New Series of Rock and Sediment Geochemical Reference Materials

Certified or reference values for sixty six to sixty seven elements and element oxides are given for geochemical reference materials recently prepared by the Institute of Geophysical and Geochemical Exploration (IGGE), including limestone (GSR-13), granitic gneiss (GSR-14), amphibolite (GSR-15), lake sediment (GSS-9) and stream sediments (GSD-1a, GSD-13, GSD-14). These samples supplement the GSR 1-6, GSD1-8 and GSD 9-12 certified reference materials already prepared and characterized by the IGGE.     

同位素稀释－感耦等离子体质谱法测定钐铕钆的研究

文章研究了地质样品中稀土元素Ｓｍ、Ｅｕ、Ｇｄ的同位素稀释－感耦等离子体质谱的测定方法。验证了同位素稀释法不受基体的影响，实验了利用Ｐ５０７树脂分离干扰元素Ｂａ、Ｌａ和Ｐｒ的条件。Ｓｍ、Ｅｕ、Ｇｄ的检出限（ｎｇ／ｇ）分别为１５、２．７１、１２；对标样ＧＳＤ－１０平行测定１０次，各元素的相对标准偏差均＜２．５％；标样测定结果与推荐值相符。     

Chemical Characterisation of the USGS Reference Glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G Using EPMA, ID-TIMS, ID-ICP-MS and LA-ICP-MS

The USGS reference glasses GSA-1G, GSC-1G, GSD-1G, GSE-1G, BCR-2G, BHVO-2G and BIR-1G were investigated by different analytical techniques. All these materials have a geological (basaltic) matrix and are therefore useful in igneous geochemistry as matrix-matched reference materials for microanalytical techniques. The new GS glasses have trace elements in groups at concentration levels of about < 0.01, 5, 50 and 500 μg g^-1. Their major element compositions have been determined by EPMA, and trace elements have been analysed by LA-ICP-MS and two isotope dilution techniques using TIMS and ICP-MS. EPMA and LA-ICP-MS analyses indicated that the USGS reference glasses are homogeneous at the μm to mm scale with respect to major (variations < 1-2%) and most trace elements (variations 1-4%). Trace element data obtained from the different analytical techniques agreed within an uncertainty of 1-5%, indicating that between method results are comparable. Therefore, the preliminary working values for the four USGS GS glasses calculated from these data have a low level of uncertainty.     

Determination of Trace Elements (Ag, B, Ge, Mo, Sn, W, Tl) in Reference Samples of Soils and Bottom Sediments by Atomic Emission Spectrometry: A Traceability and Fitness-for-Purpose Study

Reference samples of soils from the Institute of Applied Physics, Irkutsk (RIAP), the Institute of Geochemistry, Irkutsk (IGI) and the United States Geological Survey, Reston (USGS) were analysed with the aim of determining Ag, B, Ge, Mo, Sn, Tl and W abundances by an atomic emission method with air-stabilised D.C. arc excitation. Two series of reference samples of soils and bottom sediments, GSS-1-8 and GSD-1-12 (IGGE), were used to ensure the traceability link for the analytical results. Traceability was also demonstrated through the comparison of measured results by AES and ICP-MS methods. It is shown that the reference samples GSS-1-8 and GSD-1-12 satisfied the "fitness-for-purpose" criterion (uncertainty U of the certified value should be one-third to one-tenth the magnitude of routine laboratory data uncertainty S (S/U > 3-10)) and can be applied for calibrating AES techniques.     

以多硫、多碘化合物为缓冲剂发射光谱法测定化探样品中As、Sb、Bi、Cd、Tl、In 元素

本方法建立了以多硫化合物、多碘化合物为缓冲剂(液体缓冲剂),上电极为光谱纯石墨电极、下电极为光谱纯石墨加罩电极的方式,采用控制试样法绘制工作曲线,电弧发射光谱法同时测定区域地球化学样品中As、Sb、Bi、Cd、Tl、In等6元素的测定方法。方法检出限为As1.0μg/g,Sb0.2μg/g,Bi0.1μg/g,Cd0.05μg/g,Tl0.1μg/g,In0.01μg/g;精密度(RSD,n=12)为As8.36%,Sb7.17%,Bi7.60%,Cd7.39%,Tl7.13%,In6.76%。方法用于测定国家一级标准物质GSD-1～GSD-12中As、Sb、Bi、Cd、Tl、In,测定值与标准值或参考值吻合。通过对1:50000区域地球化学调查样品中As、Sb、Bi、Cd、Tl、In实际分析,结果成图效果良好,具有简便快捷、成本低、检出限低、精度高等特点。     

ID-ICP-MS测定高纯石英中微量铀的方法研究

采用一种脉冲增压微色谱柱，阴离子交换树脂，分离富集高纯石英中的微量铀，分离效果好，本底低。样品处理用低温密封闷罐酸溶。同位素稀释电感耦合等离子体质谱(ID-ICP—MS)测定高纯石英中的微量铀，方法检出限低：0．1ng/G(3σ，n=10)，分析速度快，是理想的测定微量铀的方法。     

热水解-离子色谱法连续测定地质物料中的氟、氯和硫

研究报导了一种快速、高效和无干扰地测定地质物料中氟、氯和硫的热水解离子色谱方法。自行设计和组装了热水解装置。实验研究和选择了热水解条件、离子色谱测定的最佳工作状态,从而获得了准确可靠的结果。用本法对10个地球化学标准参考样(GSR-3,6;GSS-1,3,6,8;GSD-11,12)进行分析测定,其结果与这些标样的最佳估计值和推荐值非常一致。该方法的检出限分别为:氟6.6ppm;氯30.8ppm;硫酸根36.8ppm。方法的精密度(RSD,%)对氟含量为577ppm,氯含量为70ppm和硫酸根含量为420ppm的样品来说,分别为1.8%,12.3%和3.8%。     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

勘查地球化学找矿中重要指示元素的野外快速分析法(二)银的分析方法

发展了一种可在野外快速测定0.010-50μg/g银量的新方法.此法由两个各自独立而又配套的部分组成.一是直接测定0.25-50μg/g银量的Ag-TMK-SDS三元络合物光导比色测定法;二是测定0.010-0.25μg/g银量的巯基棉分离富集微珠析出比色法.可在同一份试液中依次完成.前者检出限为0.006μg/ml(K=3);测定铜、铅和锌矿石标样GSO-Cu-1(含银3.87μg/g)、GSO-Ph-1(含银14.7μg/g)和GSO-Zn-1(含银13.5μg/g)中的银,RDS(n=11)分别为1.6%、3.7%和3.4%;后法可检出5ng/g银;测定地球化学标样GSD-3(含银0.59μg/g)中的银,RSD(n=11)为6.t%.方法较为简便、快速、准确和灵敏.用光导比色计测定,结果准确度、精度均有较大改善,且与室内原子吸收法相当.故所定方法具有广阔的应用前景.     

Measuring Hg Isotopes in Bio-Geo-Environmental Reference Materials

With the emergence of new analytical techniques and the expansion of scientific fields explored by using mercury isotopes, the community needs reference materials (RM) to validate and assure the accuracy of the results. The present work investigates (1) the characterisation of secondary RM in order to validate analytical systems, (2) the effects of two complex matrices on isotopic determination using stannous chloride cold vapour generation coupled to MC-ICP-MS (CV-MC-ICP-MS), (3) the effects of multiple digestion techniques for total Hg extraction and (4) the characterisation of nine geo-bio-environmental RM. Two secondary mono-elemental RMs analysed using two different analytical setups yielded isotopic compositions on δ²⁰²Hg of −3.54 ± 0.27‰ (CRPG-F65A, 2SD, n = 38) and +2.59 ± 0.19‰ (CRPG-RL24H, 2SD, n = 30) relative to the CRM NIST SRM 3133. These two RMs cover the whole range of Hg isotopic fractionation in natural samples and are made available to the scientific community. Complex fly ash and hydroxysulfate green rust matrices were synthesised, spiked with NIST SRM 3133, then digested and finally analysed versus the mono-elemental NIST SRM 3133 to show potential effect of these complex matrices during CV-MC-ICP-MS. Three digestions techniques, including traditional acid digestion, microwave digestion and high pressure-high temperature digestion, were applied to the lichen RM BCR-482 in order to compare advantages and drawbacks of these methods. Finally, the isotopic compositions of nine RMs including soils (NIST SRM 2711; GXR-2; GSS-4), sediment (GSD-10), jasperoid (GXR-1), ore deposit (GXR-3), fly ashes (BCR-176; BCR-176R) and lichen (BCR-482) are reported. These selected materials have δ²⁰²Hg values ranging from −1.75‰ to +0.11‰. Some RMs also presented mass-independent fractionation with Δ¹⁹⁹Hg and Δ²⁰¹Hg of up to −0.6‰.     

Trace Element Analysis of Fused Whole-Rock Glasses by Laser Ablation-ICP-MS and PIXE

The concentrations of fifty trace elements, including relatively volatile elements and transition metal elements, in fused glasses of Geological Survey of Japan rock reference materials GSJ JR-2, JA-1, JA-2, JB-1a, JB-3, JGb-1 and JF-1 were determined by particle (proton) induced X-ray emission (PIXE) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). The fused glasses were prepared by rapid fusion and subsequent quenching in welded platinum capsules and were found to be homogeneous for major elements and for trace elements with concentrations of more than 1 μg g^-1 within the observed precision (± 10% mean) on a 70 μm sampling scale. The values obtained by PIXE and LA-ICP-MS for the transition elements (Cr, Mn, Fe, Ni and Cu), the relatively volatile elements (Zn, Ga, Rb and Pb) and the refractory elements (Y, Zr, Nb and Th) with concentrations greater than a few μg g^-1 showed good agreement (within 10 % relative difference). The values for almost all the elements detected at concentrations higher than 1 μg g^-1 as determined by LA-ICP-MS also agreed well with the reference values (mean relative difference < ± 10%), except for B and Cu. The good agreement confirmed the appropriateness of the NIST SRM 600 series glass calibration reference material for LA-ICP-MS analysis of glasses with variable major-element compositions for almost all elements. The concentrations of Cu in all the samples were lower than the reference values, which was attributed to adsorption of the transition metals onto the platinum capsule during preparation.     

Influence of trace element fluxes from submarine groundwater discharge (SGD) on their inventories in coastal waters off volcanic island,Jeju, Korea

The concentrations of trace elements in groundwater and seawater were measured in a coastal embayment (Bangdu Bay) of a volcanic island (Jeju) off the southernmost coast of Korea in August and December of 2009. The concentrations of trace elements (Al, Mn, Fe, Co, Ni, and Cu) in the groundwater in summer were approximately 20-fold higher than those in winter, with good correlation to each other. Overall, the concentrations of most of the trace elements in the groundwater were 3- to 70-fold higher than those in the seawater of this Bay. Simple budget calculations showed that large fluxes of submarine groundwater discharge (SGD)-driven trace elements were responsible for the unusually enhanced concentrations of trace elements (particularly for Al, Fe and Co) in the summer seawater. The results imply that the temporal changes in SGD-driven trace element fluxes are large and may contribute considerably to the budget of trace elements in the coastal ocean, particularly off a highly permeable volcanic island.     

电感耦合等离子体发射光谱法测定稀土铌钽矿中稀土元素和钍量

用等离子体发射光谱法测定了稀土铌钽矿中的稀土元素和钍量。考察了溶样方式和称样量,选择分析线波长,确定了仪器工作条件。对共存元素的干扰量进行试验,稀土元素之间的干扰可忽略不计。精密度试验表明,各稀土元素及钍的相对标准偏差(RSD,n=11)小于10%(除Eu2O3外)。方法用于实际样品的测定,结果与等离子体质谱法及外检结果吻合。     

Soil and plant composition in the Noun river catchment basin,Western Cameroon: a contribution to the development of a biogeochemical baseline

Soils and selected edible plants of the Noun river catchment basin of western Cameroon were sampled to investigate the distribution of trace elements, based on the preliminary idea of unusual anomalies. Analytical techniques for trace elements included ICP-AES, GF-AAS, and ICP-MS. Further soil analyses comprised the mineralogy and contents of the biogenic elements carbon, nitrogen and sulphur (CNS). The trace element concentrations in the soils reflect those of the lithogeochemical background of the pluto-volcanic rocks of the region. This is consistent with the results from the mineralogical analyses and physicochemical parameters such as pH, taken in the field, which also do not suggest any geochemical anomaly. Most trace elements analyzed in the plants showed concentrations that reflect those of the soils (Al, Fe, Ti, and Rb). However, some trace elements were enriched in the plants as compared to the soils, such as Zn, Cu, Cd, Mo (excluding yam), Ni (peanut), Ba (peanut), Sr (peanut, bean), and B. Trace elements such as As, Cr, V, and Se were not bioavailable for all the analyzed plants. Besides, trace elements such as Cu, Zn, Mo, Fe, Al, Ni, B, Ti, Rb, Cs, and Ba were in the range of phytotoxicity and reached or exceeded human food tolerance level (Cu). The plants with seeds showed a higher absorption of trace elements compared to plants with tubercles.     

福建龙海杨梅产地元素地球化学特征

福建省是中国杨梅重要产地,其中龙海市浮宫杨梅因其独特品质而名扬海外,是当地的名特优农产品。以龙海杨梅产地为研究区,系统采集了35套岩石-土壤-杨梅果实样品,测定了主量组分、植物营养有益元素、有害元素以及土壤部分营养元素有效态含量。研究表明：受地质背景影响,浮宫镇及其周边杨梅产地土壤中植物营养有益元素的有效度及其有效量普遍高于东泗镇,而有害元素含量较低,为浮宫杨梅的优质高产、富硒杨梅产出提供了地质地球化学条件;土壤中植物营养元素P、Mn、Cu、Zn、S有效态含量与其全量显著正相关;研究区岩石、土壤Se含量均远高于全国平均水平,采集的35件杨梅果实样品富硒率高达74.3%;植物营养有益元素的富集系数明显高于有害元素,显示出杨梅对营养有益元素的选择性吸收以及对有害元素的阻遏作用。     

氢化物发生-原子荧光光谱法同时测定滑石中砷和汞

样品经盐酸、硝酸、氢氟酸、高氯酸溶解,盐酸提取,提取液直接上机测定。综合采用离峰背景校正法及干扰系数校正法消除各种干扰对测定的影响,电感耦合等离子体发射光谱法测定煤及煤灰样品中21个主次量及微量元素。方法检出限为0.03~5.6μg/g,精密度(RSD,n=11)为0.5%~3.6%。方法用国家一级标准物质验证,各元素的测定值与标准值吻合,满足煤分析要求。     

Concentrations of Trace Elements in Carbonate Reference Materials Coral JCp-1 and Giant Clam JCt-1 by Inductively Coupled Plasma-Mass Spectrometry

Trace elements in the Geological Survey of Japan carbonate reference materials Coral JCp-1 and Giant Clam JCt-1 were determined by inductively coupled plasma-mass spectrometry after digestion with 2% v/v HNO₃. A standard addition method was adopted in this determination in order to neutralise the Ca matrix effect. In addition, Sc, Y, In and Bi were used as internal standards to control the matrix effect and correct instrumental drift. Of the eighteen elements measured in JCp-1, precisions for fourteen elements, including Cu, Cd and Ba, were better than 10% RSD and concentrations ranged from 0.002 μg g^-1 (Cs) to 8.02 μg g^-1 (Ba). The concentrations of measured trace elements in JCt-1, except for Cu, were lower than those in JCp-1. Precisions for all elements with concentrations higher than 0.04 μg g^-1 in JCt-1 were also better than 10% RSD and concentrations were found to be between 0.001 μg g^-1 (Cs) and 4.84 μg g^-1 (Ba). The concentrations of more than fifteen trace elements in the aragonite reference materials are reported here for the first time. Both reference materials are suitable for use in geochemical studies of environmental reconstruction based upon biogenic carbonate materials.     

锗矿石和铟矿石化学成分分析标准物质研制

目前国内外没有以稀散元素锗、铟为特征元素的矿石标准物质,为了满足我国地质找矿的需求,本文采集广东省韶关凡口铅锌矿作为锗矿石候选物,广西南丹铜坑铅锌矿作为铟矿石候选物,依据国家一级标准物质技术规范,由10家实验室采用化学分析方法和现代仪器分析方法协作定值,研制了1种锗矿石标准物质(GBW07831)和1种铟矿石标准物质(GBW07833)。锗矿石标准物质定值组分为45项,铟矿石标准物质定值组分为47项,包括特征元素、共存元素、稀土元素(15项)、造岩元素和痕量元素,其中锗矿石中锗含量为21.6×10-6,铟矿石中铟含量为39.7×10-6。研制的2种标准物质丰富了我国矿石标准物质的种类,可用于锗、铟矿石化学成分分析测试的量值标准和日常质量监控。     

Distribution of trace elements in the coastal sea sediments of Maslinica Bay, Croatia

Spatial distributions of trace elements in the coastal sea sediments and water of Maslinica Bay (Southern Adriatic), Croatia and possible changes in marine flora and foraminifera communities due to pollution were investigated. Macro, micro and trace elements’ distributions in five granulometric fractions were determined for each sediment sample. Bulk sediment samples were also subjected to leaching tests. Elemental concentrations in sediments, sediment extracts and seawater were measured by source excited energy dispersive X-ray fluorescence (EDXRF). Concentrations of the elements Cr, Cu, Zn, and Pb in bulk sediment samples taken in the Maslinica Bay were from 2.1 to over six times enriched when compared with the background level determined for coarse grained carbonate sediments. A low degree of trace elements leaching determined for bulk sediments pointed to strong bonding of trace elements to sediment mineral phases. The analyses of marine flora pointed to higher eutrophication, which disturbs the balance between communities and natural habitats.     

电感耦合等离子体发射光谱法同时测定土壤样品中54种组分

用高氯酸-氢氟酸-硝酸消解样品,样品中的难溶组分被有效浸取,电感耦合等离子体发射光谱法测定土壤样品中稀土元素及稀散元素等54种组分。通过筛选分析谱线、合理设置背景扣除位置及干扰元素校正系数,改善了光谱干扰。方法经国家一级土壤标准物质分析验证,结果与标准值吻合,相对标准偏差低于6.0%。方法可测组分多,试剂用量少,简便快速,劳动强度低,能够满足基体组成复杂的区域土壤地球化学调查样品分析的要求,也为其他地球化学样品中相关组分的分析提供借鉴。