Multi-element determination of trace elements in whole blood and blood serum by TXRF

Summary The suitability of total-reflection X-ray fluorescence analysis (TXRF) for multi-element determination in whole blood and human serum has been investigated. In combination with microwave digestion with nitric acid the elements P, S, K, Ca, Fe, Cu, Zn, Se, Rb, Sr, and Pb were determined in samples from several patients. The detection limits for heavy metal traces are in the range of 0.02 –0.08 g/ml, the precision is in the range of 2 –10%. The elements Mn, Ni and Pb could additionally be determined after iron-(only necessary for whole blood) and salt-matrix separation. In this way the detection limits could be improved by more than one order of magnitude (0.002 g/ ml). The accuracy of the results and the reliability of the analytical procedures are checked with the help of several certified reference materials. In general the accuracy is in the range of 2–15%.

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Multielement-Bestimmung von Spurenelementen in Gesamtblut und Blutserum durch TXRF

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Dedicated in gratitude to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

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.     

Application of different activation analysis techniques for determination of trace elements in human blood

One of the requirements of stable isotope tracer technique is detection of two isotopes of same element. It is preferable to use instrumental techniques in order not to contaminate the samples. Different instrumental nuclear techniques namely neutron activation analysis (NAA), photon activation analysis (IPAA), and prompt gamma ray activation analysis (PGAA) were tried on human blood samples. The techniques were found to be complementary to each other, NAA being the most sensitive of the three. Zinc is choosen for validation work among the three feasible elements (Zn, Cr, Se) for stable isotope tracer technique. As NAA was not sufficient to detect two isotopes of Zn, a radiochemical separation scheme was developed later.     

Comparison of three analytical methods for the determination of trace elements in whole blood

Three different analytical techniques were compared in a study of the role of trace elements in multiple sclerosis. Data for eight elements (Cd, Co, Cr, Cu, Mg, Mn, Pb, Zn) from neutron activation, flame atomic absorption and electrothermal atomic absorption methods were compared and evaluated statistically. No difference (probability less than 0.001) was observed in the elemental values obtained. Comparison of data between suitably different analytical methods gives increased confidence in the results obtained and is of particular value when standard reference materials are not available.     

Enrichment method for trace amounts of rare earth elements using chemofiltration and XRF determination

A preconcentration method for subsequent determination of rare earth elements (REE) by X-ray fluorescence (XRF) spectrometry was developed. The method is based on using (o-[3,6-disulfo-2-hydroxy-1-naphthylazo]-benzenearsonic acid) (Thorin) as a complexing agent which is retained on a polyamide membrane by a chemofiltration process. The pH dependence of the chemofiltration of these metal ions on the membrane and other variables, such as flow-rate, contact time, kinetic of complex formation, etc. were determined. The membrane containing the chemofiltrate formed a thin film, which eliminated the interelemental effects when measured by XRF. The detection limits were 23, 23 and 49 ng/mL for Sm(III), Eu(III) and Gd(III), respectively. High enrichment factors were obtained. The method was successfully applied to the preconcentration of Sm(III), Eu(III) and Gd(III) from different samples. Received: 8 March 2000 / Revised: 9 May 2000 / Accepted: 15 May 2000     

Enrichment method for trace amounts of rare earth elements using chemofiltration and XRF determination

A preconcentration method for subsequent determination of rare earth elements (REE) by X-ray fluorescence (XRF) spectrometry was developed. The method is based on using (o-[3,6-disulfo-2-hydroxy-1-naphthylazo]-benzenearsonic acid) (Thorin) as a complexing agent which is retained on a polyamide membrane by a chemofiltration process. The pH dependence of the chemofiltration of these metal ions on the membrane and other variables, such as flow-rate, contact time, kinetic of complex formation, etc. were determined. The membrane containing the chemofiltrate formed a thin film, which eliminated the interelemental effects when measured by XRF. The detection limits were 23, 23 and 49 ng/mL for Sm(III), Eu(III) and Gd(III), respectively. High enrichment factors were obtained. The method was successfully applied to the preconcentration of Sm(III), Eu(III) and Gd(III) from different samples. Received: 8 March 2000 / Revised: 9 May 2000 / Accepted: 15 May 2000     

Development of a procedure for the multi-element determination of trace elements in wine by ICP-MS

An inductively coupled plasma mass spectrometric (ICP-MS) procedure has been developed for the determination of trace elements in wine. The procedure consists in simple 1+1 dilution of the wine and semi-quantitative analysis (without external calibration) using In as internal standard. Thirty-one elements at concentrations ranging from 0.1 mg mL(-1) to 0.5 ng mL(-1) can be determined by ICP-MS analysis with and without digestion. It was investigated whether a matrix effect observed for EtOH in the wine matrix can be overcome by application of a micro-concentric nebulizer with a membrane desolvator (MCN 6000). The results obtained for the MCN 6000 are compared with those obtained by use of a conventional Meinhard nebulizer. It is shown that the observed matrix effect can only be compensated by use of an internal standard for the Meinhard nebulizer, but not for the MCN 6000. Results for ICP-MS are compared with those obtained by total reflection X-ray fluorescence spectrometry (TXRF).     

New human hair certified reference material for methylmercury and trace elements

 A new human hair certified reference material (NIES CRM No. 13) for mercury speciation and trace element analysis was prepared at the National Institute for Environmental Studies (NIES), Environmental Agency of Japan. Scalp hair from Japanese males, which is identical with the original material for the previous human hair CRM (NIES CRM No. 5), was used. Special attention was paid to reduce contamination from a grinding vessel during the preparation procedure. A newly-prepared ceramic/Teflon disc mill was used for cryogenic grinding of the hair. 1,000 bottles (3 g each) were produced after sieving and blending of the hair powder. Certified values for total mercury and methylmercury, as well as other trace elements of toxicological and nutritional significance (antimony, cadmium, copper, lead, selenium, and zinc), were determined based on analyses from extensive collaborations. Reference values for 12 elements (aluminium, arsenic, barium, calcium, cobalt, iron, magnesium, manganese, silver, sodium, sulfur and vanadium) were also given. Received: 8 February 1996/Accepted: 4 April 1996     

New human hair certified reference material for methylmercury and trace elements

A new human hair certified reference material (NIES CRM No. 13) for mercury speciation and trace element analysis was prepared at the National Institute for Environmental Studies (NIES), Environmental Agency of Japan. Scalp hair from Japanese males, which is identical with the original material for the previous human hair CRM (NIES CRM No. 5), was used. Special attention was paid to reduce contamination from a grinding vessel during the preparation procedure. A newly-prepared ceramic/Teflon disc mill was used for cryogenic grinding of the hair. 1, 000 bottles (3 g each) were produced after sieving and blending of the hair powder. Certified values for total mercury and methylmercury, as well as other trace elements of toxicological and nutritional significance (antimony, cadmium, copper, lead, selenium, and zinc), were determined based on analyses from extensive collaborations. Reference values for 12 elements (aluminium, arsenic, barium, calcium, cobalt, iron, magnesium, manganese, silver, sodium, sulfur and vanadium) were also given.     

Analysis of nutrition-relevant trace elements in human blood and serum by means of total reflection X-ray fluorescence (TXRF) spectroscopy

In clinical service laboratories, one of the most common analytical tasks with regard to inorganic traces is the determination of the nutrition-relevant elements Fe, Cu, Zn, and Se.     

Analytical performance of a fast multi-element method for titanium and trace elements determination in cosmetics and pharmaceuticals by ICP-AES

A multi-element analytical method based on inductively coupled plasma atomic emission spectrometry (ICP-AES) was developed for trace elements in pharmaceutical tablets and cosmetics. Titanium was also included in the analytes since it is widely used in pharmaceuticals. Critical ICP conditions, like RF incident power, argon gas flow rate and nebulizer sample uptake flow rate were optimized. The most sensitive spectral line of each analyte was selected as optimum for further study. Detection limits in the low μg g⁻¹ range were obtained. Prior to chemical analysis, the samples were decomposed by acid digestion, using various mixtures of HCl, HNO₃ and HF. Yttrium was used as a suitable internal standard in order to correct for possible matrix effects. The method was applied to the analysis of six different pharmaceutical products (anti-biotic, anti-inflammatory, anti-hypertensive) in the form of tablets with film coating and also three cosmetic products like hair and face masks.     

Atomic emission analysis of human hair for the presence of trace elements

A procedure is developed for the atomic emission analysis of human hair with the preliminary acid mineralization of samples and excitation of spectra in samples of dry residues of hair mineralizate on the end face of a carbon electrode in an alternating current arch. Spectra were recorded on an MFS-8 spectrograph modernized with a MAES photodiode array. Using the developed analytical procedure, samples of hair were analyzed for the presence of Al, B, Ca, Cu, Mg, Mn, Fe, P, Pb, and Zn. The average concentrations and concentration ranges of these elements were calculated for samples collected from 42 donors. The results obtained were compared with the published data for other geographical regions.     

Determination of trace element levels in human scalp hair in occupationally exposed subjects by XRF

Trace element levels in hair of individuals living in urban areas were determined by energy dispersive XRF. Two groups of subjects were investigated, the first group was assumed to be from a healthy environment, the other one was exposed to a high level of contamination due to working conditions. The results were compared to data reported in the literature. The concentrations of Ca, Fe, Cu, Zn and Pb in the scalp hair were determined and the correlation between hair trace element levels and environmental effects was discussed. The results given by the second group show that environmental exposure effects hair trace element levels which are related to body trace element concentrations.     

Status of trace and toxic elements pollution in creek ecosystem using TXRF method

The economic development worldwide has brought in its wake many changes in the environment. Marine ecosystem which forms a part of this environment has been subjected to impact of industrialisation and urbanization. The study has been carried out in the creek ecosystem of Mumbai receiving the effluents from industrial and urban settlements. The trace elements such as P, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Pb, As, Rb and Sr were analysed in the creek water collected from the side receiving industrial effluent and discharges from the urban settlements using total reflection X-ray fluorescence spectrometry. On comparing the concentration of the trace element from the mid stream water of the creek with the water samples collected from the industrial and city effluent receiving side, it was found that the concentration of P, Ca, Mn, Fe, Co, Cu, Zn, Pb and As were found higher in the industrial side of the creek whereas V, Cr and Ni concentration were found higher in the samples collected from the side receiving city effluent.     

Comparison of trace element determination in powdered soil and grass samples by energy-dispersive XRF and by ICP-AES

Summary It is shown that trace element concentrations down to between 1 and 10 g/g can be determined in powdered soil and grass samples by XRF analysis using the Compton scattering peak to correct for small differences in matrix absorption between sample and standards. The results are compared with values obtained by ICP-AES. The precision for both methods ranges between 5 and 10%.

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Vergleich der Spurenelementbestimmung in pulverförmigen Boden- und Grasproben durch Energie-dispersive RFA und durch ICP-AES

Zusammenfassung Es wird gezeigt, daß Spurenelementkonzentrationen bis herunter zu 1 bis 10 g/g in pulverförmigen Boden- und Grasproben durch RFA bestimmt werden können unter Verwendung des Compton-Streupeaks zur Korrektur kleiner Unterschiede in den Absorptionseigenschaften der Matrix von Probe und Standards. Die Ergebnisse werden verglichen mit den Werten, die mit Hilfe der ICP-AES erhalten werden. Die Präzision liegt für beide Methoden im Bereich von 5–10%.

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On leave from Rand Afrikaans University, Johannesburg, Republic of South Africa     

Prompt gamma-ray neutron activation analysis for multi-element determination in sediment samples

A facility for the irradiation of internal targets has been installed at the research reactor FRG-of the GKSS Research Center. Thermal-neutron induced prompt gamma radiation was detected by pair spectrometer. With this experimental arrangement concentrations of the major and mino elements Na, Al, Si, K, Ca, Ti, Mn, Fe, Zn, Cl, and S, as well as of the trace constituents Cr Ni, Cu Cd, and Hg of samples from a sediment core of the Elbe River could be determined. The results indicate, that prompt gamma-ray neutron activation analysis (PGNAA) is a powerful instrumental tool for a complete characterization of the main sediment constituents and for the detection of the trace elements Cd and Hg which are of considerable ecological relevance.     

头发中微量元素的测定与糖尿病人的聚类分析研究

用ICP-发射光谱法测定了糖尿病人与非糖尿病人头发中Fe、 Mn、 Cu、 Zn、 Cr、 K、 Mg等7种微量及宏量元素, 用聚类分析法进行了多因素多水平分析, 糖尿病人与非糖尿病人基本上各自聚成一类, 误判率为5%. 结果表明, 二者之间存在着多种微量元素的显著差别, 提示在糖尿病人体内微量元素的营养状态存在一定程度的不平衡. 为多角度探讨糖尿病的病因, 开展糖尿病微量元素医学的早期判别提供科学依据.     

The use of electrothermal vaporization ICP-OES for the determination of trace elements in human hair using slurry sampling and PTFE as modifier

A procedure for the determination of trace elements in human hair has been proposed by electrothermal vaporization inductively coupled plasma optical emission spectrometry (ETV-ICP-OES) with slurry sampling. Slurry was prepared by immersing human hair with conc. HNO₃ and then adding a polytetrafluoroethylene (PTFE) slurry, which was used as a chemical modifier for the improvement of vaporization characteristic of analyte. The slurry was homogenized with an ultrasonic vibrator before the measurement. The vaporization behaviour of the analytes in slurry and solution and the main influence factors for the determination were studied with the addition of PTFE systematically. Detection limits for this method varied from 0.033?µg?g^?1 (Cu) to 3.21?µg?g^?1 (Zn) with the relative standard deviations (RSDs) of 2.8–7.1%. The proposed method was successfully applied for the determination of trace elements (Cu, Mn, Cr, Fe, Zn, Cd and Pb) in human hair with minimum chemical pretreatment and aqueous calibration. The accuracy was checked by comparing the results of this method with those using pneumatic nebulization (PN) ICP-OES after a conventional acid decomposition of the same sample. In addition, the standard reference material of human hair (GBW 07601) was analysed with good agreement between the results from the proposed method and the certified values.