments, airborne particulates and reference materials. The period covered is 1998-2002.     

Direct atomic-absorption spectrometric analysis of geological materials-a review

A review is given of the problems likely to be encountered in the atomization of solid samples of geological materials, and of the applications of this technique.     

The determination of arsenic in rocks,sediments and minerals by arsine generation and atomic absorption spectrometry

An arsine generation-atomic absorption method for the rapid and precise determination of 0.04–4000 p.p.m. arsenic in geological materials is described. The siliceous sample is decomposed with perchloric, nitric and hydrofluoric acids and potassium permanganate solution, and the residue is dissolved in dilute hydrochloric acid. Arsine is generated with potassium iodide, tin(II) chloride and zinc powder, and introduced to an argon—hydrogen flame. The method is applied to various standard rocks, NBS mineral standards, and geochemical exploration samples. The relative standard deviation is 4–14 %.