Cd, Gd and Sm Concentrations in BCR-1, BHVO-1, BIR-1, DNC-1, MAG-1, PCC-1 and W-2 by Isotope Dilution Thermal Ionisation Mass Spectrometry

Cadmium, gadolinium and samarium concentrations were determined in seven geochemical reference materials by isotope dilution thermal ionisation mass spectrometry. The results for all three elements in BCR-1 are in excellent agreement with the compiled values as well as the literature values dete-mined by isotope dilution mass spectrometry. The agreement with compiled values on the other material is generally good except for Cd where the values for BHVO-1, BIR-1, DNC-1 and W-2 need to be revised.     

MIBK负载泡塑吸附-中子活化法在金标样定值中的应用

试样经焙烧、王水分解后,在8％的王水介质中,MIBK负载泡塑吸附[AuCl_4]~-。灰化吸附泡塑或硫脲溶液解脱,用中子活化法测定Au。取10g样品,可测定0.000x～xxμg/g的Au。用于金标样的定值,具有良好的精密度和准确度。     

High-Precision Trace Element Data for the USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, DTS-1, DTS-2, GSP-1 and GSP-2 by ID-TIMS and MIC-SSMS

Different batches of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2, DTS-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1, DTS-1 and GSP-1 have been analysed by isotope dilution using thermal ionisation mass spectrometry (ID-TIMS) and by multi-ion counting spark source mass spectrometry (MIC-SSMS). The concentrations of K, Rb, Sr, Ba and the rare earth elements were determined with overall analytical uncertainties of better than 1% (ID-TIMS) and 3% (MIC-SSMS). The analyses of different aliquots and batches of BCR-2, BHVO-2, AGV-2 and GSP-2, respectively, agree within 1%, i.e. approximately the analytical uncertainties of the data. This indicates an homogeneous distribution of the trace elements in these RMs. Differences in element concentrations of up to 17% in different aliquots of the depleted RM DTS-2 are outside the analytical uncertainty of our data. They may be attributed to a slightly heterogeneous distribution of trace elements in this dunite sample. Our trace element data for BCR-2, BHVO-2, AGV-2 and GSP-2 agree within about 3% with preliminary reference values published by the USGS. They also agree within 1-6% with those of the original RMs BCR-1, BHVO-1, AGV-1 and GSP-1. Large compositional differences are found between DTS-2 and DTS-1, where the concentrations of K, Rb, Sr and the light REE differ by factors of 2 to 24.     

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.     

Sr and Pb isotopic composition of five USGS glasses (BHVO-2G, BIR-1G, BCR-2G, TB-1G, NKT-1G)

Sr isotopic compositions and Rb / Sr ratios of three USGS glasses (BHVO-2G, BIR-1G, BCR-2G) are identical to those of the original USGS reference materials. NKT-1G and TB-1G give values of 0.70351 and 0.70558, respectively. Pb isotopic ratios were measured by the standard-sample bracketing technique on an MC-ICP-MS, which give results that are comparable in accuracy and reproducibility to double spike analyses. However, assessment of the reproducibility of the technique is hampered by inhomogeneous contamination of all USGS reference materials analysed. This contamination is likely to be the reason why the USGS glasses do not all have the same Pb isotopic composition as their unfused originals. Powdered glasses, distributed for characterisation of the glasses by bulk analytical techniques, do not all have the same Pb isotopic compositions as the solid glass material, and can therefore not be used for this purpose.     

Instrumental Neutron Activation Analysis of Silicate Rock Standards AN-G, BHVO-1, QLO-1, RGM-1, and STM-1

Silicate rock standards AN-G, BHVO-1, QLO-1, RGM-1, SDC-1 and STM-1 have been analyzed for 7 REE (La, Ce, Sm, Eu, Tb, Yb and Lu), Na₂O, FeO_t, Sc, Co, Cr, Ta, Hf and Th by instrumental neutron activation analysis. The mean values are compared to those from other studies reported in the literature.     

Neodymium and Strontium Isotope Data for USGS Reference Materials BCR-1, BCR-2, BHVO-1, BHVO-2, AGV-1, AGV-2, GSP-1, GSP-2 and Eight MPI-DING Reference Glasses

We have measured ⁸⁷Sr/⁸⁶Sr and ¹⁴³ Nd/¹⁴⁴ Nd isotope ratios in different batches and aliquots of the new US Geological Survey (USGS) reference materials (RMs) BCR-2, BHVO-2, AGV-2 and GSP-2 and the original USGS RMs BCR-1, BHVO-1, AGV-1 and GSP-1 by thermal ionisation mass spectrometry. In addition, we also analysed the eight Max-Planck-Institut-Dingwell (MPI-DING) reference glasses. Nearly all isotope ratios obtained in the different aliquots and batches agree within uncertainty limits indicating excellent homogeneity of the USGS powders and the MPI-DING glasses. With the exception of GSP-2, the new USGS RMs are also indistinguishable from the ratios found in the original USGS RMs (⁸⁷Sr/⁸⁶Sr: 0.704960, 0.704958 (BCR-1, -2), 0.703436, 0.703435 (BHVO-1, -2), 0.703931, 0.703931 (AGV-1, -2); ¹⁴³ Nd/¹⁴⁴ Nd: 0.512629, 0.512633 (BCR-1, -2), 0.512957, 0.512957 (BHVO-1, -2); 0.512758, 0.512755 (AGV-1, -2)). This means that for normalisation purposes in Sr and Nd isotope geochemistry BCR-2, BHVO-2 and AGV-2 can well replace BCR-1, BHVO-1 and AGV-1 respectively.     

岩矿与单矿物中金的堆中子活化分析

痕量金的分析,目前采用的化学分析方法,由于灵敏度较差,不能满足地质上的要求。河南省局实验室的改进光谱法是目前推广的方法。中子活化分析法,由于其核的特征反应,所以具有灵敏度高、选择性好及取样量少的特点,对单矿物中金的分析是其它方法所不及的,且能进行多元素同时分析。     

中子活化分析方法测量金的活动态

探讨了金的活动态各相态（水浸出态，粘土吸附态，有机链合态，铁锰氧化物态）提取操作和中子活化分析测定的条件。列出了部分样品中金活动态分析结果和其测定精度范围，各相态的空白值和RSD（n=5)分别为：水浸出态0.030ng/g,4.5%-26.0%；粘土吸附态0.05ng/g,11.6%-25.2%；有机链合态0.06ng/g,3.7%-26.8%；铁锰氧化物态0.05ng/g,5.9%－31.6％。     

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.     

Analysis of Sulfides for Gold and Associated Trace Metals by Direct Neutron Activation With a Low-Flux Reactor

A routine method for the direct determination of Au and associated trace metals in sulfides has been developed for use with a low-flux nuclear reactor (SLOWPOKE II Reactor Facility, University of Toronto). Small samples (100–200 mg) are analysed simultaneously for Au, Ag, As, Sb, Mo, Co, Se, Cd, Fe, and Zn. Sulfides containing finely divided gold can be analysed with a high degree of precision and yield results which agree closely with commercial fire assay-atomic absorption analyses for Au. Favourable comparisons with other analytical techniques (flameless atomic absorption and emission spectrometry) are also indicated for Ag, As, and Sb. Neutron activation has the advantage of providing precise and accurate results for these elements without chemical separation or preconcentration. Analyses of 10 sulfide-bearing reference materials from CANMET, Ottawa are compared with published best values for selected trace metals including Au.     

Some Trace-Element Contents of Biotite, Btt-1, and Hornblende, Hbl-I, by Semiquantitative Spectrographic Analysis and by Instrumental Neutron Activation Analysis

Some trace-element contents of U.S. Geological Survey (USGS) samples, biotite Btt-1 and hornblende Hbl-1, were determined by both computerized semi-quantitative spectrographic analysis and instrumental neutron activation analysis. An equal number of portions of the Centre de Recherches Pétrographiques et Géochimiques (CRPG) samples, biotite Mica-Fe and phlogopite Mica-Mg, were randomized with portions of the USGS samples and analyzed simultaneously to allow direct comparisons of trace elements in the biotites. Mica-Fe has concentrations of Cs, Hf, Ta and Zn that are greater by factors of 3 or more than those in Btt- 1. Although the Co contents of the two biotites are nearly equal, the amounts of Cr, Sc, La and the rare earth elements are significantly greater in Btt-1. Mica-Mg contains larger amounts of Cs and Rb than does Hbl-1, whereas the Cr content of Hbl-1 is 15 times that of Mica-Mg. Btt-1 and Hbl-1 may be useful as comparison samples for the analysis of biotites and hornblendes after other data are available.     

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.     

金矿样品采样—加工—化验质量的综合研究

对不同类型金矿石取样方法和加工方法进行了实验研究。实验表明,对于任何一个新矿区金试样的加工制备,应查明矿石类型、主要万分、赋存状态,查清自然金粒度分布情况,通过实验制定切实可行的采样方法、加工流程,选择正确的分析方法,从而保证分析结果的准确度。     

Accurate Determination of Chlorine,Bromine and Iodine in U.S. Geological Survey Geochemical Reference Materials by Radiochemical Neutron Activation Analysis

Trace amounts of three halogens (chlorine, bromine and iodine) in seventeen U.S. Geological Survey (USGS) geochemical reference materials were determined by radiochemical neutron activation analysis (RNAA). The materials analysed were AGV‐2 (andesite), BCR‐2, BHVO‐2 and BIR‐1a (basalts), CLB‐1 (coal), COQ‐1 (carbonatite), DGPM‐1 (disseminated gold ore), DNC‐1a (dolerite), DTS‐2b (dunite), GSP‐2 (granodiorite), Nod‐A‐1 and Nod‐P‐1 (manganese nodules), QLO‐1a (quartz latite), SBC‐1 (marine shale), SDC‐1 (mica schist), SGR‐1b (shale rock) and W‐2a (diabase). The chlorine, bromine and iodine contents were determined to be 5.64 mg kg^?1 (BIR‐1a) to 4410 mg kg^?1 (Nod‐A‐1), 0.039 mg kg^?1 (BIR‐1a) to 52.1 mg kg^?1 (CLB‐1), and 0.041 mg kg^?1 (BIR‐1a) to 599 mg kg^?1 (CLB‐1), respectively. The RNAA data of the three halogens were compared with the corresponding data in the literature.     

Chromium Contents of Standard Rock Samples: A Detailed Investigation by Radiochemical Neutron Activation Analysis

The reported values for the chromium contents of standard acidic rocks show a large spread, making it difficult to assign firm recommended values. A radiochemical neutron activation analysis procedure was developed and its reliability examined critically. The method involves separation of chromium as chromyl chloride by distillation followed by precipitation as barium chromate. The chromium content of a number of international standard rocks has been determined and results obtained are critically reviewed in relation to the available data.     

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.     

Determination of Ti, K, Sm and Gd Values in Geological Survey of Japan Reference Materials by Prompt Gamma Neutron Activation Analysis

Prompt gamma neutron activation analysis was applied to the determination of the titanium, potassium, samarium and gadolinium contents of nine Geological Survey of Japan (GSJ) reference materials (JB-1, 1a, 2, 3; JA-1, 2, 3; JR-1, 2). Firstly, the values in JB-1 were determined by the standard addition method: pressed powder disks of JB-1 were used for neutron irradiation and gamma-ray measurements, after known quantities of standard reagents had been added. Secondly, the contents of eight other reference materials were determined by comparison methods using JB-1 as the comparative standard. The precision of analyses were obtained by replicate determinations on these samples. The relative standard deviation was generally less than 5%. For most samples, analysed values agreed well (< 5%) with the recommended values.     

赣南淘锡坑钨矿的石英中子活化分析研究

对赣南淘锡坑矿区V11号王牌矿脉不同中段的石英进行了中子活化分析,发现W主要与Sm、Lu、Yb、Mn、Sc、Ta、Fe等元素相关性比较好。在矿体的纵投影面上,识别出156中段和106中段各有3个浓集中心,并有从地表往深部W含量逐渐升高的趋势,显示矿液由南东往北西富集。预测枫林坑深部找矿前景较好。尝试性地进行了矿脉深部储量的预测研究,获得了 106m和56m两个中段的储量共10275.6t,加上156中段—356中段,合计V11号脉体的储量为19851.93t,与探明储量接近。可见,利用石英中子活化分析资料,有助于矿体深部储量的估算。     

Neutron Activation Analysis, Atomic Absorption and X-Ray Fluorescence Spectrometry Review for 2004–2005

These technologically mature techniques occupied a stable to modestly increasing sector of the spectrum of analytical methods in Earth and environmental sciences in 2004–5. Despite this, several notable advances were reported in this two year period. In the field of X-ray fluorescence spectrometry, these included the development of portable synchrotron and total reflection instruments, the use of pyroelectric crystals as X-ray generators, introduction of high-purity Ge detector arrays, and the development of an XRF imaging spectrometer with the capability of mapping analytes and X-ray intensity ratio. Atomic absorption s spectrometry saw major work published on high-resolution continuum source AAS (HR-CS AAS) involving the development of a xenon short-arc lamp. Other advances included the use of laser wave mixing in a graphite furnace tube (with a claimed detection limit of 10–¹⁶ g g-¹), solid sampling and ultrasound in sample preparation. Neutron activation analysis saw two innovations that may herald future growth in this technique, namely a neutron source free of a nuclear reactor and a detector operating at room temperature.