Determination of rare earth elements in hot spring water and crater lake water samples by neutron activation analysis incorporating coprecipitation process using aluminium as a collector

Hot spring water and crater lake water samples were analyzed for their rare earth elements: (REE's) by neutron activation method, which, in the irradiation, sample preparation, incorporated a coprecipitation process in which aluminium was used as a collector. Ten REE's, La, Ce, Sm, Eu, Gd, Tb, Dy, Tm, Yb and Lu, were consequently detected and determined at the ppb level with satisfactory precision. It was shown that the aluminium coprecipitation is effective in enhancing concentrations of the REE's and reducing the amounts of interfering nuclides before neutron irradiation.     

Determination of rare-earth elements in environmental samples

A procedure is suggested of extraction-chromatographic pre-separation of REE's for the next activation determination. This method was applied for analyzing geological samples, underground and surface water, some technological materials.     

Rare earth element determinations at ultratrace abundance levels in geologic materials

The geochemically very important group of rare earth elements (REE) has frequently been analyzed with activation techniques. The importance of easy and quick techniques which are able to provide reliable data at very low abundance levels has been frequently discussed. We present three different methods using activation techniques yielding REE data at very low abundance levels in geologic materials. With proper selection of counting conditions and irradiations it is possible to use pure instrumental neutron activation analysis at ppb abundance levels (depending on the type of the material). A second method involves group separation of the REE's before irradiation, which yields data for all REE's, but is rather time consuming. The best results were obtained with a group separation after activation and several counting cycles, giving data for 8 REE's. This method has the advantage of providing results even in the sub-ppb range.     

Determination of rare earth elements in hot spring and crater lake waters by epithermal neutron activation analysis

Determination of the rare earth elements (REE's) in acidic hot spring and crater lake waters by neutron activation analysis (NAA), in which activation was performed mostly by epithermal neutrons (epithermal NAA) was investigated. Nine REE's, La, Ce, Sm, Eu, Tb, Ho, Tm, Yb and Lu, out of fourteen naturally existing REE's were determined at ppb levels with satisfactory precision. The epithermal NAA was found to be more effective in the determination of Sm, Tb, Ho and Yb than normal NAA, in which activation was performed mainly by thermal neutrons. Combined use of the epithermal and normal NAA's enabled the determination of eleven REE's, La, Ce, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb and Lu.     

Determination of praseodymium,neodymium and erbium in hot spring and crater lake waters by neutron activation analysis incorporating the standard addition technique

Previously undetermined three rare earth elements (REE's), Pr, Nd and Er, in acidic hot spring and crater lake waters were determined at ppb levels by neutron actavation analysis with the standard addition technique. Errors on final detemined values were 7.1–56%. Combining the present results and the results previously obtained amounts to the determination of all 14 naturally occuring REE's in the waters.     

Rare earth element patterns in Nigerian coals

Rare Earth Elements (REE's) retain group coherence in their environment and are therefore useful geochemical markers. We report the pattern of ten REE's (La, Ce, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Lu) determined by Instrumental Neutron Activation Analysis (INAA) for coals obtained from eight mines in Nigeria, namely, Okaba, Enugu, Ogbete, Onyeama, Gombe, Lafia, Asaba and Afikpo. Our results show the existence of fractionations with the highest index of 13.19 for Lafia coal, depletion in HREE, negative Eu anomaly for most of the coals, REE patterns that are consistent with chondritic trends; prominent (Eu/Eu^*)_cn for Okaba and Gombe coals. Variations in geochemical data observed could suggest strong departures from band metamorphism during the coalification events of the Benue Trough geosynclines, where the coal deposits are all located.     

Precision and accuracy of laser ablation-ICP-MS analysis of rare earth elements with external calibration

Solid sample introduction into an ICP-MS by laser ablation is an effective method for the total analysis of rare earth elements (REEs) in soils because no digestion is needed. A problem of the method, however, is the difference of the ablated mass for each laser shot. Therefore, internal standard for the compensation of signal instability, sample preparation, and the calibration method have to be carefully chosen.The analyzed sample was a certified standard provided by IAEA (SOIL-7). The sample was mixed with an internal standard solution and polyethylene (PE), dried, homogenized in a ball-mixer/mill, and pressed to a pellet. For the calibration 5 external standards with increasing REEs concentrations (0.4–20 g/g) as well as a blank were prepared in the same way.The analysis of the pellets was performed on a VG PlasmaQuad II + with a LaserLab unit. The laser ablation-cell was modified to improve the sample particle transportation characteristics and to allow a quicker sample-exchange. The pellets were ablated from six different spots for 60 s each with a laser-repetition rate of 4 Hz.The correlation coefficients of the calibration curves based on 5 standards, were better than 0.995. The concentrations c_A of the 15 REEs in the soil sample were determined with an average relative confidence interval 100(CI)/c_A of 6.95%, as a figure for the precision. This good precision have been obtained with a new laser ablation cell, which will be described in detail.With 2 exceptions (Ce and La) the measured concentrations were within the confidence intervals (CI) of the certified values. Therefore, with respect to accuracy and precision, the presented method offers a convenient way to analyze homogeneous and powdered soil samples for REE's without digestion. Since a good calibration for the REE determination may be obtained, the laser sampling variance (within the sample) is less significant than the analytical variance. Automation of the method is possible by construction of an autosampler based on the modified laser cell.Presented in part at the 1993 European Winter Conference on Plasma Spectrochemistry, Granada, Spain     

Determination of epichlorohydrin in water and sewage samples

The simple, quick and effective methods for the analysis of epichlorohydrin (ECH) in water and sewage samples with the use of gas chromatography have been presented. From among all the methods developed, the procedures for monitoring drinking-water quality and the methods which allow the determination of epichlorohydrin in sewage samples have been selected.

The limits of ECH detection have been determined by direct aqueous injection (DAI) into the chromatographic column and an analysis with the application of a flame ionization detector (FID), a mass spectrometry detector (MS), an electron capture detector (ECD) and atomic emission detection (AED) detectors. The method allows the determination of ECH in water samples at the concentration level of 0.1 mg l⁻¹. Moreover, the developed methods of water samples preparation for chromatographic analysis using the following extraction methods: headspace (HS), stripping with adsorption on solid phase, liquid–liquid extraction (LLE), solid phase extraction (SPE) and solid phase microextraction (SPME) have been evaluated. The limits of ECH detection for each procedure with the application of gas chromatography (GC) combined with various detectors have been determined and their statistical evaluation has been presented. The SPME method allowed us to determine ECH in water samples at the concentration levels of 1.0 ng l⁻¹.

The results of studies on the choice of the selective methods allowing ECH analysis in sewage samples have been demonstrated. The applied SPME method was found to be a quick and effective technique to determine micro trace amounts of ECH in samples containing high amounts of various organic compounds.     

Simple and rapid determination of phosphorus in meat samples by WD-XRF method

The wavelength dispersive X-ray fluorescence (WD-XRF) method for phosphorus determination in meat samples has been described. The effects of sample pretreatment on the XRF analysis have been discussed. The phosphorus content determined in meat samples ranged from 603 ± 6 to 613 ± 19 mg P/100g dry mass (d.m.), depending on the sample preparation technique. The meat samples spiked with phosphates have been used for the calibration procedure. The accuracy was determined against a number of certified reference materials (SMRD 2000, RF 8414, NIST-1568A, and NIST-1549), and recovery was assayed using the standard addition procedure. The proposed method has been compared with the standard spectrophotometric method (PN-ISO 13730, 1999) of total phosphorus determination. The sample pretreatment procedure has been reduced to minimum the presented results suggest the WD-XRF method can be an alternative to the spectrophotometric analysis.     

Voltammetric determination of platinum in inorganic complexes and in water, geological and biological matrices using laboratory- and field-based instrumentation

The extremely sensitive catalytic hydrogen ion reduction wave observed after the formation of a platinum-formazone complex at a mercury electrode in a hydrazine-formaldehyde-H2SO4 medium has been utilised to determine platinum voltammetrically in well characterised platinum inorganic complexes (oxidation states O, II and IV) and in biological, geological and water samples. Experimental conditions have been optimised and sample-treatment procedures for various matrices have been critically evaluated for the quantification of platinum by the standard additions method. The determination of platinum in geological samples by this method has been compared with an inductively coupled plasma mass spectrometric method. Both conventional and portable field-based instrumentation have been used in the studies, and the possibility of developing a field-based method for the determination of platinum has been investigated. Despite the inherent sensitivity of the method, which enables concentrations down to 0.01 p.p.b. to be detected in simple matrices, natural levels in water and biological materials, where matrix effects suppress the voltammetric response, are often below the detection limit.     

用ICP-AES法测定首饰金的成分

本文报道采用ICP-AES法直接同时测定首饰金中合金无素及主要杂质元素含量,通过计算求得金含量。确定了仪器的最佳工作条件,进行了干扰试验。方法适用于18k～99.99%成色的首饰金。测定的RSD为<0.01%(对于高纯度金祥n=10)～0.2%(对于10k金样n=10)之间,分析结果表明,方法准确、快速、简便且样品消耗量少。     

Spectrophotometric assay of Isoproturon and Metoxuron in technical grade and formulation samples using 3-methylbenzothiozolin-2-one hydrazone hydrochloride

A spectrophotometric method for the assay of Isoproturon and Metoxuron in technical grade and formulation samples has been developed using the oxidative coupling reaction with 3-methylbenzothiozolin-2-one hydrazone hydrochloride (MBTH). The reaction variables have been optimized and the reaction mechanism is discussed. The method is simple, rapid and has been successfully applied for the assay of Isoproturon and Metoxuron in commercial grade technical and formulated samples. The percent relative standard deviation is found to be in the range 0.34-1.00 for Isoproturon and 0.33-0.57 for Metoxuron.     

Rare earth element patterns in lake sediments as studied by neutron activation analysis

Using instrumental neutron activation analysis, the vertical distribution of La, Ce, Nd, Sm, Eu, Tb, Yb and Lu was determined in 3 well dated sedimentary cores collected from Laguna Mar Chiquita, Argentina. Validation of the methodology was done using the Soil 7 (IAEA) reference material. The REE contents vary according to core location and lithological units, depending on the proportion of fluvial terrigenous components in the lake sediments. Lithologies with higher proportion of terrigenous components show higher REE concentrations, suggesting that the dominant REE carrier phase might be a detrital mineral. There is a consistent value of about 1.2 for (La/Yb)_N and (LREE/HREE)_N ratios for all sediments at the three sites, indicating a slight LREE enrichment in relation to the average shale NASC. Ce/Ce* values are close to 1.0, meaning that Ce behaves similarly to other light REE's.     

Method development for the determination of manganese, cobalt and copper in green coffee comparing direct solid sampling electrothermal atomic absorption spectrometry and inductively coupled plasma optical emission spectrometry

A method has been developed for the determination of cobalt, copper and manganese in green coffee using direct solid sampling electrothermal atomic absorption spectrometry (SS-ET AAS). The motivation for the study was that only a few elements might be suitable to determine the origin of green coffee so that the multi-element techniques usually applied for this purpose might not be necessary. The three elements have been chosen as test elements as they were found to be significant in previous investigations. A number of botanical certified reference materials (CRM) and pre-analyzed samples of green coffee have been used for method validation, and inductively coupled plasma optical emission spectrometry (ICP OES) after microwave-assisted acid digestion of the samples as reference method. Calibration against aqueous standards could be used for the determination of Mn and Co by SS-ET AAS, but calibration against solid CRM was necessary for the determination of Cu. No significant difference was found between the results obtained with the proposed method and certified or independently determined values. The limits of detection for Mn, Cu and Co were 0.012, 0.006 and 0.004 μg g⁻¹ using SS-ET AAS and 0.015, 0.13 and 0.10 μg g⁻¹ using ICP OES. Seven samples of Brazilian green coffee have been analyzed, and there was no significant difference between the values obtained with SS-ET AAS and ICP OES for Mn and Cu. ICP OES could not be used as a reference method for Co, as essentially all values were below the limit of quantification of this technique.     

酚醛类高分子复合材料中残余三甲胺的萃取及气相分析

 根据相平衡的原理 ,建立了酚醛类高分子复合材料中残余三甲胺含量的分析方法。测试过程包括预处理、萃取及气相分析。复合材料经过一定的预处理后 ,恒温 16h ,吸附在其中的三甲胺充分转移到液相 ,最后用气相测试液相中三甲胺的浓度。方法准确灵敏 ,测试结果符合微量分析的要求 ,可用于实际样品的测试。     

Radioisotope x-ray fluorescence analysis of ancient pottery from Tel Kouzama site in Damascus, Syria

The radioisotope X-ray fluorescence method has been utilized in the analysis of thirty nine archaeological pottery fragment samples from Tel Kouzama site, Damascus city, Syria. The samples were irradiated by a 109Cd radioisotope source (-9 10(8) Bq) for 1000 s. 17 chemical elements were determined. These elemental concentrations have been processed using two multivariate statistical methods, cluster and factor analysis in order to determine similarities and correlation between the various samples. Factor analysis confirms that samples were correctly classified by cluster analysis. These two methods suggest that samples can be considered to be manufactured using four different sources of raw material.     

GC/MS and chemometrics in archaeometry

Summary 100 mg amounts of glue on two copper-age arrowheads have been investigated by means of gas-chromatography/mass spectrometry and chemometrics. The samples have been identified as birch bark derivatives, but the distribution patterns of triterpenoids and steroids show significant differences to similar samples from younger archaeological periods that can be explained by the use of a different species of birch and a different method of preparation.     

Determination of short chain aliphatic acids in silage effluents by ion exclusion chromatography

Summary Short chain aliphatic acids are important components of the dissolved organic matter in silage effluents. Although ion exclusion chromatography offers some advantages for the analysis of these compounds, no attempt has yet been made to prove the suitability of this method for silage effluent analysis. In order to gain experience in this field, the separation characteristics of a Dionex ion exclusion column (IonPac-ICE As5) have been evaluated, the separation conditions have been improved, and several sample clean-up methods have been checked.Ten effluents generated during silaging of five different crops were collected from Bavarian farms and analyzed. Lactic and acetic acids were the predominant aliphatic acids. Pyruvic, formic, propionic, and succinic acid were detected in all samples, whereas glyceric and iso-citric acid were found in a few samples only.If some restrictions of substance specificity and separation efficiency can be accepted, the analytical method presented will be a reliable tool for the analysis of carboxylic acids in silage effluents.     

Use of the Eurachem guide on method validation for determination of uranium in environmental samples

Three analytical methods for determination of uranium in environmental samples by a fluorescence technique have been validated and compared in accordance with the Eurachem Guide on method validation. The first method depends on uranium separation from iron using the mercury anode technique; in the other two methods uranium is separated from iron on an anion exchange column by use of either a solution of hydrochloric acid containing ascorbic acid and hydrazine hydrate or a dilute sulfuric acid solution. Detection limits, repeatability, reproducibility, and recovery coefficient were the main validation characteristics. The results showed that better statistical values can be achieved by using the third method. Control charts for in-house control samples and international intercomparison samples have also shown that the third method is more statistically stable with time. In addition, uncertainties of measurement were estimated and compared for the three methods. It was found that the Eurachem Guide and comparison of quality statistical validation data can be good tools for selection of the appropriate method for an application.     

Determination of residual chlorine in greywater using o-tolidine

The determination of chlorine with o-tolidine in greywater has been studied, and a batch method and a sequential injection method have been proposed. It was found that the reaction of o-tolidine with chlorine was slower in a greywater matrix. Grey water samples must be filtered before analysis, or alternatively, a blank of sample must be measured. The samples are very unstable, and after 2 h of storage in dark conditions at 4 degrees C the chlorine concentration can diminish. The standard addition method, in some samples gave unsatisfactory results as a consequence of matrix effects. It was concluded that samples with a total organic carbon (TOC) higher than 60 mgCl(-1) can not be accurately analysed using these methods. However, samples with a TOC lower than 60 mgCl(-1) gave 100+/-3% recoveries. The linear range of the methods was 0-3.0 and 0-5.0 mgCl(2)l(-1), and the limit of quantification 0.2 and 0.5 mgCl(2)l(-1), for the batch method and the sequential injection method, respectively. This is the first paper devoted to grey water from the analytical chemistry point of view.