A proposed sampling constant for use in geochemical analysis

The error in a determination of an element in a rock or mineral sample depends on the analytical error, the weight of sample analysed, and the nature and history of the laboratory sample. The most probable result is not independent of the weight of sample analysed. This is due to the fact that trace constituents often reside in isolated mineral grains. The chance of such mineral grains appearing in any one analysed sample becomes more remote as the sample weight decreases, even when rock or mineral samples are reduced to fine powders. Such subsampling errors can be controlled through the use of sampling constants. These may be estimated by several procedures, including repetitive determination of a constituent and physical measurement of relevant sample characteristics. Sampling constants can be usefully employed during the establishment and certification of reference samples or standards. When subsampling is deficient, analytical results may yield erroneously low values, sometimes with high precision. High precision never implies high accuracy; it may be a symptom of gross error.     

Instrumental neutron activation analysis of some rock samples from Akwana and Arufu areas,Middle Benue Trough,Nigeria

Twenty nine (29) major, minor and trace elements including rare earth elements (REEs) were determined by INAA in rock samples from Akwana and Arufu areas, Middle Benue Trough, Nigeria. The rock units are located within the lead-fluorite and baryte mineralisation there. The concentrations of the major elements in the tertiary basalt (TB) and dolerite are similar while the elemental abundance in the granite gnesses is completely different. The elemental concentrations in the rock samples do not show any known relationship with fluorite abundance. The concentrations of some elements in both tertiary basalt and dolerite show them to be derived from alkali basaltic liquid. The chondritic normalised REE distribution patterns for the TB are similar to those of BCR-1 but the chondritic relative REE abundance is more enriched in TB than in the BCR-1. The chondritic normalised REE distribution patterns for the granite gneisses are also compared to those of the standard granite samples.     

Rapid laser fluorometric method for the determination of uranium in soil, ultrabasic rock, plant ash, coal fly ash and red mud samples

A simple and rapid laser fluorometric determination of trace and ultra trace level of uranium in a wide variety of low uranium content materials like soil, basic and ultra basic rocks, plant ash, coal fly ash and red mud samples is described. Interference studies of some common major, minor and trace elements likely to be present in different, geological materials on uranium fluorescence are studied using different fluorescence enhancing reagents like sodium pyrophosphate, orthophosphoric acid, penta sodium tri-polyphosphate and sodium hexametaphosphate. The accurate determination of very low uranium content samples which are rich in iron, manganese and calcium, is possible only after the selective separation of uranium. Conditions suitable for the quantitative single step extraction of 25 ng to 20 μg uranium with tri-n-octylphosphine oxide and single step quantitative stripping with dilute neutral sodium pyrophosphate, which also acts as fluorescence enhancing reagent is studied. The aqueous strip is used for the direct laser fluorometric measurement without any further pretreatment. The procedure is applied for the determination of uranium in soil, basalt, plant ash, coal fly ash and red mud samples. The accuracy of the proposed method is checked by analyzing certain standard reference materials as well as synthetic sample with known quantity of uranium. The accuracy and reproducibility of the method are fairly good with RSD ranging from 3 to 5% depend upon the concentration of uranium.     

Determination and interpretation of environmental water samples contaminated by uranium mining activities

Interpretation of environmental behavior of uranium is based on several steps of data analysis and statistical inference. First step is sampling and analyzing of uranium in field samples by routine laboratory methods. Such methods have to fulfill multiple requirements like robustness, efficiency, low detection limit and precision. A comparison of different approaches in assigning uncertainty to experimentally obtained analytical data shows that classical error estimation is not significantly inferior to more sophisticated modern techniques like inverse regression or orthogonal regression. A second step is the correlation of analytical data with current state of insight into environmental behavior of uranium. Such a correlation furthers the choice of adequate geochemical models and quality of geochemical data base for subsequent detailed analysis, e.g. by geochemical modeling. An appraisal of the individual steps in this complex analysis is given on the basis of statistical procedures for calibration and an E_H-pH diagram of uranium for atmospheric conditions. Received: 30 July 1998 / Revised: 18 November 1998 / Accepted: 26 November 1998     

Determination and interpretation of environmental water samples contaminated by uranium mining activities

Interpretation of environmental behavior of uranium is based on several steps of data analysis and statistical inference. First step is sampling and analyzing of uranium in field samples by routine laboratory methods. Such methods have to fulfill multiple requirements like robustness, efficiency, low detection limit and precision. A comparison of different approaches in assigning uncertainty to experimentally obtained analytical data shows that classical error estimation is not significantly inferior to more sophisticated modern techniques like inverse regression or orthogonal regression. A second step is the correlation of analytical data with current state of insight into environmental behavior of uranium. Such a correlation furthers the choice of adequate geochemical models and quality of geochemical data base for subsequent detailed analysis, e.g. by geochemical modeling. An appraisal of the individual steps in this complex analysis is given on the basis of statistical procedures for calibration and an E_H-pH diagram of uranium for atmospheric conditions.     

电感耦合等离子体原子发射光谱法(ICP-AES)测定玄武岩中的8种微量元素

采用硝酸-盐酸-氢氟酸高压封闭消解样品,电感耦合等离子体原子发射光谱法测定玄武岩中的8种微量元素。实验确定了方法的分解条件以及测定元素的检出限及干扰条件。用国家一级标准物质GBW07105(玄武岩)进行方法验证,检测结果与标准值基本吻合,符合地质矿产开发的要求。     

Determination de l'enrichissement de l'uranium par comptage du rayonnement Cerenkov

A method for the measurement of²³⁵U in dilute uranium solutions based on Cerenkov radiation is described. It is applicable to solutions treated in fuel element production where the enrichment factor of the uranium solution is to be known, thus to solutions of uranyl nitrate not containing other fission products.      

Laser-induced breakdown spectroscopy measurements of uranium and thorium powders and uranium ore

Laser-induced breakdown spectroscopy (LIBS) was used to analyze depleted uranium and thorium oxide powders and uranium ore as a potential rapid in situ analysis technique in nuclear production facilities, environmental sampling, and in-field forensic applications. Material such as pressed pellets and metals, has been extensively studied using LIBS due to the high density of the material and more stable laser-induced plasma formation. Powders, on the other hand, are difficult to analyze using LIBS since ejection and removal of the powder occur in the laser interaction region. The capability of analyzing powders is important in allowing for rapid analysis of suspicious materials, environmental samples, or trace contamination on surfaces since it most closely represents field samples (soil, small particles, debris etc.). The rapid, in situ analysis of samples, including nuclear materials, also reduces costs in sample collection, transportation, sample preparation, and analysis time. Here we demonstrate the detection of actinides in oxide powders and within a uranium ore sample as both pressed pellets and powders on carbon adhesive discs for spectral comparison. The acquired LIBS spectra for both forms of the samples differ in overall intensity but yield a similar distribution of atomic emission spectral lines.     

A comparison of slurry sampling electrothermal vaporization and slurry nebulization inductively coupled plasma mass spectrometry for the direct determination of trace impurities in titanium dioxide powder

A comparison of slurry sampling (SS)-ETV-ICP-MS and slurry nebulization (SN)-ICP-MS for direct determination of trace impurities in titanium dioxide powder is made. The particle size effect, matrix effect and analytical characteristics of SSETV-ICP-MS and SN-ICP-MS are compared. The results have shown that SSETV-ICP-MS has a lower particle size effect and matrix effect compared to SN-ICP-MS. The analytical performance of the two methods reveals that SSETV-ICP-MS and SN-ICP-MS have similar relative detection limits (in the nanogram per liter level); however, the former has a lower absolute detection limit than the latter. Although the precision for SSETV-ICP-MS is a little worse than that for SN-ICP-MS, it is still acceptable for real sample analysis. The two methods were successfully applied for the determination of trace impurities in titanium dioxide powder samples with particle sizes of less than 50 nm, but only SSETV-ICP-MS could be applied for the determination of trace impurities in titanium dioxide powder samples with a particle size of 1 microm.     

Determination of plutonium by isotopic dilution mass spectrometry following TTA-extraction

Isotopic dilution mass spectrometry has been applied to assess the plutonium concentration in samples such as those obtained from the dissolution of irradiated uranium fuels in a reprocessing plant. Prior to the analysis, plutonium is taken through a redox cycle and is separated from uranium and fission products by extraction into TTA-xylene. The extraction procedure, the standardization of the spike solution and the mass assay of the plutonium are described; typical results under plant conditions are given. The overall precision of a single measurement of the plutonium concentration is 0.6%, expressed as relative standard deviation, including the plant sampling error, dilution error and analytical error.     

X射线荧光光谱法同时测定矿石中铀和钍

建立了X射线荧光光谱法测定矿石样品中铀、钍含量的快速分析方法。采用高压粉末制样法,对不同含量的放射性样品的压片压力、粒径、含水率、用量等处理条件到进行单因素实验。在400 MPa压力下压制,克服了低压制样的弊端,制备的样片表面光滑、致密,大幅改善了制样重现性,有效地减少了部分基体效应,铀校准曲线的标准偏差从0.053%降到0.0071%,钍校准曲线的标准偏差从0.062%降到0.0057%。经国家一级标准物质验证,表明方法准确、可靠,能满足样品中铀、钍含量日常分析要求。     

同位素稀释等离子体质谱法测定地质样品中痕量硼

建立了同位素稀释等离子体质谱法（ID—ICP—MS）测定地质样品中痕量硼的方法。采用减压排空色谱柱分离样品中的大量基体,以减少基体效应的影响,具有试剂用量少、分离速度快、效果好等特点。对两个标准物质GSD-4和GSD-8的测定结果表明,其与参考值吻合得较好,相对偏差均小于6％。3个不同样品的测定结果表明,该方法具有较好的准确度和精密度。     

Analytical application of DHOA for the determination of trace metallic constituents in U based fuel materials by ICP-AES

DHOA (Di-n-hexyl-octanamide) is one of the alternative extractants to TBP (tri-n-butyl phosphate) known for the extraction of uranium from moderate nitric acid medium without significant extraction of the fission products. Analytical application of DHOA was explored to develop a methodology for determination of trace metallic constituents in uranium based nuclear materials. This involved the separation of uranium matrix by 1.1 M DHOA-dodecane followed by the analysis of the raffinate for trace constituents by Inductively Coupled Plasma Atomic Emission Spectrometry (ICP-AES). A systematic study showed that four contacts of 1.1 M DHOA-dodecane were required for quantitative extraction of U from 4 M HNO₃ feed for the sample size of 1 g in 10 mL. The feasibility of using DHOA for extraction of U from trace metallic constituents in U based fuel materials without losing trace quantities of analytes of interest was studied by using synthetic samples after appropriate spiking of common impurities and critical elements at their required specification limits (common elements—5 ppm, critical elements—1 ppm). A systematic study was carried out to compare the analytical performance of DHOA with TBP, which revealed that DHOA could successfully be employed for the determination of 19 trace constituents with lower estimation limits of 5 ppm for common impurities and 1 ppm for critical elements.     

X-ray fluorescence analysis in environmental radiological surveillance using HPGe detectors

X-ray fluorescence (XRF) has been proven to be a valuable tool for determining trace quantities of heavy metals, such as uranium and lead, in different types of samples. The present paper demonstrates the applicability of XRF spectrometry to measure the concentrations of these heavy metals in samples from natural ore and soil. The values of uranium concentrations in rock from the Peña Blanca uranium ore, in Chihuahua, México, were calculated for the purpose of precertifying the rock powders samples. The comparison with other techniques, such as inductively coupled plasma atomic emission spectrometry, atomic absorption spectrometry, alpha spectrometry and electron microscopy, was used to complete the precertification process, so that the sample powders may be used as secondary standards. The source-sample-detector geometry and the incident angle are the most important factors for obtaining low detection limits. The selected system uses a ⁵⁷Co source of about 0.1 mCi to excite the K X-rays from uranium and lead. X-rays were recorded on a CANBERRA HPGe coaxial detector. The comparative results for two incident angles (90° and 180°) performed previously by other authors show that the best geometry is the backscattering geometry. In the present paper, using EGS4 code system with Monte Carlo simulation, it was possible to determine the location and distribution of background produced by the Compton edge in the optimized geometry. This procedure allowed to find the minimum detectable concentration of uranium and lead, which was experimentally calculated using standards. The possibility of performing in vivo measurements rapidly and easily, as well as the factors affecting accuracy and the minimum detectable concentration in several samples are also discussed.     

Tree ring microanalysis by LA–ICP–MS for environmental monitoring: validation or refutation? Two case histories

An empirical approach is presented for validating trace metal profiles in tree rings for use as environmental archives. Concentration profiles of Zn, Cd, Cu, Pb and U in tree rings and lake sediments are compared for assessing the reliability of the former as an environmental proxy. Laser ablation sampling in conjunction with inductively coupled plasma mass spectrometry (LA–ICP–MS) is used for the direct analysis of tree rings. An optimised analytical protocol is devised with particular emphasis on sample preparation and quantification strategy. Significant correlations in the two environmental archives were found for zinc, copper and uranium, while cadmium and lead temporal trends, although showing enrichment in recent years, do not agree with the concentration profiles in lacustrine sediment cores. A chemical model based on metal affinity for hard type ligands present in wood is proposed to explain these results. Moreover, spring and winter wood are analysed separately thanks to the high spatial resolution of laser ablation sampling. As a result, enhanced metal loadings are shown to lead to intraring differences in trace metal concentrations.     

Chemometric investigation of systematic error in the analysis of biological materials by flame and electrothermal atomic absorption spectrometry

Systematic errors observed when using flame atomic absorption spectrometry (FAAS) and electrothermal atomic spectrometry (ETAAS) for the analysis of biological solid materials (seafood products) were evaluated. The effect of the sample pre-treatment method (microwave-assisted acid digestion, ultrasound-assisted acid leaching and slurry sampling) as well as the number of times that a certain pre-treatment process is repeated, were two factors evaluated. They give information about the effect of the sample pre-treatment on the uncertainty in the analysis. In addition, the number of measurements (i.e., number of times that an acid digest, an acid leachate or aqueous slurry are analysed) and the calibration technique used (aqueous calibration method or standard addition technique) were other two variables taken into account. This last factor gives information about the effect of the calibration on the results, while the replicate measurements showed the repeatability. A fifth variable named as sample matrix tests the influence of the matrix sample on the systematic error through the use of different reference materials. This variable allows the study of the effect of the trace element concentrations on the uncertainty because the trace elements contents are different in each reference material. Experimental design and principal component analysis approaches were used as chemometric tools. It has been found that the use of the slurry sampling technique in ETAAS and FAAS and the determination of high element concentrations by ETAAS have led to poor precision.     

Anion analysis in uranium ore concentrates by ion chromatography

In the present exploratory study, the applicability of anionic impurities for attributing nuclear material to a certain chemical process or origin has been investigated. Anions (e.g., nitrate, sulphate, fluoride, chloride) originate from acids or salt solutions that are used for processing of solutions containing uranium or plutonium. The study focuses on uranium ore concentrates (“yellow cakes”) originating from different mines. Uranium is mined from different types of ore body and depending on the type of rock, different chemical processes for leaching, dissolving and precipitating the uranium need to be applied. Consequently, the anionic patterns observed in the products of these processes (the “ore concentrates”) are different. The concentrations of different anionic species were measured by ion chromatography using conductivity detection. The results show clear differences of anion concentrations and patterns between samples from different uranium mines. Besides this, differences between sampling campaigns in a same mine were also observed indicating that the uranium ore is not homogeneous in a mine. These within-mine variations, however, were smaller than the between-mine variations.     

Spectral interference study of uranium on other analytes by using CCD based ICP-AES

Due to the multi-electronic nature, uranium is having line rich emission spectra and is expected to interfere during the determination of analytes at the trace level in uranium matrix. Therefore, chemical separation of uranium followed by the determination of trace metallic impurities in the raffinate by ICP-AES is generally adopted procedure in nuclear industries. There is restriction on choosing alternate analytical lines of elements by photomultiplier tube based ICP-AES associated with the polychromator while monochromator needs significant time to scan different analytical lines of all the elements. Since charged coupled detector (CCD) consists of array of pixels, it is having more option in choosing alternative analytical lines of the analytes. Therefore, an attempt was made to study the spectral interference of uranium on different analytical lines of analytes viz. Al, Ga, In, Si, Li, Ti, Mg, Sr, K, Ce, Nd, Lu, Sc, V, Er, Y, Ba, Bi, Pb, W, La, Tl, Sn, Yb, Mo, Sb, Pr and Zr; and the correction factors were evaluated (where ever necessary) using CCD based ICP-AES technique. The sensitivity and the detection limits of the analytical channels of the elements in presence of uranium matrix were calculated. The present study also deals with the identification of suitable analytical lines of uranium and its detection limits.