Study of Sediment Samples Using Instrumental Photon Activiation Multi-Elemental Analysis

Abstract

Instrumental Photon Activation Analysis (IPAA) has been used in many fields including environmental geochemistry. In the analysis of soil and sediment samples, the sensitivity of IPAA is comparable to that of standard methods such as atomic absorption spectroscopy. A major advantage of IPAA is that minimal sample processing is required and multi-element analyses can be obtained. In this work, the method of Internal Standard Coupled with Standard Addition Method (ISM-SAM) was applied to IPAA analysis of sediment samples. The equation used in ISM-SAM was derived in detail and the relationship between the elemental mass and the gamma peak counts in the measured spectra was established. It was found that accurate results can be obtained even when the sample and the reference are irradiated at different photon fluxes and measured in different geometries. The ISM-SAM equation was refined to better quantify the relationship between the addition amount and the uncertainty. Applying refined ISM-SAM, a sediment sample from Hudson River was analyzed. The concentrations of Ni, Pb, Zr, Ca, Fe, Mg, Na, Ti, As, Cr, Ce, Co, Rb, and Zn were determined and compared with the results obtained from Atomic Absorption analysis of total acid digests. For elements analyzed by both methods, excellent agreement was found. Meanwhile, the detection limits of photon activation analysis for selected elements were obtained based on the present experimental conditions.     

Optimal use of instrumental neutron and photon activation analyses for multielement determinations in sewage sludges

A combination of instrumental neutron activation analysis (INAA) and instrumental photon activation analysis (IPAA) methods has been developed for multielement determinations in a variety of sludges and fertilizers. The precision and accuracy of both the methods have been evaluated by analyzing replicate samples, NBS standard reference materials, and an interlaboratory intercomparison sewage sludge sample. The concentration rages of up to 50 elements in raw and chemical sludges, sludge-based fertilizers, and other organic and inorganic fertilizers are reported here. The advantages and limitations of the INAA and IPAA methods are also discussed here.     

Determination of noble metals in silicate rocks, ores and metallurgical samples by simultaneous multi-element graphite furnace atomic absorption spectrometry with Zeeman background correction

A new method has been developed for rapid determination of mug/g and ng/g amounts of noble metals in silicate rocks, ores and metallurgical samples by attacking with hydrofluoric acid and aqua regia, preconcentration by ion-exchange chromatography and measuring in a simultaneous multi-element graphite furnace atomic absorption spectrometer equipped with a polarized Zeeman background correction device which eliminated interferences from any incompletely separated common elements. The method was tested for Ru, Rh, Pt, Ir, Pd, Ag and Au with three Canadian certified reference materials, and then applied to the determination of ng/g amounts of these elements in four new Canadian candidate reference materials.     

Rapid determination of uranium at the nanogram level in geological and biological materials

A rapid method for the determination of uranium at nanogram levels in geological and biological materials is described. The method is based on the separation of 23.5 min²³⁹U, produced on neutron activation, by solvent extraction with TBP from nitric acid medium in the presence of HF, which prevents interference from Th; a number of other possibly interfering elements were shown to be negligibly extracted. The method is selective and sensitive enough for the determination of nanogram levels of uranium in soils, ores and biological samples. Results for some standard reference materials were in good agreement with certified values. Presented at the International Conference on Analytical Chemistry, Interan '76, Prague, August 1976.     

Sample Preparation and X-Ray Fluorescence Analysis of Sulfide Ores

Sulfide ores with varied concentrations, including four ore reference materials (zinc, copper, and iron sulfides) and two copper-nickel and iron sulfide samples, were used to develop an improved method for their analysis by X-ray fluorescence. The optimum conditions were established for the fusion of homogeneous stable glass disks. Different weights of silica were added to the samples, which were then fused with a lithium borate flux. The amount of silica varied from 1:20 for samples with low sulfur concentrations to 1:5 for those with high concentrations. The weight ratio of sample (including silica) to lithium tetraborate was 1:14. Lithium nitrate was used as a pre-oxidizing reagent to prevent degradation of platinum–gold crucibles. After pre-oxidation at 580°C for 13 minutes, the temperature was increased to 1100°C for 12 minutes. The relative standard deviations for major and trace elements were generally better than 5% and 10%, respectively.     

Multielemental analysis of metallurgical samples by thermal neutron activation

Instrumental neutron activation analysis (INAA) was applied to investigated a total of 16 samples of raw materials, intermediate and final products involved in metallurgical processes in Romanian Iron and Stell works Sidex Galatzy: iron ores and pellets from different regions of the world, cast iron, slag and steels. A series of chemical elements was determined in the analyzed samples: Al, As, Ce, Co, Cr, Fe, La, Mn, Na, Sc, Sm, V, W. A qualitative discussion regarding the passing of from elements with different chemical affinity for oxygen compared to that of iron, from the raw materials to slag or to finite products is presented.     

Rapid dissolution procedure for base-metals-bearing complex materials for quality control assessment

A less labour-intensive method, involving a mixture of 1.0 g MnO₂ + 20 mL HCl (11), is proposed for decomposing seven ores and six metallurgical products for accurate and precise estimation of copper, lead, zinc, cobalt and nickel for quality control assessment. Twentyone international reference materials were also analysed. Results of regression analyses are presented and intermethod comparison studies reveal that the probability of results being different compared with a reference method was less than 1%. Sample decomposition is straightforward and the method has been found to be very simple, rapid and easily adaptable, as it involves no separation of the analyte from the matrix elements.     

碱熔-电感耦合等离子体发射光谱法测定锡矿石中锡

本文采用过氧化钠碱熔消解样品,电感耦合等离子体发射光谱( ICP-AES)法,对锡矿石中锡含量进行了测定。当样品称样量为0.2g时加入2g过氧化钠就能使样品消解完全。为避免水解对测定结果的影响,样品处理后应尽快进行测定。本方法测定锡的检出限为38.4mg/ kg,12次平行测定的相对标准偏差小于5%,对标准物质的测定结果也令人满意。     

电感耦合等离子体发射质谱法测定钨矿石中的钨华

建立电感耦合等离子体发射质谱法测定钨矿石中钨华的含量。用氨水溶液对矿石样品进行浸取分离,将浸取液稀释10倍体积后测定,以3%盐酸溶液作为测定介质。WO3的质量浓度在0~100 ng/m L范围内与信号强度呈良好的线性关系,相关系数为0.999 9,方法检出限为0.5 ng/m L。用该方法对5个钨矿石样品和2个标准物质样品中的钨华进行测定,测定结果的相对标准偏差为2.15%~9.46%(n=12),且与经典方法极谱法测定结果的相对偏差小于10%。该方法快速、简便,精确度较高,可用于钨矿石中钨华的测定。     

Fractionation studies of trace elements in Polish uranium-bearing geological materials: potential environmental impact

The samples of U deposits from Podlasie Depression (East Poland) and Peribaltic Syneclise (Northeast Poland) were studied to state the U and accompanied metal content and to estimate a potential environmental impact caused by the studied area. Sequential extraction is an effective method for assessing the heavy metal behaviour in environment in such environmental materials as soils, sediments, different wastes and ores.

The modified Bureau of Reference of the European Commission sequential extraction procedure has been used for fractionation study of nine elements (U, V, Mn, Co, Ni, Cu, Zn, Cd and Pb) in two kinds of U ores: dictyonema shale and sandstone. The total content and the content in each fraction of metals of interest were determined by the inductively coupled plasma mass spectrometry method.

The obtained results show the high mobility of such elements as Co, Zn and Ni in shale and U, Co and Mn in sandstone. These results make it possible to assess the environmental risk associated with heavy metals occurring in tested U-bearing ores.     

Spectrophotometric determination of germanium in ores, concentrates, zinc-processing products and related materials with phenylfluorone and cetyltrimethylammonium bromide after separation by iron collection and heptane extraction of germanium tetrachloride

A method for determining approximately 0.2 microg/g or more of germanium in ores, concentrates, zinc-processing products and related materials is described. The sample is decomposed by fusion with sodium peroxide and the cooled melt is dissolved in dilute sulphuric acid. Silica, if > 50 mg, is removed by volatilization with hydrofluoric acid. Germanium is separated from sodium salts by co-precipitation with hydrous ferric oxide, the precipitate is dissolved in 3M hydrochloric acid and germanium is subsequently separated from iron(III) and other co-precipitated elements by a single heptane extraction of germanium tetrachloride from approximately 9.4M hydrochloric acid. The extract is washed with 12M hydrochloric acid to remove residual iron(III), then germanium is stripped with water and determined spectrophotometrically with phenylfluorone in a 1.4M hydrochloric acid-0.002M cetyltrimethylammonium bromide medium in the presence of ascorbic acid as a reductant for co-extracted chlorine. The apparent molar absorptivity of the complex is 1.71 x 10(4) l.mole(-1).mm(-1) at 507 nm, the wavelength of maximum absorption. Up to 5 mg of tin(IV), 10 mg of antimony(V) and tungsten(VI) and approximately 50 mg of silica do not interfere. Germanium values are given for some Canadian certified reference ores, concentrates and iron-formation samples and for a metallurgical dust.     

Trace element content of phosphorite reference materials (BCR-RM-032, PRH and IAEA-434)

Analysis of geological materials requires the use of matrix specific reference materials (RMs). Phosphate rocks (PR), the basic ingredient of phosphate fertilizers, are very important in agriculture. A project was undertaken to study the PRs of the Hazara Deposits of Pakistan. Due to the unavailability of phosphate rock reference materials (PR-RMs) with a large number of certified elements, validation of the results was problematic when carrying out elemental analysis of PR samples and their derived products. Therefore a parallel study was performed to determine the composition of three phosphate based RMs; BCR-RM-032 (Natural Moroccan Phosphorite), IAEA-434 (Phosphogypsum) and PRH (a local PR-RM from the Hazara Deposits of Pakistan). Instrumental Neutron Activation Analysis was used for this purpose and more than 30 elements including rare earth elements were determined in the three PR samples.     

Untersuchungen zur gleichzeitigen Bestimmung von Molybd?n und Wolfram in Proben mit schwierigen Matrices mit induktiv gekoppeltem Plasma

Summary Inaccurate values are often obtained in the determination of molybdenum and tungsten in difficult complex matrices — ores, processing and metallurgical products. The main reason for this effect is due to spectral interferences. Background equivalent concentrations caused by changes of background nearby the measured spectral line are calculated for the established interferent matrix elements. It is possible with the applied sample treatment to perform successful analyses of samples with very variable matrix composition.     

Determination of impurities in uranium matrices by time-of-flight ICP-MS using matrix-matched method

The analysis of impurities in uranium matrices is performed in a variety of fields, e.g., for quality control in the production stream converting uranium ores to fuels, as element signatures in nuclear forensics and safeguards, and for non-proliferation control. We have investigated the capabilities of time-of-flight ICP-MS for the analysis of impurities in uranium matrices using a matrix-matched method. The method was applied to the New Brunswick Laboratory CRM 124(1–7) series. For the seven certified reference materials, an overall precision and accuracy of approximately 5% and 14%, respectively, were obtained for 18 analyzed elements.     

Comparison of the role of photon and neutron activation analyses for elemental characterization of geological,biological and environmental materials

The potential of photon activation analysis (PAA) for multielement trace analysis can hardly compare with that of neutron activation analysis (NAA). However, PAA appears superior over NAA for the determination of a number of elements, namely C, N, O, F, Mg, Si, Ca, Ti, Ni, Sr, Y, Zr, Nb, Sn, Tl and Pb in geological, environmental and biological materials. Most of these and other elements can be determined using nondestructive, instrumental PAA (IPAA), especially in geological materials. The possibilities of IPAA for multielement analysis using photoexitation and other photonuclear reactions are reviewed and compared with those of instrumental NAA (INAA), namely for geological materials. The need for and usefulness of radiochemical PAA (RPAA) procedures are also discussed.     

X射线荧光光谱法同时快速测定锑矿石中伴生及有害元素

采用粉末压片制样,波长色散型X射线荧光光谱法测定锑矿石中9个次量伴生及有害元素Cu、Pb、Zn、As、Co、Ni、W、Ba、S.选用国家标准物质和人工合成标准参考物质建立校准工作曲线,采用经验系数法和散射线内标法校正基体效应和元素重叠干扰.方法的检出限低、精密度(RSD,n=12)小于5%,测定结果与参考值或化学值一致性良好.与化学法相比,操作简单、快速、准确度高,精密度好,有效解决化学法在锑矿石伴生、有害等微量组分分析中过程烦琐、干扰严重等问题.     

Determination of trace elements in various materials by activation analysis

Recent works on the trace analysis of various materials by activation analysis are summarized. INAA and IPAA are applied for the multielement determination of various standard reference materials and electronic materials. As an example, the analytical results of pepperbush and fluoride glass are shown. In activation analysis using chemical separation, the destructive neutron activation analysis coupled with isotope addition technique is presented and applied to the determination of trace impurities in indium phosphide. Selective substoichiometry and substoichiometric separagtions of some elements are also introduced.     

Determination of minor elements in steelmaking flue dusts using laser ablation inductively coupled plasma mass spectrometry

Element determination in solid waste products from the steel industry usually involves the time-consuming step of preparing a solution of the solid. Laser ablation (LA) inductively coupled plasma mass spectrometry (ICP-MS) has been applied to the analysis of Cr, Ni, Cu, As, Cd and Sn, elements of importance from the point of view of their impact on the environment, in electric arc furnace flue dust (EAFD). A simple method of sample preparation as pressed pellets using a mixture of cellulose and paraffin as binder material was applied. Calibration standards were prepared spiking multielement solution standards to a 1:1 ZnO + Fe₂O₃ synthetic matrix. The wet powder was dried and mechanically homogenised. Quantitative analysis were based on external calibration using a set of matrix matched calibration standards with Rh as a internal standard. Results obtained using only one-point for calibration without matrix matched, needing less time for standardization and data processing, are also presented. Data are calculated for flue dust reference materials: CRM 876-1 (EAFD), AG-6203 (EAFD), AG-6201 (cupola dust) and AG-SX3705 (coke ashes), and for two representative electrical arc furnace flue dusts samples from Spanish steelmaking companies: MS-1 and MS-2. For the reference materials, an acceptable agreement with certificate values was achieved, and the results for the MS samples matched with those obtained from conventional nebulization solutions (CN). The analytical precision was found to be better than 7% R.S.D. both within a single pellet and between several pellets of the same sample for all the elements.     

Simultaneous determination of chromium, selenium, and molybdenum in nutritional products by inductively coupled plasma/mass spectrometry: single-laboratory validation

An inductively coupled plasma/MS method was developed for the simultaneous determination of Cr, Se, and Mo in infant formulas and other nutritional products. All samples were digested using a closed vessel microwave oven system, together with Ni and Te internal standards. The practical quantitation limits for Cr, Se, and Mo were 0.4, 0.2, and 0.4 ng/mL, respectively; dilution factors were 250 for powders and 50 for liquids. The Cr, Se, and Mo concentrations in 10 nutritional products were within specification limits, and within-day and day-to-day (6 independent days) precision values were <5% RSD. For two control samples, the observed precision was < or = 2% RSD over 10 independent days. In three National Institute of Standards and Technology standard reference materials, Cr, Se, and Mo results were within the certified limits. The average sample spike recoveries for 10 nutritional products ranged from 93 to 107%. Robustness studies showed a minimal effect from concomitant easily ionized element concentrations. However, the choice of internal standard and matrix matching carbon content were critical to obtaining accurate Se results. All indications are that this method would be a suitable candidate as a global reference method for the determination of these trace elements in nutritional products.     

Determination of cadmium, lead, iron, nickel and chromium in selected food matrices by plasma spectrometric techniques

In the frame of a study aimed at investigating the transfer of metal contaminants through the food chain and the effects of food processing, five elements, namely Cd, Pb, Fe, Ni and Cr, were accurately determined in (i) durum wheat grain and derived products, (ii) wheat-based reference materials, (iii) drinking water, used both as an ingredient and for technological purposes in the investigated industrial process. Microwave closed vessel digestion was selected as the dissolution technique for solid samples, whereas water samples were acidified with ultrapure nitric acid and analysed directly. As several analytes had to be quantified at trace or ultratrace levels, inductively coupled plasma mass spectrometry (ICP-MS) was resorted to for analytical determinations. Overall, this straightforward analytical approach enabled to detect the often small changes in element concentration associated with the different technological steps of processing. Nevertheless, detection of heavily interfered elements, especially Cr, as well as analyte quantification at ultratrace-level level in water, posed analytical challenges that required suited analytical solutions.Changes in the sample introduction system and complementary use of inductively coupled plasma atomic emission spectrometry (ICP-AES) straightforwardly overcame the difficulties in determining the analytes in the selected food matrixes. The benefits of ultrasonic nebulization in reducing the effects of problematic spectral interferences were demonstrated. Overall, a robust and high-throughput analytical method was outlined.