Neutron Activation Analysis, Atomic Absorption and X-Ray Fluorescence Spectrometry Review for 2003

This review for the year 2003 deals with three relatively well-established, mature, analytical techniques (neutron activation analysis, atomic absorption spectrometry and X-ray fluorescence spectrometry) that nevertheless remain very important for the characterisation of geological and environmental samples. Developments in neutron activation analysis included modification to the technique in relation to the determination of platinum-group elements, as well as consideration of sample size in ore grade estimation. A considerable body of literature was published on the application of atomic absorption spectrometry in the analysis of environmental samples. Many of these proposed technical and methodological improvements, notably in extraction procedures. X-ray fluorescence spectrometry saw developments in in situ analysis, synchrotron micro-XRF (μ-SRXRF) and a confocal X-ray set-up for 3D elemental imaging. XRF technologies were used in the analysis of geological samples, reference materials, glasses, solutes and environmental materials.     

黑色页岩样品中痕量级铂族元素地球化学成分标准物质研制

介绍了黑色页岩样品中6个铂族元素铂、钯、钌、锇、铑、铱的标准物质研制过程。黑色页岩样品采自贵州黄家湾,为一次采集、一次混样的原始样品,随机抽取包装好后的样品进行检验与定值。均匀性、稳定性符合要求后,按照国际标准化组织(ISO)34、35指南的基本要求和我国一级标准物质的技术规范,采用多个实验室协同测试的定值方式,利用不同原理的分析方法对此样品的6个铂族元素进行定值。以各实验室组数据作为最小统计单元,用Grubbs准则、Dixon法检验剔除离群数据,Shapiro-Wilk法检验各元素数据分布的正态性。检验结果100%的元素呈正态或近似正态分布。定值的6个元素均符合标准值水平。     

The Preparation and Certification of Two Samples of Chromium Ore

The preparation of two chromium ores as reference materials is described and the procedures used in the measurement of the homogeneity of the samples are outlined. Statistical analysis of the data submitted by 32 laboratories that resulted in the certification of the samples is presented. Certified values have been assigned for 11 constituents in the one sample and for 10 in the other sample. Provisional values have been assigned for FeO in both samples and CaO in one of the samples.     

地下水中无机多元素测定监控样的制备与应用

根据中国地质调查局正在组织开展全国性1:50000～1:250000地下水污染调查评价工作中对重点区要求必测的无机元素项目要求,用天然基体的地下水制备地下水无机多元素测定监控样。采集的地下水经初步分析后,进行有关组分的添加处理,制备需要研制的实验室监控样品。通过均匀性和稳定性检验,判定监控样的均匀性良好,在监测期间内性质稳定。探讨了该监控样在地下水无机元素测定质量监控工作中可以用于校准仪器、评价测量方法的准确度和用作分析质量保证。     

光石沟晶质铀矿:一种潜在的铀矿物电子探针定量分析标准样品

电子探针定量分析是采用元素A在待测样品中的特征X射线强度与标准样品中元素A特征X射线强度相比较而进行的,要实现未知样品的元素定量分析必须要具有相应的标准样品,目前可用于铀元素分析的电子探针分析标准样品极少,且缺乏与天然矿物成分、结构近似的标准样品。国际和国内已经制定了电子探针标准物质研制的规范(GB/T 4930—2008/ISO14595:2003),按该规范规定的方法研究了产于陕西光石沟铀矿床的晶质铀矿,结果表明:这些晶质铀矿晶形发育好,颗粒大,具备良好的纯度、均匀性和稳定性。随机选择30个颗粒进行均匀性检测,UO₂和PbO在95%的置信区间的平均浓度不确定度分别为0.275%和0.060%,具备非常好的均匀性;该晶质铀矿在电子探针电子束长时间(如360s)轰击下和在自然条件下存放,均具有良好的稳定性;采用五家实验室化学分析定值方法确定了该晶质铀矿的化学成分,并计算了不确定度,主量元素UO₂为(86.80±0.36)%,PbO为(4.80±0.07)%,其他元素也给出了参考值。综合以上研究结果:产于光石沟铀矿床的晶质铀矿满足GB/T 4930—2008关于电子探针定量分析标准样品的各项判据,是一个潜在的适用于铀矿物化学成分电子探针定量分析使用的天然矿物标准样品。     

石榴石钇(Y)元素电子探针分析及应用——以佛子岭石榴云母片岩为例SCIEI北大核心CSCD

石榴石是最重要的造岩矿物之一,通常能够保留早期的矿物结构和物质并记录较为晚期的变形和变质反应。石榴石钇(Y)元素环带特征丰富、复杂,不同的环带特征通常暗示不同的形成环境或经历了不同的变质事件,是变质演化历史研究的重要媒介之一。以往的研究中,多以LA-ICP-MS作为石榴石Y元素的主要分析手段,EPMA主要用于主量元素的分析。但是,LA-ICP-MS的束斑尺寸(44μm)和基底效应较EPMA(0~5μm)大,当石榴石颗粒小、包体和裂隙发育或成分环带以微区尺寸内存在较大变化时,大束斑更容易覆盖某些特殊信息。通过对石榴石Y元素测试参数的调试和标样验证,最终确定峰位测试时长和背景测试时长分别为140s和70s,并进行了PHA谱峰干扰剥离,降低检测限至54×10^(-6)。本文将通过对比佛子岭石榴云母片岩(LD025)4颗石榴石的EPMA主、微量原位分析(Ca、Mg、Mn、Fe、Y、Al、Si、Cr、Ti、Na)和LA-ICP-MS石榴石Y元素分析结果,论证EPMA分析Y元素的可行性。石榴石X-ray Mapping和主量成分剖面揭示该4颗石榴石均为生长环带,Mn呈钟形分带,Y与X Sps呈强烈正相关性,与X Grs、X Alm、X Prp相关性不清晰。EPMA和LA-ICP-MS分析结果显示Y含量曲线在核部和幔部具有良好的一致性,Grt1~Grt3中Y均表现出自核部(500×10^(-6)~1200×10^(-6))向幔部(200×10^(-6)~500×10^(-6))逐渐降低,极边部Y含量低(20×10^(-6)~200×10^(-6))且变化复杂;Grt4中Y含量差异相对较小(180×10^(-6)~450×10^(-6)),仅在边部出现不同程度的升降。因EPMA对于Y元素含量较低(<200×10^(-6))时灵敏度不够或者LA-ICP-MS束斑尺寸大容易掩盖边部窄带成分真实变化等原因,二者在边部Y元素差异较大。分别对EPMA和LA-ICP-MS的分析结果应用Grt-Xtm温度计和Grt单矿物压力计获得的变质PT结果显示Grt1~Grt3(核-幔-边)和Grt4(核-边)均记录较为完整、统一的温压演化过程。M1→M2→M3的变质温压变化分别为T=530~544℃、P=0.78~0.82GPa→T=577~616℃、P=0.89~0.98GPa→T=631~661℃、P=1.01~1.07GPa,表现为顺时针演化型式,M1至M3反映的是一个“暖俯冲”过程。根据温度评价结果,Grt1~Grt3(1.2~1.4mm,自形程度高)形成时间应早于Grt4(0.8mm,自形程度低)。由此可知,大颗粒的石榴石Y元素含量及变化特征通常更容易揭示相对完整的变质演化历史。本次研究为变泥质岩演化历史、变质温压评价等研究提供了不同视角和思路,结合EPMA主量(矿物成分、X-ray mapping、BSE分析)和微量元素(Y等)分析能够更加精准、全面地解读地质信息。     

基于污染指数法和GIS技术评价江西德兴矿区土壤重金属污染

以江西德兴大型矿区为例,进行大尺度的土壤环境调查和重金属污染评价。系统采集该区域919个土壤样品,在应用X荧光光谱仪和电感耦合等离子原子发射光谱仪为主体的分析配套方案分析土壤样品中重金属含量的基础上,采用单因子污染指数法和综合污染指数法,分别从原始含量、污染指数以及基于GIS的污染空间分析3个方面进行该矿区的土壤重金属污染评价。结果表明,矿山开采对该区的土壤环境造成了不同程度的As、Cd、Zn、Cu重金属污染。污染区域主要分布在德兴铜钼和铅锌矿区、乐安河下游乐平附近的煤矿区以及南部电化学厂附近。     

An Automated Iridium-Strip Heater for LA-ICP-MS Bulk Analysis of Geological Samples

In this paper we describe a flux‐free fusion technique for the highly precise LA‐ICP‐MS bulk analysis of geological samples. For this purpose we have developed an automated iridium‐strip heater with temperature and melt time control. To optimise the homogeneity of the fused glasses and to reduce possible depletion of volatile elements during melting, we undertook experiments with basaltic rock and glass powders using different melting temperatures (1300–1700 °C) and melting times (5‐80 s). Major and trace element microanalysis was performed using EPMA and LA‐ICP‐MS. Homogeneous glasses were obtained for temperatures ≥ 1500 °C and melting times ≥ 10 s. High loss (20‐90%) of highly volatile elements (e.g., Cs, Ge, Sn, Pb) was observed for high melting temperatures (≥ 1600 °C) and long melting times (80 s). Standard melting conditions (1600 °C, 10 s) represent a compromise, as the glasses were homogeneous with respect to major and trace elements and, at the same time, were not depleted in elements with condensation temperatures (at a pressure of 10^?4 bar) higher than about 900 K (e.g., Zr, Hf, Ba, Sr, REE, U, Mo, Ni, Rb, Ga). Several international geological reference materials with SiO₂ ranging between 47% m/m and 59% m/m were prepared using our standard melting conditions (1600 °C, 10 s) and subsequently analysed by LA‐ICP‐MS. These samples also include the new Brazilian basaltic reference material BRP‐1. Matrix‐matched calibration of the LA‐ICP‐MS data was performed using the basaltic reference glasses KL2‐G, ML3B‐G, BCR‐2G and BHVO‐2G. Most analytical data agreed within uncertainty at the 95% confidence level with the GeoReM preferred values published in the GeoReM database for reference materials of geological and environmental interest. To demonstrate routine bulk LA‐ICP‐MS analyses of geochemical and cosmochemical samples using the whole rock fusion technique, we also present trace element data for ocean island basalts from Lanai (Hawaii) and of Martian meteorites.     

微珠比色法用于野外现场天然水样和化探样品中微量铁的分析

针对野外现场分析的要求,选择微珠比色技术用于江河天然水样和化探样品中铁的分析。以向红菲啰啉为显色剂,硫代硫酸钠掩蔽铜的干扰,方法摩尔吸光系数为1×105L.mol-1.cm-1,精密度(RSD,n=10)为2.5%,适用于0.001μg/g以上的铁的测定。方法用于江河天然水样和化探样品中铁的测定,结果与分光光度法相符。方法在拟定的过程中注意了降低环境污染、降低成本和提高方法的可操作性。建立的方法干扰少,选择性好,对实验环境条件要求不高,满足野外现场分析应用。对于天然水可直接测定;但一般的化探样品由于铁含量较高,需要稀释后再测定。     

Chemical weathering of granite under acid rainfall environment, Korea

Chemical weathering was investigated by collecting samples from five selected weathering profiles in a high elevation granitic environment located in Seoul, Korea. The overall changes of chemistry and mineralogical textures were examined reflecting weathering degrees of the samples, using polarization microscopy, X-ray diffraction (XRD), electron probe micro analysis (EPMA), X-ray fluorescence spectroscopy (XRF), and inductively coupled plasma–mass spectroscopy (ICP–MS). The chemical distribution in the weathering profiles shows that few trace elements are slightly immobile, whereas most major (particularly Ca and Na) and trace elements are mobile from the beginning of the granite weathering. On the other hand, there were mineralogical changes initiated from a plagioclase breakdown, which shows a characteristic circular dissolved pattern caused by a preferential leaching of Ca cation along grain boundaries and zoning. The biotite in that region is also supposed to be sensitive to exterior environmental condition and may be easily dissolved by acidic percolated water. As a result, it seems that some rock-forming minerals in the granitic rock located in Seoul are significantly unstable due to the environmental condition of acidic rainfall and steep slopes, where they are susceptible to be dissolved incongruently leading some elements to be highly depleted.     

Particle Size Distributions of Clay-rich Sediments and Pure Clay Minerals: A Comparison of Grain Size Analysis with Sedimentation Field-Flow Fractionation

Two clay-rich coastal sediment samples have been characterised together with three pure clays identified as major components of the sediment samples. The mineralogy of the sediments was determined by X-ray diffraction, and their bulk properties measured (organic carbon content, leachable iron and manganese, surface area and cation exchange capacity). A simple approach is used to model the properties of the sediments from those of their pure clay components. Good agreement is found for cation exchange capacity and specific surface area indicating that the clay minerals are the most important constituents influencing the sediments' surface properties. Particle size distributions were assessed by conventional grain size analysis, and also by Sedimentation Field-Flow Fractionation (SedFFF). These two approaches yield sharply differing size distributions; in particular, conventional grainsize analysis indicates a much greater proportion of submicron particles. Similar results are obtained from analysis of pure clays. The most likely reason for this is artifacts introduced in the unavoidable 1 m prefractionation used for SedFFF.     

Research on the Occurrence of Titanium in Coal-Measure Kaoline in Songyi, Hubei

Using X-ray diffraction (XRD) analysis and an electron-probe microanalyser (EPMA), this research found that the main independent mineral of titanium (Ti) in the kaoline of Songyi is anatase. The granularity of anatase is from 0.5 um to 1.5 um, and some exceed 10 um. This research provides important scientific evidence for the exploitation of the coal-measure kaoline in the Sooth China.     

基于X射线荧光光谱法测定常见生物样品中常量和微量元素

基于大米、小麦、玉米等23种国家生物成分系列标准物质,探讨了X射线荧光光谱法在常见生物样品中常量和微量元素测定中的应用。在对各待测元素的激发电流电压、分析线、背景位置、干扰谱线、分析晶体、准直器、探测器和脉冲高度分布等条件进行分析的基础上,采用粉末压片法制样,基于回归曲线法和康普顿散射线内标法求取各待测元素的标准曲线常数、元素间吸收效应的影响系数和谱重叠系数。结果表明:国家生物成分系列标准物质具有足够宽的含量范围和适当的含量梯度,基本能覆盖常见生物样品中各元素的含量范围。方法检出限能够保证测定结果的有效性,测量精密度为2.62%～14.79%,且标准物质各元素的测定值与标准值基本相符。方法具有简便、灵敏和准确的特点,能够满足分析的需求。     

Investigation of elemental enrichment and ecological risk assessment of surface soils in two industrial port cities,southwest Iran

In recent years, there has been a rapid growth in the two industrial port cities of Iran, the port of Mahshahr and the port of Imam Khomeini. In spite of their importance for the economy, the two cities require monitoring and assessment from an environmental and human health perspective. In this study, environmental quality and heavy metals pollution of soils influenced by human activities were investigated. A total of 30 soil samples were collected and subjected to detail physicochemical characterization. The results showed high levels of heavy metals in the urban soils of port of Mahshahr (POM) and elevated respective levels in surface soils of the port of Imam Khomeini (PIK) with Ni being significantly higher than those in POM. The integrated pollution index (IPI) values of metals ranged from 1.22 to 1.87 in POM and 1.52 to 3.31in PIK, 50% of soil samples in PIK were classified as highly polluted, and all of the soil samples in PM were classified as moderately polluted. These results are in accordance with Enrichment Factor (EF) values, which showed the role of anthropogenic activities in the soil heavy metal enrichment. Moreover, the highest potential ecological risk index (RI) was found in the sites of petrochemical industries in PIK indicating serious metal contamination. Statistical analysis showed that heavy metals were mainly controlled by human activities. The results showed more dense industrial activity in PIK is responsible for higher pollution. This study establishes a benchmark against which future monitoring and remediation programs can be based on. Because of proximity to the Persian Gulf, continued the release of contaminants into the region, could have adverse biological health effects.     

Comparison of Synchrotron Radiation X-Ray Fluorescence with Conventional Techniques for the Analysis of Sedimentary Samples

A comparison is made of elemental analyses of sediment samples (lake bottom sediments and sediments from the petroliferous Bazhenovka Formation) by five competitive methods (synchrotron radiation X-ray fluorescence (SR-XRF), INAA, ICP-MS, AAS and traditional XRF). The object of this study was to identify the most suitable analytical techniques for applications in sedimentary geochemistry. Advantages and shortcomings of the five techniques were considered with respect to applications related to studies of palaeo-climate changes recorded in sedimentary cores from Lake Baikal and the geochemical stratigraphy of the Bazhenovka Formation, which is rich in organic material. We have concluded that SR-XRF was the best technique for producing extensive analytical data series, from the point of view of its speed, ease of application, cost, non-destructive nature and sensitivity, which allowed for the simultaneous determination of more than twenty elements of geochemical interest in small samples of sediments. An additional benefit of the method was demonstrated when used for the independent certification of geological reference materials. International reference samples BIL-1 and SDO-1 were certified by means of this method without use of reference materials. Analyses were based on the physics of the theory of energy transport.     

Multi-Element Reference Samples of Black Shale

This paper describes the creation of two new reference samples of black shale, SCHS-1 and SLg-1, collected in the Bodaibo Region of Irkutsk District (Siberia, Russia). These samples have been developed as State Standard Samples to meet the requirements of Russia's Normative Documents, so that they can be recognised by the Russian State Certification Agency and included on the State Register of certified reference materials. SCHS-1 was produced from shale of the Khomolkho suite; SLg-1 represents the average composition of the Sukhoy Log gold deposit (within Au mineralisation). The homogeneity was assessed by applying the concept of potential inhomogeneity, and the inhomogeneity uncertainties (σ_inhom) for the indicator elements that were estimated experimentally by silicate XRF analysis. It was found that a majority of the indicator elements was characterised by σ_inhom/Δ_p < 1/8 (Δ_p is the permissible certification uncertainty), and so σ_inhom was neglected for the indicator elements and all other elements that were included in their respective group. The value of σ_inhom calculated for Fe (σ_inhom,Fe/Δ_p > 1 /8) was taken into consideration for the noble metals and their associated elements (e.g., Ag, As, Au, etc.). More than fifty laboratories (thirty-seven from Russia) were involved in the interlaboratory experiment (ILE) to analyse these reference samples. The data obtained from the ILE allowed SCHS-1 and SLg-1 to be certified for, fifty-one and forty-three elements, respectively, as State Standard Samples.     

湖相碳酸盐岩元素测试方法研究

湖相碳酸盐岩因形成于大陆环境,通常陆源硅酸盐组分含量较高并影响元素组成特征,不应简单地套用海相碳酸盐岩的方法进行元素测试。对柴西茫东地区红山梁剖面始新统下干柴沟组-中新统下油砂山组湖相碳酸盐岩采用酸溶法、电子探针、LA等多手段进行的地球化学综合研究,结果显示,各种测试方法应用于湖相碳酸盐岩分析时都存在适用性与局限性问题。酸溶法的局限性在于所获得的K等碱金属元素含量不能用于后续分析。而对微区测试方法而言,首先LA与探针两种微区测试方法能否进行数据上的通用需要比较二者的相关性;其次由于光斑大小的限制,对泥晶组分而言,需在判断陆源的干扰程度并进行相应扣除后,才能反映沉积水体的元素组成特征。因此,在分析陆源硅酸盐组分对湖相碳酸盐岩元素含量影响程度的基础上,提出两种排除陆源硅酸盐组分对泥晶组分元素含量影响的方法,可以实现微区测试方法在湖相碳酸盐岩中的有效应用。     

The detection of roadside pollution of rapidly growing city in arid region using the magnetic proxies

This work is a complementary investigation to the earlier urban soil survey for a rapidly growing city of relatively high traffic density. Therefore, it aims to apply the environmental magnetism approach to assess the roadside pollution at a known polluted site. The used magnetic proxies are the initial magnetic susceptibility and saturation magnetization. The results prove the applicability of this method in detecting roadside pollution. The shape and magnitude of the magnetic signals was affected by the topography and prevailing wind direction that caused the magnetic peaks to be shifted accordingly. Particle size was found to affect the magnetic material content, where sand size (63–150 μm) bears the highest magnetic signals relative to smaller silt size (<63 μm). The magnetic anomalies coincided positively with heavy metal pollution in the studied site, which might indicate that the magnetic materials serve as an effective proxy for the metallic pollution (i.e., Fe, Ni, Pb, Cu, and Zn) originated mainly from vehicular sources.     

determination of Trace Elements in Eight Chinese Stream-Sediment Reference Samples by Energy-Dispersive X-Ray Spectrometry

Concentrations of twelve trace elements (Cr, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, La and Ce) in eight Chinese stream-sediment reference samples have been determined by energy-dispersive X-ray fluorescence spectrometry. The samples were analyzed directly and non-destructively in loose powder form. Compton scatter radiation was used as an internal standard to compensate for variations in sample matrix, particle size, packing density, and instrumental operating characteristics. The results agree well with the Chinese recommended values.     

平朔露天煤矿复垦区土壤中多环芳烃分布特征、来源解析及风险分析

原煤的开采、储存、运输及其加工利用过程是多环芳烃(PAHs)污染的主要来源。由于缺乏相关系统调查数据,其对煤矿复垦区土壤环境质量的影响尚不明确。平朔煤矿复垦土地主要作为耕地利用,了解其PAHs污染状况直接关系粮食安全和人体健康。该研究通过野外实地调查,开展了平朔煤矿复垦区表层土壤中多环芳烃(PAHs)的毒性风险分析研究。在整个平朔煤矿45 km2范围内,以500 m×500 m间距为基准,按照不同用地类型,采集了0~20 cm深度土壤样品179个,再按照1 km×1 km单元格组合后分析。使用安捷伦高分辨气相色谱低分辨质谱进行目标物的检测。加入代用标准2氟联苯(2 FBP)以进行回收率控制。研究结果表明：土壤中16种EPA PAHs的含量范围为213.60~2 513.20 ng·g-1,均值为717.09 ng·g-1。PAHs成分特征显示主要以3~4环为主(52%),5~6环次之(42%),2环所占比例最低(6%)。使用相关分析法判定,主要污染来源为原煤。毒性风险分析结果显示,平朔煤矿土壤PAHs存在一定生态风险,当土地重新作为农田加以利用时,需要加以关注。