Development of a Matrix‐Matched Sphalerite Reference Material (MUL‐ZnS‐1) for Calibration of In Situ Trace Element Measurements by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Sphalerite (ZnS) is an abundant ore mineral and an important carrier of elements such as Ge, Ga and In used in high‐technology applications. In situ measurements of trace elements in natural sphalerite samples using LA‐ICP‐MS are hampered by a lack of homogenous matrix‐matched sulfide reference materials available for calibration. The preparation of the MUL‐ZnS1 calibration material containing the trace elements V, Cr, Mn, Co, Ni, Cu, Ga, Ge, As, Se, Mo, Ag, Cd, In, Sn, Sb, Tl and Pb besides Zn, Fe and S is reported. Commercially available ZnS, FeS, CdS products were used as the major components, whereas the trace elements were added by doping with single‐element ICP‐MS standard solutions and natural mineral powders. The resulting powder mixture was pressed to pellets and sintered at 400 °C for 100 h using argon as an inert gas. To confirm the homogeneity of major and trace element distributions within the MUL‐ZnS1 calibration material, measurements were performed using EPMA, solution ICP‐MS, ICP‐OES and LA‐ICP‐MS. The results show that MUL‐ZnS‐1 is an appropriate material for calibrating trace element determination in sphalerite using LA‐ICP‐MS.     

X射线荧光光谱用人工标准物质的研制

使用高纯物质人工合成的方法,成功研制了4个人工标准物质。该系列标准物质涵盖了钛、钒、锰、铬、钴、镍、铜、锌、砷、铅、铋、铷、锶、钇、锆、铌、钼、钨、钕、钽、铪、镱、锡、钡、铯、镓、锗、镧、铈等29个元素,不同分析元素的含量范围可扩大到0.00x%~8%。该系列标准物质不仅可以补充自然标准的不足,扩展校准曲线含量范围,而且能够修正干扰系数,解决了准确计算分析元素之间的干扰和仪器校正带来的实际困难。用4个人工标准物质取代单元素人工标准的配制方法,减少标准数量,节约了资源以及标准配制的时间,避免了X射线荧光光谱分析工作者的重复劳动,提高了工作效率。研制的4个标准物质经检验均匀性和稳定性良好,量值准确可靠,已被国家质量监督检验检疫总局批准为国家一级标准物质。     

Determination of Trace Elements in Calcite Using Solution and Laser Ablation ICP-MS: Calibration to NIST SRM Glass and USGS MACS Carbonate, and Application to Real Landfill Calcite

We report new data on the trace element concentrations of Mg, Cr, Mn, Co, Ni, Cu, Zn, Sr, Cd, Ba, La, Ce, Nd, Pb and U in USGS carbonate reference materials (MACS-1 and MACS-2) and compare solution ICP-MS and LA-ICP-MS trace element determinations on landfill calcites using calibration to different reference materials (MACS-1 and MACS-2 carbonate and NIST SRM 612 glass). Very good agreement (differences below 10% relative) was found between laser ablation and solution ICP-MS data for MACS-1 with higher concentrations of trace elements (values between 100 and 150 μg g⁻¹), with the exception of Cu and Zn. Similarly good agreement was found for MACS-2 with lower trace element concentrations (units to tens of μg g⁻¹), with the exception of Cr, Co and Zn. The MACS-1 reference material for calibration of LA-ICP-MS was found to be extremely useful for in situ determination of trace elements in real-world carbonate samples (landfill calcites), especially those present in calcite in higher concentrations (Mn, Sr, Ba; < 5% RSD). Less accurate determinations were generally obtained for trace elements present at low concentrations (∼ units of μg g⁻¹). In addition, good agreement was observed between the instrument calibration to MACS and NIST SRM 612 glass for in situ measurements of trace elements in landfill calcites K-2, K-3 and K-4 (differences below 15% relative for most elements). Thus, the application of MACS carbonate reference materials is promising and points to the need for the development of new carbonate reference materials for laser ablation ICP-MS.     

微波消解-电感耦合等离子体质谱法测定植物样品中微量元素

采用过氧化氢-硝酸作溶剂,微波消解样品,外标方法校准,电感耦合等离子体质谱法同时测定植物样品中硼、镉、铜、钴、铬、钼、锂、镍、铅、镧、锗11个微量元素。确定了微波消解仪和等离子体质谱仪的最佳工作参数,研究了有机残留物和共存离子的干扰和消除方法,选择了各元素的测定同位素,以45Sc和103Rh双内标补偿基体效应,建立了样品测定方法。方法检出限(10s)在5~150 ng/g,相对标准偏差(RSD,n=12)在1.27%~5.27%。对多种国家一级生物标准物质进行分析验证,测定值与标准值相符。方法适用于植物的果实、根、茎、叶等不同类型样品中多种微量元素的测定。     

激光剥蚀电感耦合等离子体质谱元素微区分析标准物质研究进展

激光剥蚀电感耦合等离子体质谱(LA-ICP-MS)是目前地球科学分析领域的重要技术手段,元素微区分析标准物质研制是该分析技术发展的重要方向。本文对当前LA-ICP-MS元素微区分析标准物质的种类、元素分布以及应用上的优缺点和标准物质的制备方法进行了评述。现有的有证标准物质数量不多、种类不齐全,部分元素浓度较低,定值不确定度较大,应用上受到较大的局限性;研制标准也不成熟,均匀性检验方面尚未有统一的方法。本文参照岩石粉末标准物质均匀性检验方法提出了两步均匀性检验法,同时指出在标准物质种类方面,铂族元素及Au元素浓度适当、Pb-S等不同硫化物基体标准物质,以及化学成分不同的碳酸岩和磷酸岩基体标准物质是当前的迫切需求;在标准物质研制技术方面,纳米岩石粉末压片技术的研发、原位微区分析标准物质(固体)均匀性检验判别标准研究是亟待解决的问题。     

GBW10010a大米标准物质复(研)制及数据特征

随着我国对生态文明建设的重视,自然资源综合调查势在必行,对生物标准物质亦提出了新的需求。当前相关调研工作已经大面积开展,自然资源综合调查、农产品与食品安全评价都需要对生物样品元素组成进行准确测试,需要以生物标准物质作为生物成分测试量值比对和溯源的基础,因此对生物基体标准物质的需求量大幅增加。大米作为主要粮食之一,其食品安全日益受到重视,对大米中的化学成分进行准确的分析测试具有重要的现实意义,因而对大米标准物质的需求量尤为突出,但目前大米成分分析标准物质已供不应求。本文严格按照《标准物质定值的通用原则及统计学原理》（JJF 1343—2012）和《地质分析标准物质的研制》（JJF 1646—2017）等相关规范要求,开展了GBW10010a大米成分分析标准物质的复（研）制工作,包括样品采集、加工制备、均匀性检验、稳定性检验、多家实验室协作定值测试及不确定度评定等关键环节。结果表明：本次复（研）制的大米标准物质定值成分多样、量值准确可靠,符合国家一级标准物质的要求。GBW10010a共定值54项主微量元素,包括Ag、Al、As、B、Ba、Be、Bi、Ca、Cd、Ce、Co、Cr、Cs、Cu、Dy、Er、Eu、Fe、Gd、Ge、Hg、Ho、K、La、Li、Ho、Mg、Mn、Mo、N、Na、Nb、Nd、Ni、P、Pb、Pr、Rb、S、Sb、Sc、Se、Si、Sm、Sr、Tb、Th、Tl、Tm、U、V、Y、Yb、Zn,其中的39项元素给出了标准值及不确定度,包括Ag、Al、As、B、Ba、Ca、Cd、Ce、Co、Cs、Cu、Dy、Er、Fe、Hg、K、Li、Mg、Mn、Mo、N、Na、Nd、Ni、P、Pb、Pr、Rb、S、Sb、Se、Si、Sm、Sr、Tb、Tl、Y、Yb、Zn;15项元素提供参考值,包括Be、Bi、Cr、Eu、Gd、Ge、Ho、Ho、La、Nb、Sc、Th、Tm、U、V。与原有GBW10010大米标准物质相比较,GBW10010a中As、Cd、Co、Cr、Cu、Hg、Mn、Mo、Ni、Zn等重金属元素含量显著下降,其中Cd、Cu、Zn降幅较大,分别下降约39%、43%、38.7%,一定程度上反映了农田生态环境的改善。本批标准物质定值元素总数量增加了6项,新增定值元素Ag、Nb（Nb给出参考值）,并且各项元素不确定度范围整体上有所缩小,如Al、Cd、Cu、Fe、K、Mg、Mo、Na、P、Pb、Se、Zn等对生物易有影响的重要元素,表明了地质分析测试方法技术的进步及定值水平的提高。本批标准物质定值元素涵盖了具有生物效应的大部分主微量元素,适用于农业生态环境地球化学调查与评价、生物样品测试、农产品质量与食品安全评价样品测试时的分析仪器校正、分析方法评价和分析质量监控等多个领域。     

Natural Clinopyroxene Reference Materials for In Situ Microanalysis

Two clinopyroxene megacrysts, DMP-2 and DMP-3, were collected from Cenozoic alkali basalts in the Hannuoba region of China. They were characterised for major and trace element compositions for in situ microanalysis. EPMA and LA-ICP-MS analyses indicate homogeneity in the element mass fractions in both clinopyroxene samples. Bulk analyses using various techniques (XRF, ICP-OES and solution ICP-MS) also reveal good consistency in their major and trace element data. They, thus, can be used as potential reference materials for elemental in situ microanalysis. Accordingly, element mass fractions are recommended for thirty-two elements.     

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.     

Pedo-geochemical baseline content levels and soil quality reference values of trace elements in soils from the Mediterranean (Castilla La Mancha, Spain)

To evaluate trace element soil contamination, geochemical baseline contents and reference values need to be established. Pedo-geochemical baseline levels of trace elements in 72 soil samples of 24 soil profiles from the Mediterranean, Castilla La Mancha, are assessed and soil quality reference values are calculated. Reference value contents (in mg kg^?1) were: Sc 50.8; V 123.2; Cr 113.4; Co 20.8; Ni 42.6; Cu 27.0; Zn 86.5; Ga 26.7; Ge 1.3; As 16.7; Se 1.4; Br 20.1; Rb 234.7; Sr 1868.4; Y 38.3; Zr 413.1; Nb 18.7; Mo 2.0; Ag 7.8; Cd 4.4; Sn 8.7; Sb 5.7; I 25.4; Cs 14.2; Ba 1049.3; La 348.4; Ce 97.9; Nd 40.1; Sm 10.7; Yb 4.2; Hf 10.0; Ta 4.0; W 5.5; Tl 2.3; Pb 44.2; Bi 2.2; Th 21.6; U 10.3. The contents obtained for some elements are below or close to the detection limit: Co, Ge, Se, Mo, Ag, Cd, Sb, Yb, Hf, Ta, W, Tl and Bi. The element content ranges (the maximum value minus the minimum value) are: Sc 55.0, V 196.0, Cr 346.0, Co 64.4, Ni 188.7, Cu 49.5, Zn 102.3, Ga 28.7, Ge 1.5, As 26.4, Se 0.9, Br 33.0 Rb 432.7, Sr 3372.6, Y 39.8, Zr 523.2, Nb 59.7, Mo 3.9, Ag 10.1, Cd 1.8, Sn 75.2, Sb 9.9, I 68.0, Cs 17.6, Ba 1394.9, La 51.3, Ce 93.5, Nd 52.5, Sm 11.2, Yb 4.2, Hf 11.3, Ta 6.3, W 5.2, Tl 2.1, Pb 96.4, Bi 3.0, Th 24.4, U 16.4 (in mg kg^?1). The spatial distribution of the elements was affected mainly by the nature of the bedrock and by pedological processes. The upper limit of expected background variation for each trace element in the soil is documented, as is its range as a criterion for evaluating which sites may require decontamination.     

Determination of Ga,Ge, Mo,Ag, Cd,In, Sn,Sb, W,Tl and Bi in USGS Whole‐Rock Reference Materials by Standard Addition ICP‐MS

A procedure for determining a wide range of chalcophile and siderophile elements in typical crustal rocks using standard addition and ICP‐SFMS (inductively coupled plasma sector field mass spectrometry) is presented. New results for Ga, Ge, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi abundances in USGS whole‐rock reference materials AGV‐2, BHVO‐1, BIR‐1, G‐2, GSP‐1 and W‐2 are reported using this analytical procedure. Intermediate precision of means based on multiple dissolved aliquots of each USGS reference material was 10% RSD or better for Ga, Ge, In and Sn in all, and similarly good for Ag, Cd, Sb, Tl and Bi in most reference materials. Poorer intermediate precision of Mo and W measurements in several reference materials is probably due to higher analytical blanks on these elements and powder heterogeneity due to a sulfide‐related nugget effect in the specific case of Mo in GSP‐1. Results for all elements fell within the range of available published data with the exception of Ag, which yielded systematically higher concentrations than found in the literature for five of the six reference materials, likely reflecting interference from unresolved polyatomic species.     

Preparation of a Synthetic Titanite Glass Calibration Material for In Situ Microanalysis by Direct Fusion in Graphite Electrodes: A Preliminary Characterisation by EPMA and LA-ICP-MS

This paper describes a technique for the preparation of a titanite (CaTiSiO₅) glass calibration material for use in in situ microanalysis of major, minor, and trace elements in geological materials. The starting composition was a titanite matrix doped with minor and trace elements at ∼ 200 μg g^-1. The elements Sc, Y, REEs, Th and U were added in the form of nitrates in solution, and the elements V, Cr, Mn, Fe, Co, Ni, Zr, Nb, Hf and W were added as solid oxides. The synthetic titanite glass was produced by direct fusion by resistance heating in graphite electrodes at 1600-1700 °C, and quenched in air. Backscattered electron images indicate good homogeneity, with no signs of separate phases or vesicles, and analysis of the major elements Ca, Ti and Si by electron microprobe showed relative standard deviations between 0.5 and 0.7%, based on six independent measurements. Deviations from nominal concentrations for Ca, Si and Ti were measured to -1.2, -3.3 and -0.8%, respectively. The homogeneity of the trace elements in the glass was assessed by LA-ICP-MS analyses, using NIST SRM 610, 612 and 616 as external calibrators, and Ca as the internal standard element. Determinations were made both with a quadrupole mass spectrometer and a sector field instrument, and both raster and spot modes of analysis were used. For the majority of doped elements, precision was better than 10%, and relative deviations from nominal values were, with few exceptions, between 5 and 10%.     

Preparation of Synthetic Calibration Materials for Use in the Microanalysis of Oxide Minerals by Direct Fusion in High-Purity Graphite Electrodes: Preliminary Results for Quartz and Rutile

This paper describes a technique for the preparation of synthetic calibration materials for use in laser ablation inductively coupled plasma-mass spectrometry (LA-ICP-MS) and other microtechniques for mineral analysis. The method is based on direct fusion in high-purity graphite electrodes, and the requisite temperatures for melting are obtained by resistance heating using a welding rectifier as the power source. The technique has been tested on quartz (SiO₂) and rutile (TiO₂) for a relatively large range of elements, including all the rare earth elements. Different starting materials for preparation of calibration materials were studied, and it is shown that many natural materials form separate phases during fusion, resulting in unusable calibration materials for microanalysis. However, calibration materials prepared fully synthetically from oxides and/or element nitrates in solution were found to be of good homogeneity, and this preparation technique was used throughout in this work. The quality of the calibration materials for quartz and rutile was assessed by LA-ICP-MS, using Si and Ti as internal standard elements respectively. The NIST SRM 612 and 614 glass standards were used to assess the accuracy of the calibration materials for quartz. Calibration curves based on two independently prepared sets of calibration materials and the two NIST glasses are shown for a number of elements, demonstrating excellent agreement between the NIST glasses and the synthetically prepared quartz glasses. Vesicles are shown to form in the SiO₂ glasses, but this does not influence their value as calibration materials, provided that a reference element is used as an internal standard. The advantages of fusion in high-purity graphite electrodes are emphasised, particularly the very high sublimation point of graphite, its very high state of purity, the very short melting and quench time, the speed and simplicity of the method, and the low risk of introducing impurities. Extension of the method to other minerals and applications is discussed.     

电感耦合等离子体质谱法测定地质样品中锗和镉的干扰及校正

采用HF-HClO₄-HNO₃分解样品,8 mol/L HNO₃提取剂,外标法校准,电感耦合等离子体质谱法同时测定地球化学样品中锗和镉。选择¹⁰³Rh为内标,确定了最佳仪器参数,研究了Zn、Zr、Sn、Ce、Nd、Sm对Ge和Cd的干扰,试验选择质量数⁷⁴Ge和¹¹⁴Cd作为测定同位素,采用数学公式校正法校正了来自Nd和Sm的二次电离离子对Ge的干扰、Sn对Cd的同质异位素干扰。方法检出限（10s）分别为Ge 30 ng/L、Cd 15 ng/L,精密度（RSD,n=15）为Ge 1.35%、Cd 1.47%。对多种国家一级标准物质进行分析验证,结果与标准值相符。方法适用于地质样品中微量锗和镉的测定。     

粉末压片制样-波长色散X射线荧光光谱法测定斑岩型钼铜矿中主次量元素钼铜铅锌砷镍硫

采用粉末压片制样,波长色散X射线荧光光谱法测定西藏某斑岩型钼铜矿中7个主次量元素Mo、Cu、Pb、Zn、As、Ni、S。选择钼矿石、铜矿石国家标准物质及自配标准物质建立工作曲线,使用康普顿散射线作内标,同时采用经验系数法校正基体效应及粒度效应。方法经国家标准物质、自配标准参考物质验证,测定值与标准值吻合,方法分析精密度(RSD,n=12)小于2.18%,与化学法相比,样品不需进行化学前处理,操作简单、快速、准确度高、精密度好,能满足钼铜矿的实际分析需要。利用国家标准物质配制合成了7个校准标准样品,有效地解决了方法建立过程中标准样品种类和数量不足的问题。     

Natural Obsidian Glass as an External Accuracy Reference Material in Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Compared with solution ICP‐MS, LA‐ICP‐MS studies have thus far reported comparatively few external reference data for accuracy estimates of experiments. This is largely the result of a paucity of available reference materials of natural composition. Here, we report an evaluation of natural glass (obsidian) as an inexpensive and widely available external reference material. The homogeneity of over forty elements in six different obsidian samples was assessed by LA‐ICP‐MS. Accuracy was tested with two obsidian samples that were fully characterised by electron probe microanalysis and solution ICP‐MS. Laser ablation experiments were performed with a variety of ablation parameters (fluence, spot sizes, ablation repetition rates) and calibration approaches (natural vs. synthetic reference materials, and different internal standard elements) to determine the best practice for obsidian analysis. Furthermore, the samples were analysed using two different laser wavelengths (193 nm and 213 nm) to compare the effect of potential ablation‐related phenomena (e.g., fractionation). Our data indicate that ablation with fluences larger than 6 J cm^?2 and repetition rates of 5 or 10 Hz resulted in the most accurate results. Furthermore, synthetic NIST SRM 611 and 612 glasses worked better as reference materials compared with lower SiO₂ content reference materials (e.g., BHVO‐2G or GOR128‐G). The very similar SiO₂ content of the NIST SRM glasses and obsidian (i.e., matrix and compositional match) seems to be the first‐order control on the ablation behaviour and, hence, the accuracy of the data. The use of different internal standard elements for the quantification of the obsidian data showed that Si and Na yielded accurate results for most elements. Nevertheless, for the analysis of samples with high SiO₂ concentrations, it is recommended to use Si as the internal standard because it can be more precisely determined by electron probe microanalysis. At the scale of typical LA analyses, the six obsidian samples proved to be surprisingly homogenous. Analyses with a spot size of 80 μm resulted in relative standard deviations (% RSD) better than 8% for all but the most depleted elements (e.g., Sc, V, Ni, Cr, Cu, Cd) in these evolved glasses. The combined characteristics render obsidian a suitable, inexpensive and widely available, external quality‐control material in LA‐ICP‐MS analysis for many applications. Moreover, obsidian glass is suited for tuning purposes, and well‐characterised obsidian could even be used as a matrix‐matched reference material for a considerable number of elements in studies of samples with high SiO₂ contents.     

碳酸盐岩样品中镍和钪的电感耦合等离子体质谱分析与干扰校正方法

电感耦合等离子体质谱法(ICP-MS)已在碳酸盐岩微量元素测试中得到了广泛应用。然而,采用ICP-MS分析碳酸盐岩中含量较低的Ni(1.6~50.5μg/g)和Sc(0.3~6μg/g)时,信号值会受到高含量CaO(可高达56%)和MgO(可高达21%)的显著干扰,使测试值远高于真实值,从而无法获得准确的待测元素含量。为解决这一问题,本文通过实验探寻测试中的主要干扰因素,再据此确定相应的校正方法。首先,利用Ca和Mg的单标系列对碳酸盐岩ICP-MS测试中的高含量Ca、Mg对Ni、Sc的干扰分别进行研究,发现高含量Mg对Ni和Sc的测试存在基体效应的非质谱干扰;而高含量Ca则形成氧化物、氢氧化物及多原子离子对Ni和Sc形成质谱干扰,并且这一干扰程度与溶液中Ca含量呈良好的线性关系。然后,进一步选择碳酸盐岩国家一级标准物质作为校正载体以消除Mg的基体效应,同时根据样品溶液中CaO含量与Ni、Sc受干扰程度呈现的良好线性关系,提出了扣除拟合干扰的校正方法。相对于前人仅利用单标对实际样品进行干扰校正而言,本方法采用国家一级标准物质作为校正载体,克服了基体效应的干扰。并经GBW07108等五个碳酸盐岩国家一级标准物质验证,测定值与认定值相符,相对标准偏差(RSD,n=10)小于5.5%。将未知碳酸盐岩样品的校正结果与电感耦合等离子体发射光谱法(ICP-OES)及X射线荧光光谱法(XRF)测试结果进行对比,相对偏差均小于15%。该校正方法简单易行,测定结果准确可靠。     

Four Natural Chromite Reference Materials for the Determination of the First-Row Transition Elements and Gallium by LA-ICP-MS

Four natural chromite samples (LBS13-04, LBS13-06 and LBS13-13) from the Luobusa ophiolite (China) and 16SW2-6 from the Stillwater Complex (USA) were developed as reference materials for in situ element microanalysis. Approximately 8 g of chromite fragments with grain sizes of 0.5–1.5 mm from each chromite sample were separated under a binocular microscope and analysed by EPMA, XRF, LA-ICP-MS and solution nebulisation ICP-MS techniques for major and trace elements at six laboratories. The results show that the four chromite samples are homogeneous with respect to MgO, Al₂O₃, Cr₂O₃, FeO, Sc, Ti, V, Mn, Co, Ni, Zn and Ga. These samples are thus suitable to be used as reference materials for in situ microanalysis.     

Trace elements in high-S subbituminous coals from the teruel Mining District, northeast Spain

The elemental composition of high temperature ash (750°C) and forms of S were studied in 25 coal seams from the Escucha Formation (Middle Albian) in the Teruel Mining District, northeast Spain. The principal analytical method was ICP-MS, but ICP-ES was also used in the determination of some trace elements. The analytical data show wide ranges of trace element cotnents among the coal seams studied, even in the vertical profile of a single coal seam. These wide ranges of the trace element concentrations are attributed to both syngenetic and epigenetic processes.When a comparison was made between the average trace element contents of the Teruel Mining District coals, and those of the average content in worldwide coals, the Teruel coals show slightly higher concentrations of Be and U, and lower concentrations of Ba, Cd, Mn, Pb, Sr and Zr. Further, three main groups of trace elements were differentiated on the basis of the inorganic/organic association: (1) trace elements with inorganic affinity; Ba, Ce, Co, Cr, La, Mn, Ni, Rb and Zr. Between these, Ba, Ce, Cr and Rb show a well defined correlation with the clay mineral content, and Co and Ni with pyritic-S content; (2) trace elements with an intermediate (mixed) affinity; As, Cd, Cu, Dy, Er, Eu, Gd, Ge, Ho, Lu, Mo, Nd, Pb, Pr, Sb, Sm, Sr, Tb, Th, Tm, U, Yb and Zn. In this group, As, Cd, Cu, Ge, Mo, Th, U and Zn show a weak trend associated with the mineral matter and Sr with the organic matter; and (3) Be shows an organic affinity. The high mineral matter content (21.3% HTA) of the Teruel coals may account for the great number of elements with inorganic affinity. This classification represents a general trend, but the results show that the affinities of some trace elements (e.g. As, Sb and Zn) may vary from one coal seam to another in the Teruel Mining District.     

BAM‐S005 Type A and B: New Silicate Reference Glasses for Microanalysis

To test whether the silicate reference glasses BAM‐S005‐A and BAM‐S005‐B from BAM (The Federal Institute for Materials Research and Testing, Germany) are suitable materials for microanalysis, we investigated the homogeneity of these reference glasses using the microanalytical techniques EPMA, LA‐ICP‐MS and SIMS. Our study indicated that all major and most trace elements are homogeneously distributed at micrometre sampling scale in both types of glass. However, some trace elements (e.g., Cs, Cl, Cr, Mo and Ni) seem to be inhomogeneously distributed. We also determined the composition of BAM‐S005‐A and BAM‐S005‐B. The EPMA data of major elements confirmed the information values specified by the certificate. With the exception of Sr, Ba, Ce and Pb, our trace element data by LA‐ICP‐MS were also in agreement with the certified values within the stated uncertainty limits. The reasons for the discrepancy in these four elements are still unclear. In addition, we report new data for twenty‐two further trace elements, for which the concentrations were not certified. Based on our investigation, we suggest that both of these materials are suitable for many microanalytical applications.     

电感耦合等离子体发射光谱法测定工业硅中微量元素

采用电感耦合等离子体发射光谱法同时测定工业硅中可能存在的铝、铁、钙、镁、钾、钠、磷、钡、铍、镉、铈、钴、铬、铜、锂、锰、钼、镍、铅、钛、钒、钨、锌、砷、锶、铼、锑、硼28个微量元素,并以差减法计算基体硅的含量,实现了对试样基体及杂质元素含量的同时测定。方法对28个微量元素的回收率为94.0%～103.4%,精密度(RSD,n=10)低于3.0%。方法经国家实物标准物质验证,测定值与标准值基本相符。