Instrumental Neutron Activation Analysis of Estuarine Sediment as a Proposed Reference Material for Environmental Studies

The International Atomic Energy Agency (IAEA) Marine Environmental Studies Laboratory (MEL) organised an intercomparison exercise, through its Analytical Quality Control Services (AQCS), for the determination of trace elements in estuarine sediment IAEA-405, well suited for the characterisation of sediments. The instrumental neutron activation analysis technique (INAA) was developed using a 27 kW low power research reactor. Forty elements in the sediment were determined with a measurement precision varying from 1.8% to 12.3%. IAEA reference materials SL-1 and SD-M-2/TM were analysed throughout this work as quality assurance samples.     

Determination of Lithium in the NRCC Marine Sediments: MESS-1, BCSS-1, PACS-1 and the NIST River Sediment: SRM 2704

NRCC marine sediment reference materials: MESS-1, BCSS-1, PACS-1 and the NIST river sediment: SRM 2704 have been analyzed in replicate for lithium (Li) by flame atomic absorption spectrophotometry. Precision (% coefficient of variation) for the NRCC SRM's was <1.5%, and the NIST SRM was 4.3%. Results from replicate acid dissolution of the SRM's in Teflon bombs using boiling water and microwave heating showed no difference in Li concentration between the two methods.     

电感耦合等离子体发射光谱法直接测定铜矿石中银铜铅锌

采用硝酸-氢氟酸-高氯酸混合酸消化处理样品,电感耦合等离子体发射光谱法同时测定了铜矿石中的银、铜、铅和锌。较系统地研究了仪器的最佳化工作参数,采用基体匹配和校正因子相结合的办法校正样品的基体干扰和光谱干扰。方法检出限为:银3.15μg/g,铜4.00μg/g,铅12.0μg/g,锌6.00μg/g(稀释因子500),精密度(RSD,n=12)在0.38%~4.55%。方法经国家一级多金属矿石标准物质验证,测定值与标准值吻合,结果准确可靠。     

Preparation and Certification of Reference Materials (GBW07397, GBW07398, GBW07399 and GBW07400) for Selenium and Other Trace Element Mass Fractions

The preparation and characterisation of certified reference materials of four selenium‐rich rocks (GBW07397 to GBW07400) are described in this paper. The raw materials were derived from selenium‐rich rocks in two famous seleniferous regions, Enshi Prefecture, Hubei Province and Ziyang County, Shaanxi Province, China. Sample homogeneity and stability were tested by inductively coupled plasma‐mass spectrometry and atomic fluorescence spectrometry. The determined element mass fractions included selenium, arsenic, copper, zinc, molybdenum, cadmium, lead, vanadium and silver. Except for silver, the results of analysis of variance (ANOVA) and the relative standard deviations of the element mass fractions showed that the four materials exhibited good homogeneity and stability. Ten laboratories were involved in an interlaboratory comparison scheme for certification. Eight element mass fractions in the selenium‐rich rocks were assigned as certified values, while only indicative values were obtained for Ag mass fractions. The certified values and expanded uncertainties for the selenium mass fractions in GBW07397–GBW07400 are 0.96 ± 0.05, 1.03 ± 0.05, 49 ± 4 and 38.5 ± 1.9 μg g^?1, respectively.     

Chemical Characterisation of NIST Silicate Glass Certified Reference Material SRM 610 by ICP-MS, TIMS, LIMS, SSMS, INAA, AAS and PIXE

National Institute of Science and Technology (NIST) silicate glass SRM 610 is widely used as a certified reference material for various micro-analytical techniques such as SIMS or laser ablation ICP-MS. SRM 610 has been nominally doped with sixty one trace elements at the 500 μg g⁻¹ level, but certified concentration data exist for only a few of these elements. This study reports concentration data for fifty nine trace elements obtained by ICP-MS, SSMS, LIMS, TIMS, INAA, AAS, and PIXE analyses of two different SRM 610 wafers. Most elements fall within a 10% band around a median value of about 440 μg g⁻¹. The REE concentrations are shown to be constant to 3% (1 σ), thus emphasizing the value of SRM 610 as a reference material for REE analyses.
Comparison of our values with published data suggests that different SRM 610 wafers are, within errors, chemically identical for most elements. Exceptions to this general rule appear to be restricted to elements which were partly lost during the production of the glass, e.g. Ag and Br. On the basis of six independent determinations of Rb concentrations, which are systematically lower by a few percent than the reported NIST value, we argue that the certified Rb concentration may not be representative for all distributed SRM 610 wafers.     

AG-MP-1M阴离子交换树脂分离-表面热电质谱法测定沉积物中的铅同位素组成

利用新型阴离子交换树脂分离沉积物中的重金属Pb,采用表面热电离质谱法(TIMS)测定了沉积物样品中的Pb同位素组成。新型树脂为大孔径阴离子树脂AG-MP-1M,淋洗液采用低浓度的盐酸,避免了使用难以纯化的氢溴酸,可有效地降低试剂空白。通过对铅同位素标准物质NIST NBS-981的重复测试,方法的精密度(<0.5%,2s)和准确度均达到了应用研究的要求。对5个实际沉积物样品中的铅同位素组成进行测定,获得了理想的分析效果。     

样品量的大小对铜锌同位素测定值的影响

利用多接收电感耦合等离子体质谱法测定铜、锌同位素比值时,样品量的大小对其同位素测定值存在一定的影响。本研究中使用不同量的实验室标准溶液(CAGS-Cu、CAGS-Zn)过柱,并以该标准溶液为基准,采用标准-样品交叉法测定铜、锌同位素比值。结果表明,当铜、锌的样品量小到一定程度时,其同位素测定值偏离真值;当铜、锌的样品量足够大时,其同位素测定值趋于真值。流程本底对同位素测定值的影响可忽略不计,同时也不存在同质异位素干扰,说明这一现象极可能来自所用试剂和离子交换树脂的杂质组分产生的基质效应。在本文报道的实验条件下,当铜的样品量≥4μg、锌的样品量≥1μg时才能够确保铜、锌同位素测定结果的准确性。这一现象是否在其他同位素体系的测试过程存在,是个值得注意的问题。     

Determination of REE, Y, Nb, Zr, Hf, Ta, Th and U in Geological Reference Materials LSHC-1 and Amf-1 by Solution and Laser Ablation ICP-MS

This paper presents data on REE and Y, Nb, Zr, Hf, Ta, Th and U abundances for two candidate reference materials (RMs), spinel lherzolite LSHC-1 and amphibole Amf-1, being currently developed at the Institute of Geochemistry SB RAS, Irkutsk. To determine the contents of these elements inductively coupled plasma-mass spectrometry was applied with: (i) solution nebulisation (solution ICP-MS) and (ii) laser ablation (LA-ICP-MS) of fused glass disks. The precision of results obtained by both techniques was better than 6% RSD for most elements. Accuracy was assessed by using the geochemical RMs JB-2, JGb-1 (GSJ) and MAG-1 (USGS). The trace element results by solution ICP-MS for JGb-1 and JB-2 agree with reference values presented by Imai et al. (1995, this Journal) within 1–10%. Significant differences were found for Nb and Ta determinations. The accuracy of LA-ICP-MS results evaluated by RM MAG-1 was within 4%, except for Eu (about 10%). The analytical results obtained for LSHC-1 and Amf-1 by solution ICP-MS and LA-ICP-MS were in good agreement with each other and with INAA and XRF data presented for the certification of these RMs. They can be considered as the indicative values for assigning certified values to the above-mentioned RMs.     

Mass Fractions of Forty‐Six Major and Trace Elements,Including Rare Earth Elements,in Sediment and Soil Reference Materials Used in Environmental Studies

Development of new techniques, enabling simultaneous determination of large numbers of elements in environmental samples, can force analysts to use certified reference materials that do not contain all the elements of interest. In this paper, the mass fractions of forty‐six major and trace elements, including rare earth elements (REE), are presented in one soil (NCS DC 77302 also known as GBW 07410) and five sediment (Metranal‐1, IAEA 405, MESS‐3, NCS DC 73309 also known as GBW 07311 and NCS DC 75301 also known as GBW 07314) certified reference materials determined by high resolution inductively coupled plasma‐mass spectrometry. The selected certified materials represent a spectrum of geological matrices often analysed in environmental studies. Measured elements include certified elements, elements listed with information values as well as new elements absent from certificates, including REEs and some other elements. REE + Y mass fractions in the river sediment reference material Metranal‐1 are reported for the first time. The results obtained are in agreement with available certified or information values.     

粉末压片制样-X射线荧光光谱法测定铁矿石中锌砷锰

应用X射线荧光光谱仪测定铁矿石中的锌、砷、锰含量,采用粉末压片法制样,并研究了制样的条件,确定了仪器最佳参数,建立了标准曲线。经国家实物标准铁矿石样品验证,测定值与标准值吻合,三元素的偏差均小于±0.007%;精密度试验表明相对标准偏差(n=10)均小于2.80%。大量实验数据表明,压片制样-X射线荧光光谱法测定锌、砷、锰元素的精密度高,准确可靠。该方法在检测准确度和分析速度上可以满足钢厂生产要求。     

Determination of the Trace Refractory Elements V, Nb and Ta in Environmental Samples by ICP-MS After Separation and Preconcentration with Nanometre-Sized Alumina Microcolumns Following Chemical Modification by Gallic Acid

Nanometre-sized alumina was chemically modified with gallic acid (GA) and used as a solid phase adsorption material for the determination of trace amounts of V, Nb and Ta in natural water, soil and stream sediment samples by inductively coupled plasma-mass spectrometry. The effects of pH, sample flow rate and volume, elution solution and interfering ions on the recovery of the analytes were investigated. The results showed that V, Nb and Ta could be adsorbed at pH 4.0 and recovered with 1 ml of 2.0 mol l^-1 HCl. Under optimised conditions, the adsorption capacity of GA-modified nanometre-sized Al₂O₃ was found to be 7.0, 8.9, 13.3 mg g^-1 for V, Nb and Ta, respectively. The limits of detection were as low as 0.25, 0.24 and 0.66 ng l^-1 for V, Nb and Ta, respectively with a concentration factor of fifty. The recovery of V, Nb and Ta for spiked water samples was between 85.7 and 116%. The developed method has also been applied to the determination of trace V, Nb and Ta in soil and stream sediment certified materials, and the determined values were in a good agreement with the certified values.     

松辽盆地西部斜坡带烃类微渗漏遥感信息提取

松辽盆地西部斜坡带位于吉林省西部白城地区。20多口探井证实，油气显示主要集中在东北部套保地区，油气显示最井是洮13井，其次为洮5井和洮5井和洮6井。烃类微渗漏遥感直接探测技术是一种直接找油方法，是90年代以来发展的一种新方法，目前已被国内外石油勘探部门广泛应用。通过对液态、气态、固态石油物质光谱特性的分析，采用比值处理，加TM4／TM7、TM4／TM5、TM4／TM3来增强微弱的烃类微渗漏异常；并将波段的比值或原波段进行彩色合成提取了研究区烃类微渗漏异常，其结果与已知钻孔的含油气情况一一对应，同时在研究区西部角发现一些新的油气渗漏异常区，可作为研究区油气勘探进一步工作的优先靶区，对研究区的油气勘探有较好的指导意义。     

SZ-1型同位素X射线荧光分析仪分析多金属结核中锰铁钴镍铜

采用低分辨率能量色散Ｘ射线荧光分析仪和偏最小二乘法对太平洋多金属结核中的Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ和Ｃｕ等元素进行了现场分析,并对所用仪器的性能和方法的可靠性作了评价。方法经国家级标准物质验证,其测定值与标准值相符,ＲＳＤ（ｎ＝４２）各元素均小于１．０％,分析结果满足现场分析中矿物品位的测定要求。     

不同氢化反应条件下原子发射光谱同时测定锗锡砷锑铋

研究了不同氢化反应条件下电感耦合等离子体原子发射光谱同时测定锗,,锡,砷,锑和铋的方法。主要对锗,锡的氢化反应酸度,缓冲溶液的选择,动态线性范围,氧化剂的选择,共存元素的干扰及其消除进行实验。方法经国家一级标准物质分析验证,结果与标准值基本相符。     

The Preparation of Marine Geological Certified Reference Materials - Polymetallic Nodule GSPN-1 and Marine Sediment GSMS-1 from the Central Pacific Ocean*

This report describes the location, collection, preparation, homogeneity testing, analysis, data-processing and assignment of certified values of a polymetallic nodule (GSPN-1) and marine sediment (GSMS-1). Materials used in the preparation of these reference materials were collected in 1986 and 1987 from the central Pacific Ocean, by the Chinese Ministry of Geology and Mineral Resources (MGMR). A total of fifty one recommended element concentrations and five proposed concentrations are reported for GSPN-1. For GSMS-1, a total of fifty recommended and seven proposed values are presented.     

发射光谱法同时测定地球化学样品中微量银铍硼锡铋钼

采用垂直电极装样,二米平面光栅交流电弧摄谱测定地质样品中的微量元素银、铍、硼、锡、铋、钼,以三氧化二铝、焦硫酸钾、氟化钠、碳粉和硫粉作缓冲剂,锑、锗作内标。方法检出限为:银0.019μg/g、铍0.11μg/g、硼0.85μg/g、锡0.26μg/g、铋0.031μg/g、钼0.12μg/g。各元素12次测定的相对标准偏差(RSD)均小于10%。用水系沉积物、土壤、岩石国家一级标准物质进行验证,测定值与标准值基本一致,符合多目标地球化学填图的质量要求。     

New Chinese National Reference Materials for Hydrogen and Oxygen Isotopes in Water

The Institute of Hydrogeology and Environmental Geology, Chinese Academy of Geological Sciences recently prepared four certified reference materials for hydrogen and oxygen stable isotopes in water, which are called ‘China Standard Water' (CSW)‐HO1–HO4 (hereafter referred to as HO1–HO4). These reference materials are intended for calibration purposes and provide reference values of their relative difference in ²H/¹H and ¹⁸O/¹⁶O isotope‐amount ratios expressed in delta notation, normalised to the VSMOW–SLAP scale. The certified values of the reference materials were determined by an interlaboratory comparison of results from eleven participating laboratories. This paper describes in detail the production and certification procedure of the four reference materials. The first analytical data for the reference materials are also provided using a variety of analytical techniques, namely CO₂–H₂O equilibration and laser spectroscopy for δ¹⁸O and Cr reduction, as well as H₂–H₂O equilibration, laser spectroscopy, and high‐temperature conversion for δ²H. The reference values for materials HO1–HO4 and their associated uncertainties are assigned.     

微波消解-电感耦合等离子体发射光谱法同时测定白云石中铁铝钙镁钾钠硫

采用微波消解白云石样品，电感耦合等离子体发射光谱法测定其中铁、铝、钙、镁、钾、钠、硫的氧化物，对微波消解条件和等离子体发射光谱仪的工作条件进行了选择，克服了常规化学分析方法步骤繁琐、耗时长、工作量大的不足。利用所建立的方法快速分析了白云石中铁、铝、钙、镁、钾、钠、硫的含量，结果与标准值或化学法相符，10次测定的相对标准偏差（RSD）7种元素均小于1％，可以满足生产和科研的要求。     

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.     

等离子体发射光谱法同时测定大洋富钴结壳中硅锰铁钙镁铝钛

大洋富钴结壳试样经ＨＣｌ＋ＨＮＯ３＋ＨＦ溶解,在０．２ｍｏｌ／ＬＨＦ和０．１３ｍｏｌ／ＬＨ３ＢＯ３介质中,用感耦等离子发射光谱法同时测定Ｓｉ、Ｍｎ、Ｆｅ、Ｃａ、Ｍｇ、Ａｌ、Ｔｉ元素的含量。方法经国家标准物质ＧＢＷ０７２４９大洋多金属结核验证,其结果与标准值相符,精密度ＲＳＤ〈３．２％（ｎ＝６）;已应用于太平洋富钴结壳中多元素分析。