Determination of trace elements in inorganic and organic materials by x-ray fluorescence spectroscopy

A new, almost universally applicable method for the trace analysis of inorganic and organic materials is described. The trace element (or elements) together with a suitable coprecipitating element is isolated from interfering elements by precipitation with a suitable organic or inorganic precipitant. The precipitate is then filtered on a paper disk and the collected trace element (or elements) is determined by X-ray analysis.     

Determination of trace elements in the water cycle by total-reflection x-ray fluorescence spectrometry

The determination of trace elements in the various stages of the water cycle is very important. Economic procedures for multi-element determinations of trace elements in various matrices are needed. The applications of total-reflection x-ray fluorescence spectrometry in this general area are reviewed briefly, with examples relating to rain, river and sea waters, sediments, particulate matter and manganese nodules and crusts, as well as mussel tissue. Up to 25 elements can be determined; these are S, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Pb, Se, Rb, Sr, Y, Zr, Mo, Ag, Cd, Sb and Ba. Preliminary treatments of the various matrices are described. Accuracy checks by analysis of reference standards and by application of independent techniques are reported.     

Determination of trace elements in macrozoobenthos samples by total reflection X-ray fluorescence analysis

The paper describes the analysis of a set of metals in macrozoobenthos samples from a river in Western Austria by using total reflection X-ray fluorescence analysis (TXRF). Metal concentrations in aquatic insect larvae from an industrially contaminated site are significantly higher than in larvae from a reference site. Furthermore, species-specific differences in metal accumulation were found. TXRF allows multi-element analysis of very low metal concentrations in very small sample masses (e.g. single aquatic insect larvae with a dry weight of only a few milligrams). Due to its multi-element capability and high sensitivity total reflection X-ray fluorescence analysis is a valuable tool for biomonitoring studies of metal contamination in aquatic ecosystems.     

Determination of trace siderophile elements in rock and meteorite samples by radiochemical neutron activation analysis

A simple and effective radiochemical procedure for radiochemical neutron activation analysis (RNAA) of ultra-trace siderophile elements (Ru, Re, Os and Ir) and rare earth elements (REEs) in rock and meteorite samples is presented. To design the procedure, several separation schemes of siderophile elements were examined by using radioactive tracers. By applying the procedure to rock and meteorite samples, we have determined Ru, Re, Os, Ir and REEs, and confirmed that our values were in agreement with the literature values. Our detection limits for Ru, Re, Os, La, Sm and Eu are significantly low compared with those for ICP-MS.     

Determination of trace elements in blood samples by TXRF analysis

Trace elements were determined by TXRF in whole blood samples in a randomly non-occupational exposed population living in the Metropolitan Zone of the Mexico Valley (MZMV). Arithmetic and geometric means of S, Ca, Cu, Zn, Rb and Pb concentrations, were on the reported range values for non-occupational population in other countries, while those of K and Br were higher, possibly due to dietary habits and geographical or environmental factors. The noticeable decline in blood lead level (91%) should be positively perceived. As a part of the Quality Control Program, a certified IAEA-A13 was tested. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of trace elements in ambient aerosol samples

A microwave-assisted digestion procedure using HNO₃, HF, and H₂O₂ has been developed for analysis of elements in ambient particulate matter (PM). The samples are collected on cellulose filters and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The ICP-MS is calibrated with external standards, and recovery of analytes is tested with NIST SRM 1648 Urban Dust. This method has been used to quantify the airborne concentrations of a large number of elements, including Ag, As, Ba, Be, Ca, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Ni, Pb, Rb, Se, Sb, Sr, Ti, Tl, V, and Zn. For the majority of these elements, recovery of the NIST SRM is within 15% of the certified values.     

Determination of trace amounts of mercury in rock samples

Summary A precise and accurate method is described for the measurement of ng quantities of mercury in inorganic samples such as rock, mineral ores and soil. The mercury is distilled from pulverized samples and collected on a silver gauze absorber. The mercury is then rapidly desorbed from the silver element using heat, and it is carried by gas entrainment into the measuring cell of an ultraviolet absorption analyzer. Readout of the mercury content can be made by measurement of peak heights on a strip chart recording, but more elegantly and accurately by the digital printout from a GC integrator. Calibration of the instrumental assembly, by injection of measured quantities of saturated mercury vapor, is simple, rapid and accurate.

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Zusammenfassung Eine genaue Methode zur Bestimmung von Nanogrammengen Quecksilber in anorganischem Material wie Gesteinen, Erzen und Bodenproben wurde beschrieben. Aus den gepulverten Proben wird das Hg abdestilliert und auf einem Silberdrahtnetz gesammelt. Dann wird es rasch durch Erwärmen desorbiert und mit einem Gasstrom in die Meßzelle eines UV-Ab-sorptionsgerätes geleitet. Die Ermittlung des Quecksilbergehaltes kann aus der Peakhöhe eines Schreibers, besser mit dem Digitalzähler eines GC-Integrators erfolgen. Die Eichung des Gerätes durch Einleiten gemessener Mengen von gesättigtem Quecksilberdampf ist einfach rasch und genau.

     

Determination of trace metals in water using x-ray fluorescence spectrometry

A simple, rapid and accurate method for water analysis is proposed. The analytical procedure for the determination of Fe, Mn, Zn, Cu, Cd, As, Pb and Se in water in concentrations as low as a few ppM involves precipitation with a carrier of the metals by diethyldithiocarbamate (DDTC) or 1-(2-pyridylazo)-2-naphthol (PAN) and filitration through a Millipore filter. The precipitates collected on the filter disc are examined by X-ray fluorescence analysis. PAN is excellent for the determination of several metal ions at the ppM level, and DDTC can be used with tartrate as a masking agent if water samples contain large amounts of iron(III).     

粉末压饼LA-ICP-MS测定土壤样品中微量元素

研究了采用粉末压饼制样LA-ICP-MS测定土壤样品中多元素的分析方法.在土壤样品中事先加入已知含量的In,并以聚四氟乙烯(PTFE)为粘合剂,在200 KN的压力下制备用于激光剥蚀的压饼.详细讨论了粉末压饼样品中元素的均一性及元素相对信号响应.所建立的方法用于土壤标准参考物质固体样品的直接分析,测定值与参考值具有较好的一致性.     

Using x-ray analogs of elements to be determined in the x-ray fluorescence analysis of liquid samples

To construct calibration characteristics in x-ray fluorescence analysis, it is proposed to use calibration samples that contain compounds of chemical elements whose bright characteristic lines are close in wavelength to the analytical lines of the analytes. This approach is efficient in determining rare and expensive elements. The proposed approach is checked experimentally in the determination of W, Re, Er, and Yb in solutions.     

固相微萃取-原子荧光测定鱼样品中痕量甲基汞

研制了一种用HF处理石英纤维表面的萃取纤维和一次性微量注射器组成的固相微萃取装置,研究了用甲基聚硅氧烷作为萃取头涂层对氢化甲基汞的萃取,得到的最佳条件是：在室温条件下,缓冲液的pH值为5、萃取时间为lh、NaCl的用量为2g、洗脱时间为50min、KBH4质量浓度为60g／L。在上述优化条件下,甲基汞的萃取率可以达到70％,检出限为0.17ng。测定了鱼样品中甲基汞,所测鱼虾中甲基汞的质量分数为12．4～53．4ng／g,加标回收率为87．6％～112．8％。     

阻抑荧光猝灭法测定环境水样中痕量砷

在H2SO4介质中,KIO4氧化吖啶黄,使体系褪色并伴随荧光猝灭,痕量的As(Ⅲ)能显著阻抑此反应,据此建立了一种新的荧光法测定痕量As(Ⅲ)。本文对该体系的实验条件进行了详细研究。在最佳条件下,方法的线性范围为5.0～400μg/L,检出限为2.4μg/L。方法已用于环境水样中痕量As(Ⅲ)的测定,加标回收率为94.2%～102.6%。     

Determination of trace elements in carbonate reference samples by instrumental neutron activation analysis

Twenty elements (Sm, U, As, Sb, La, Ce, Yb, Th, Cr, Eu, Hf, Ba, Cs, Tb, Sc, Rb, Fe, Zn, Ta, Co) have been determined by instrumental neutron activation analysis in GSJ/AIST carbonate reference samples, JCp-1 (Coral) and JCt-1 (Giant Clam), together with JLk-1 (Lake Sediment), JDo-1 (Dolomite) and JLs-1 (Limestone) reference samples.     

Determination of major,minor and trace elements in Iraqi vegetable samples by INAA

Our aim was to discover a method of separating zirconium(IV) and uranium(VI) from solutions. It is known that Zr(IV) and U(VI) are effectively extracted by tertiary amines from weak acidic sulfate solutions but the possibility of extraction decreases with increasing acidity. The transition from tertiary amine to primary amine Primene JMT enables the extraction of Zr also from more acidic solution. If both Zr and U are present in an aqueous solution, Zr is extracted preferentially and only the free part of the amine can convert uranium to an extract. The separation described below was carried out by preferentially stripping zirconium from the organic phase. The application of nitrate solution (2M HNO₃) to eliminate Zr from the solvent was tested. This method does not demand any special regeneration of the extraction agent and the amine nitrate, formed in the organic phase, can be used for further extraction of Zr without modification. Using this method of separation, a solution for producing pure ZrOCl₂·8H₂O was obtained.     

超声雾化-ICP-AES测定植物样品中的微量元素

研究了超声雾化-ICP-AES测定植物样品中As、Pb、Se、Bi、Ge、Mo的方法。对样品的测定条件进行了优化。在选定的仪器工作参数下,加标回收率达到95.5%~103%,RSD均小于3%。     

Determination of gold in geological samples by x-ray fluorescence spectrometry after extraction with tributyl phosphate

The behaviour of gold and elements impeding its x-ray fluorescence spectrometric (XRF) determination, namely zinc, lead and arsenic, was studied during their extraction from hydrochloric acid, nitric acid, and aqua regia solutions using tributyl phosphate as a solid extractant [SE(TBP)]. Extraction of gold from pulps after aqua regia leaching was found to be the most favourable approach for the quantitative and selective recovery of gold. The gold distribution ratio, D_Au, is ca. 10⁴ ml g^?1. For extraction from hydrochloric acid solutions the D_Au value also exceeds 10⁴ in the whole range of gold concentrations studied (10^?8?10^?4 M), but it decreases substantially with increasing extraction temperature, from 5 × 10⁵ ml g^?1 at 20°C to 9 × 10³ ml g^?1 at 70°C. An anomalously high distribution ratio of lead, D_Pb ≈ 10³ ml g^?1, was observed during extraction from hydrochloric solutions in the presence of chlorine. This could be explained by the formation of the chloro complexes of lead(IV). An XRF method for the determination of gold in natural samples was developed, which includes back-extraction of gold from SE(TBP) using a hot 0.025 M thiourea solution, providing a thin sample layer for secondary XRF. For 25 g of sample material the limit of determination is 10 ng g^?1 (10^?6%). The accuracy of the technique was checked using different reference materials. The results agreed within 10%.     

Determination of trace elements in small water samples by total reflexion X-ray fluorescence (TXRF) and by neutron activation analysis (NAA)

The problems encountered in the determination of trace elements in small sample volumes of the order of 1 to 10 l (e.g. in droplets of water) are discussed. Total reflexion X-ray fluorescence (TXRF) and neutron activation analysis (NAA) are applied for the determination of Na, Mg, K, Ca, Mn, Fe, Co, and Cu in concentrations of 0.01 to 10 mg/L in 1 to 10 L of water. The applied methods are described, the results are discussed and the advantages of TXRF are brought forward.     

Determination of rare earths and other trace elements in samples of Antarctica by neutron activation analysis

The concentrations of REE and other trace elements have been determined in samples of Antarctica by Instrumental Neutron Activation Analysis (INAA). The samples were collected from the West Lake area near Great Wall Station. The samples include sediment, residual plants, rock and soil taken from the bottom of the lake to 3.4 m deep. The amounts of samples were very rare. In order to get more information, reactor NAA using both short and long irradiations with K₀ standardization has been adopted. Nine rare-earth elements (REE) namely La, Ce, Nd, Sm, Eu, Tb, Dy, Yb, and Lu as well as other trace elements (As, Au, Ba, Br, Co, Cr, Hf, Sc, Se, Th, V, Zn) have been determined. The concentrations and distribution patterns of REE in the samples have been given.