Determination of Elemental Concentrations in Nine CMEA Rock and Ore Standards,in NBS 98 Plastic Clay and in Fired Clay Gent (FCG) by Instrumental Neutron Activation Analysis*

Data for as many as 31 elements were determined by instrumental thermal neutron activation analysis for nine European Council for Mutual Economic Assistance (CMEA) rock and ore standards. The National Bureau of Standards plastic clay 98 and the University of Gent fired clay FCG were also analyzed. Synthetic, multielement standards were used and USGS rock standards provided reference samples. Correction factors for uranium fission products on cerium and molybdenum, and also for less commonly encountered spectral interferences, such as those due to the 213 ppm tantalum in granitoid 2B, were evaluated.     

高精度测量岩石样品Ce同位素组成的TIMS方法

介绍了对岩石样品的Ce同位素组成进行高精度测量的TIMS方法.采用α-羟基异丁酸(α-HIBA) 离子交换法分离和纯化岩石样品中的La、Ce元素, Ce同位素组成和La、Ce含量测定在Triton热电离质谱仪上完成.质谱标样JMC304的138Ce/142Ce比值统计值为0.0225762±0.0000015, 与大部分文献值一致.应用该方法对USGS玄武岩标样BCR-2和峨眉山玄武岩EQB的138Ce/142Ce比值和La、Ce含量进行了分析, 其结果分别为: 0.0225572±0.0000010、25.2±0.3μg/g、55.8±0.9μg/g和0.0225755±0.0000003、54.2±0.4μg/g、117.4±1.3μg/g.BCR-2的La、Ce含量测定结果与其证书值在误差范围内一致, 其分析精度为0.001%~0.005%.所有样品的140Ce/142Ce比值测定结果统计值为7.9439±0.0002, 介于文献最低值7.941与最高值7.947之间, 可能代表了该比值的最佳估计值.      

Isotope Dilution MC-ICP-MS Rare Earth Element Analysis of Geochemical Reference Materials NIST SRM 610, NIST SRM 612, NIST SRM 614, BHVO-2G, BHVO-2, BCR-2G, JB-2, WS-E, W-2, AGV-1 and AGV-2

We present data for the concentrations of eleven rare earth elements (La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Lu) in eleven international geochemical reference materials obtained by isotope dilution multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). We have analysed both rock powders and synthetic silicate glasses, and the latter provide precise data to support the use of these as reference materials for in situ trace element determination techniques. Our data also provide precise measurements of the abundance of mono-isotopic Pr in both glasses and powders, which allows more accurate constraints on the anomalous redox-related behaviour of Ce during geochemical processes. All materials were analysed in replicate providing data that typically reproduce to better than one percent. Sm/Nd ratios in all these materials also reproduce to better than 0.2% and are accurate to < 0.2% and can thus be used as calibrants for Sm-Nd geochronology. Our analyses agree well with existing data on these reference materials. In particular, for NIST SRM 610, USGS BHVO-2, AGV-1 and AGV-2, our measured REE abundances are typically within < 2% (and mostly 1%) of REE concentrations previously determined by isotope dilution analysis and thermal ionisation mass spectrometry, consistent with the higher degree of precision and accuracy obtained from isotope dilution techniques. Close agreement of results between basaltic glass reference materials USGS BHVO-2G and BCR-2G and the BHVO-2 and BCR-2 powders from which they were created suggests that little fractionation, concentration or dilution of REE contents occurred during glass manufacture.     

Precise determination of uranium in rocks and minerals by neutron activation analysis using 133I fission product

A radiochemical neutron activation technique for uranium determination in rock and mineral samples is presented. The method is based on an alkaline fusion, a selective oxidation of iodine by a sodium-nitrite solution, followed by an iodine distillation technique for the isolation of the ¹³³I produced in fission. The outlined scheme is rapid, sensitive and reliable. Determination of uranium in U.S. Geological Survey standard rocks (G-1, W-1, G-2, BCR-1, AGV-1, GSP-1), C.R.P.G. Nancy geochemical standards (GA, GH, BR, Mica-Fe, Mica-Mg), C.A.A.S. reference syenite rocks (SY-1, SY-2, SY-3) and other analysed rock samples are reported. These results are compared with those obtained by other methods.     

Determination of Niobium in 15 USGS Standard Rocks by NEutron Activation Analysis

The niobium concentrations in 15 U.S.G.S. standard rocks were measured by neutron activation analysis. The niobium was separated from the rock matrix (in the presence of ⁹⁵Nb tracer, which was used to measure the fraction recovered) before irradiation to improve the sensitivity. Results of this work are compared with those obtained by other techniques. Some results obtained by multielement X-ray fluorescence procedures agree well with the present data, but a systematic disagreement exists between these and the spectrophotometric data.     

TRACE ELEMENT DETERMINATIONS FOR USGS BASALT BHVO-1 AND NIST STANDARD REFERENCE MATERIALS 278, 688 AND 694 BY INDUCTIVELY COUPLED PLASMA-MASS SPECTROMETRY

Results are presented for 26 to 30 trace elements determined in four rock reference materials of geochemical interest: USGS Basalt BHVO-1, Rhyolite Obsidian NIST 278, Basalt NIST688, and Phosphate Rock NIST694. Determinations were made by inductively coupled plasma mass spectrometry (ICP-MS). Good agreement was obtained among solution standard comparison and standard addition analytical techniques, and among samples prepared with different dissolution methods. Generally good agreement was obtained between determined trace element values and values reported in the literature.     

Suppression of Matrix Effects in ICP-MS by High Power Operation of ICP: Application to Precise Determination of Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U at ng g-1 Levels in Milligram Silicate Samples

We found that the suppression of signals for ⁸⁸Sr, ¹⁴⁰Ce and ²³⁸U in rock solution caused by rock matrix in ICP-MS (matrix effects) was reduced at high power operation (1.7 kW) of the ICP. To make the signal suppression by the matrix negligible, minimum dilution factors (DF) of the rock solution for Sr, Ce and U were 600, 400 and 113 at 1.1, 1.4 and 1.7 kW, respectively. Based on these findings, a rapid and precise determination method for Rb, Sr, Y, Cs, Ba, REE, Pb, Th and U using FI (flow injection)-ICP-MS was developed. The amount of the sample solution required for FI-ICP-MS was 0.2 ml, so that 1.8 mg sample was sufficient for analysis with a detection limit of several ng g^-1. Using this method, we determined the trace element concentrations in the USGS rock reference materials, DTS-1, PCC-1, BCR-1 and AGV-1, and the GSJ rock reference materials, JP-1, JB-1, -2, -3, JA-1, -2 and -3. The reproducibilities (RSD %) in replicate analyses (n=5) of BCR-1, AGV-1, JB-1, -2, -3, JA-1, -2, and -3 were < 6 %, and typically 2.5%. The difference between the average concentrations of this study for BCR-1 and those of the reference values were < 2%. Therefore, it was concluded that the method can give reliable data for trace elements in silicate rocks.     

Determination of Trace Elements in Selected Geological Reference Materials by Instrumental Neutron Activation Analysis

Data are presented for eight rare earth elements and ten other elements in 22 reference samples recently distributed by the University of Liege (Belgian sedimentary rock reference samples), the Geological and Mining Service (Suriname), the Geological Survey of Japan and the Venezuelan laterite. Determinations were made using a well characterised, high precision, neutron activation analysis technique.     

XRF AND INAA DETERMINATIONS OF MAJOR AND TRACE ELEMENTS IN GEOLOGICAL SURVEY OF JAPAN IGNEOUS AND SEDIMENTARY ROCK STANDARDS

Major and trace element analyses have been obtained by wavelength dispersive X-ray fluorescence for the Geological Survey of Japan Igneous rock series and selected samples from the Sedimentary rock series reference samples. Additional trace element data for the Igneous rock series were obtained by instrumental neutron activation analysis. Samples were analyzed multiple times for 10 major elements (with loss-on-ignition) and the following trace elements; As, Ba, Ce, Co, Cr, Cs, Cu, Eu, Ga, Hf, La, Lu, Nb, Nd, Ni, Pb, Rb, Sb, Sc, Sm, Sr, Ta, Tb, Th, U, V, W, Y, Yb, Zn and Zr.     

Instrumental Neutron Activation Determination of 23 Elements in 8 New USGS Standard Rocks

The trace elements Ce, Co, Cr, Cs, Dy, Eu, Gd, Hf, La, Nd, Ni, Rb, Sb, Sc, Sm, Ta, Tb, Th, Tm, U, V, Yb and Zr have been determined by instrumental neutron activation analysis and U by delayed neutron counting in the USGS standard rock samples STM-1, RGM-1, QLO-1, SDC-1, BHVO-1, SCo-1, SGR-1 and MAG-1. The results are compared with those found in the literature.     

La-Ce法岩石标准物质和Ce同位素标准溶液研制

报道了La-Ce法岩石标准物质的研制结果。标准物质选自峨眉山玄武岩中的新鲜微晶玄武岩（编号EQB）,具有间隐结构,矿物组成相对均一。岩石经粉碎和均一化加工,成为粉末后分装成1000小瓶。经均匀性和稳定性检验合格后,对该岩石标准物质的Ce同位素比值和La、Ce元素含量进行了测定和定值统计,其结果分别表示为：138Ce／142Ce=0．0225755±0．0000003,Ce=（117．4±1．3）μg／g,La=（55．8±0．9）μg／g。对二氧化铈化学试剂进行了溶液制备,以用于Ce同位素分析仪器标准物质。标准溶液编号为CBRICeO2,其138Ce／142Ce比值的测定统计值为0．0225748±0．0000006。为检验所制标准物质分析数据的准确度,对国际标样进行了比对测量,其中JMC304标准溶液的138Ce／142Ce比值测定结果为0．0225762±0．0000015,USGS玄武岩标样BCR-2的La和Ce元素含量测定结果分别为（25．2±0．6）μg／g（2σ）和（54．2±0．8）μg／g（2σ）,所获数值与文献报道值或证书值在误差范围内相符。     

LA, CE, SM, EU, TB, YB AND LU CONTENT OF FIFTEEN FRENCH GEOCHEMICAL REFERENCE SAMPLES DETERMINED BY NEUTRON ACTIVATION ANALYSIS

La, Ce, Sm, Eu, Tb, Yb and Lu content of fifteen silicate reference standards were determined using neutron activation analysis. For samples poor in rare-earth elements, radiochemical neutron activation analysis was applied. In most cases, the comparison of these results with those published is satisfactory.     

Determination of Elemental Composition of NBS 278 and NBS 688 Via Neutron Activation and X-Ray Fluorescence

Data on NBS Standard Reference Materials 278 (Obsidian) and 688 (Basalt) are presented. Ten major elements, 24 trace elements, iron oxides, and water content were determined using X-ray fluorescence, instrumental thermal neutron activation analysis, delayed neutron assay, spectrophotometry, and coulometry. Good agreement between X-ray fluorescence and neutron activation, and with NBS certified values or recent literature consensus values was obtained.     

岩石样品Hf化学分离及MC-ICP-MS同位素分析：离子交换色谱法的应用

介绍的离子交换色谱分离岩石样品Lu-Hf的方法，是对现有方法的改进。整个流程以使用HCl为主，配合少量HF，即可达到有效地分离Hf和Lu的目的，Lu和Hf的回收率在90％以上。经MC—ICP。MS分析，每个国际岩石标样的两个平行样获得了在误差范围内一致^176 Hf／^177 Hf比值，其中BHVO-1、BHVO-2和BCR-2的^176 Hf／^177 Hf比值与国内外文献报道的结果在误差范围内一致。     

Gold in BHVO-1, BIR-1, DNC-1 and BCR-1 by Fire-Assay Preconcentration Neutron Activation Analysis: Sample Size vs. Accuracy

Four mafic USGS rock standards (BHVO-1, BIR-1, DNC-1, BCR-1) were analyzed at three sample sizes (1, 5, and 10 g) for gold by neutron activation analysis subsequent to fire-assay concentration. The results indicate that large samples, in the order of 10 g, are required to produce consistent results, although analyses of variance indicate that sample sizes of 5 g may be used effectively. The analysis of 1 g samples resulted in a large range of values and high standard deviations. BCR-1 was found to be the most homogeneous of the four standards for gold, followed in decreasing order by BIR-1, DNC-1, and BHVO-1. Data for Ir in BIR-1 and DNC-1 are also presented.     

新一代高精度高灵敏度的表面热电离质谱仪(Triton TI)的Nd同位素测定

利用在南京大学成矿作用研究国家重点实验室建立的新一代高精度高灵敏度的表面热电离质谱仪 (TritonTI) ,可以实现比以往更高精度的Nd同位素测定。 3个国际溶液标样的反复测定结果NdLaJolla :14 3 Nd/ 14 4 Nd为 0 .5 1184 2± 4 ;NdJN di 1:14 3 Nd/ 14 4 Nd为 0 .5 12 10 4± 6 ;NdJMC :14 3 Nd/ 14 4 Nd为 0 .5 115 87± 10。 1个国际岩石标样的测试结果BCR 2 :14 3 Nd/ 14 4 Nd为 0 5 12 6 2 4± 3。上述测试结果与国际上很多实验室的测试结果一致 ,但测试精度优于以往。综合分析表明 ,利用这一最新型号的表面热电离质谱仪 (TritonTI) ,可以实现高精度的Nd同位素组成测试 ,测试精度一般优于 5× 10 -6。     

Rare Earth and Other Trace Element Content of NRCC HISS-1 Sandy Marine Sediment Reference Material

The National Research Council (NRC), Ottawa, Canada sandy marine sediment reference material HISS-1 was characterised for thirty-seven trace elements by neutron activation optimised irradiation, cooling and counting protocols using the low power Miniature Neutron Source Reactor (MNSR) as a neutron source. This INAA methodology quantified twenty additional elements including ten rare earth (Ce, Dy, Eu, Ho, La, Lu, Nd, Sm, Tb and Yb) and ten other elements (Ba, Br, Cs, Ga, Hf, Rb, Sc, Ta, Th and Zr) missing in the final NRCC certification. A large number of values produced by different irradiation schemes together with the use of certified reference materials in the quantification step that showed good precision, provided confidence in the results. The reliability of the REE data was checked by plotting chondrite-normalised graphs.     

Certificate of Analysis of the Reference Material BRP-1 (Basalt Ribeirão Preto)

Reference materials (RM) are essential to achieve traceability of measurements. Specific uses of RM in analytical laboratories are the validation of methods, the calibration of instruments, the quality control and the demonstration of proficiency. This paper describes the certification of a new geochemical reference material, named BRP-1 (Basalt Ribeirão Preto), and acts as the certificate of analysis for this RM. The rock sample was crushed and pulverised at the USGS (Denver, USA), homogenised and split into 1920 bottles, with 55 g each. BRP-1 was transported back to Brazil and the homogeneity between and within bottles was assessed to demonstrate sufficient homogeneity for certification. The chemical characterisation was performed by twenty-five laboratories. Each laboratory received two bottles of BRP-1 and one of BCR-2 (Basalt Columbia River) used for quality control (QC). Reference values and uncertainties were calculated for forty-four constituents of BRP-1, following ISO Guide 35 recommendations and the IAG Protocol. The calculation of each reference value included data of proven traceability from at least ten laboratories using two or more analytical techniques and the uncertainties combines the characterisation and between bottle homogeneity contributions.     

Variation of rare earth concentrations in pigeonitic and hypersthenic rock series from Izu-Hakone region,Japan

The abundances of rare earth elements in 5 each of aphyric volcanic rocks of pigeonitic and hypersthenic rock series from Izu-Hakone region have been determined by neutron activation analysis. Pigeonitic rock series show rare earth patterns with relative depletion of lighter rare earths (low lanthanum type) and large increase in rare earth abundances with differentiation. Hypersthenic rock series show higher lanthanum abundances (high lanthanum type) compared with pigeonitic rock series. The differences in rare earth patterns between two rock series are compatible with the theory of independent magmatic generation of these two series. Variation of rare earth patterns in both series have been examined by a model of magmatic differentiation based on the observed rare earth partition coefficients.     

Laser Ablation and Solution ICP-MS Determination of Rare Earth Elements in USGS BIR-1G, BHVO-2G and BCR-2G Glass Reference Materials

Data are reported for rare earth elements (REE) in three geological glass reference materials (BIR-1G, BHVO-2G and BCR-2G) using a UV (266 nm) laser ablation ICP-MS system and the classical (HF-HClO₄) acid decomposition method, followed by conventional nebulisation ICP-MS. External calibration of laser ablation analyses was performed using NIST SRM reference materials with internal standardisation using ²⁹Si and ⁴⁴Ca. Replicate analyses of reference basaltic glasses yielded an analytical precision of 1-5% (RSD) for all the elements by solution ICP-MS and 1-8% (RSD) by laser ablation ICP-MS. The relative differences between the REE concentrations measured by solution and laser ablation ICP-MS compared with the reference values were generally less than 11 % for most elements. The largest deviations occurred for La determined by solution ICP-MS in BIR-1G. The results of both solution and laser ablation ICP-MS agreed well, generally better than 7%, with the exception of La, Pr and Sm in BIR-1G. The measured REE laser ablation data for BIR-1G, BHVO-2G and BCR-2G agreed with the previously published data on these basaltic reference glasses, within a range of 0-10% for most elements. No significant influences were observed for the predicted spectral interferences on some REE isotopes in the analysis of basaltic glasses.