Evaluation of sample preparation (grinding and sieving) of bivalves, coffee and cowpea beans for multi-element analysis

Elemental analyses of food samples require several pre-treatment steps that constitute a great potential source of errors. In this study, the influence of cryogenic, ball and knife mill devices and also sieving using different sizes of sieve (100, 300 and 500 μm) was evaluated for samples of bivalves, coffee and cowpea beans. A two-factor ANOVA was performed in each sample to test for differences between macro, micro and trace element concentrations determined by ICP OES. Results showed that the efficiency of the particle size reduction and sample homogeneity depends on the milling device and the nature of samples. Food samples may present segregation after comminution, and sieving might become a necessary step. Nevertheless, the sieve aperture has to be chosen cautiously, once it might influence the final element concentration. Overall, the expected results by employing cryogenic grinding, such as rapid sample homogenization and small particle size generated were also observed for ball mill. Contamination can be a critical issue for some elements and need to be evaluated individually.     

Search for a possible correlation between geographical area of domicile and trace element composition of human blood serum as determined by pixe

An investigation was undertaken to measure the trace elements in the blood samples by particle induced X-ray emission (PIXE). From the measured concentrations an attempt was made to group the blood specimens by pattern recognition methods as a first step in the search for a possible correlation between the geographical area of domicile and trace elemnt composition. The trend indicated that children with lower Fe and Br contents were similar in their trace element pattern, were predominantly from two district, had lower ferritin values and were breast fed longer than the remaining children in the survey.     

Certification of a second-generation biological reference material (freeze-dried human serum) for trace element determinations

The certification of a second-generation biological reference material (freeze-dried human serum) for trace element determinations is described. The material was prepared under rigorously controlled conditions to avoid extraneous additions. Analytical data were obtained by the authors as well as by numerous other intra- and extra-mural investigators, solicited on the basis of established experience in determining selected elements. For 14 trace elements (aluminium, chromium, manganese, iron, cobalt, copper, zinc, arsenic, selenium, bromine, rubidium, molybdenum, cadmium and caesium) certified values (in ng g^?1 or μg g^?1 dry weight) are listed; for an additional element (nickel) a best estimate (in ng g^? dry weight) is added. Trace element concentrations in the material, which is available to the scientific community, closely approximate those in normal, lyophilized blood plasma or serum samples. The material thus provides the means to check the accuracy and precision of analytical procedures for quantifying low-level trace elements in the best possible conditions and to detect errors that can easily be overlooked when reference materials with higher levels of trace elements are used. In addition, and in contrast to already existing biological reference materials with high levels of trace elements, it offers the possibility of identifying unsuspected errors at the sample preparation stage.     

Preliminary homogeneity study of in-house reference material using neutron activation analysis and X-ray fluorescence

Summary Although many biological reference materials for quality control of trace element analysis are commercially available, there is still a need for additional local materials for special matrices. In the Latin American region a preliminary study has been commenced involving analytical strategies for the characterization of in-house reference material. A biological sample, prepared in Brazil, constitutes the first regional attempt to prepare reference material. It was analyzed by neutron activation analysis (NAA) and X-ray fluorescence (XRF) to verify its homogeneity. The determination of the trace elements and certain major elements was carried out by instrumental NAA. Trace elements such as Cd, Mn, Mo and Cu were determined using NAA with radiochemical separations to improve the sensitivity and precision. XRF was applied only to major constituents and some trace elements with concentration of more than 10 g/g. From a total of 18 elements analyzed, only Fe, Cr and Sc were not homogeneously distributed.     

Isotope-dilution ICP–MS for trace element determination and speciation: from a reference method to a routine method?

This critical review discusses the conditions under which inductively coupled plasma–isotope dilution mass spectrometry (ICP–IDMS) is suitable as a routine method for trace element and element-speciation analysis. It can, in general, be concluded that ICP–IDMS has high potential for routine analysis of trace elements if the accuracy of results is of predominant analytical importance. Hyphenated techniques with ICP–IDMS suffer both from lack of commercially available isotope-labeled spike compounds for species-specific isotope dilution and from the more complicated system set-up required for species-unspecific ICP–IDMS analysis. Coupling of gas or liquid chromatography with species-specific ICP–IDMS, however, enables validation of analytical methods involving species transformations which cannot easily be performed by other methods. The potential and limitations of ICP–IDMS are demonstrated by recently published results and by some unpublished investigations by our group. It has been shown that possible loss of silicon as volatile SiF₄ during decomposition of a sample by use of hydrofluoric acid has no effect on trace silicon determination if the isotope-dilution step occurs during digestion in a closed system. For powder samples, laser ablation ICP–IDMS can be applied with an accuracy comparable with that only available from matrix-matched standardization, whereas the accuracy of electrothermal vaporization ICP–IDMS was strongly dependent on the element determined. The significance of easy synthesis of isotope-labeled spike compounds for species-specific ICP–IDMS is demonstrated for monomethylmercury and Cr(VI). Isotope-exchange reactions between different element species can prevent the successful application of ICP–IDMS, as is shown for iodinated hydrocarbons. It is also shown for monomethylmercury that species transformations during sample-pretreatment steps can be followed by species-specific ICP–IDMS without loss of accuracy. A relatively simple and time-efficient procedure for determination of monomethylmercury in environmental and biological samples is discussed. The method, which entails a rapid microwave-assisted isotope dilution step and in-situ extraction of the derivatized species, has good potential for routine application in the future.     

Determination of gadolinium in river water by SPE preconcentration and ICP-MS

An analytical scheme was developed for the determination of Gd-diethylenetriaminepentaacetate (Gd-DTPA), Gd and the other rare earth elements (REE) in river water by inductively coupled plasma (quadrupole) mass spectrometry (ICP-Q-MS). The preconcentration step was essential, since the limits of detection of this multielemental analytical technique are higher than the trace concentrations of the interesting elements in river water.Solid phase extraction (SPE) with different commercially available complexing agents (Chelex 100, Toyopearl and ethylhexylphosphates) was employed for the preconcentration of REE. The investigations revealed that complex stability (varying in dependence of the pH value) has a strong influence on the degree of the enrichment of Gd-DTPA. Based on acidified water samples (pH<3) a procedure using ethylhexylphosphates was proposed for the preconcentration of Gd and REE from surface water samples. For this purpose C₁₈-cartridges loaded with ethylhexylphosphates were used, resulting in an enrichment factor of 40.     

Laser secondary neutral mass spectrometry for copper detection in micro‐scale biopsies

Disease progression and clinical diagnostics of a number of hereditable metabolic diseases are determined by organ involvement in disturbed deposition of certain molecules. Current clinical imaging is unable to visualize this maldistribution with sufficient specificity and sensitivity, such as in Wilson's disease. The quest for understanding cellular Cu distribution in these patients requires element‐ and molecule‐specific images with nanometer‐scale spatial resolution. We have used a new cryo‐mass spectrometric instrument with an integrated cryosectioning chamber for preparation and analysis of frozen hydrated samples of Wilson's disease tissue. With laser post‐ionization secondary neutral mass spectrometry (laser‐SNMS), we were able to image Cu and other intrinsic elements and molecules in less than 1 mg of frozen hydrated liver tissue from a murine model of Wilson's disease. A 40–50 times higher Cu concentration was measured in the disease tissue as compared to the control mouse. Furthermore, major histomorphological changes were observed using this advanced nano‐science tool. The results showed that the combination of in‐vacuum cryosectioning and cryo‐laser‐SNMS technologies is particularly well suited for identifying specific cell structures and imaging trace element concentrations with subcellular resolution and upper‐parts‐per‐billion sensitivity in biological samples. This technology can provide a novel diagnostic tool for clinical applications in various diseases involving trace elements. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of the concentrations of trace and doping elements in GaAs by neutron activation analysis

The concentrations of ten trace and dopant elements in GaAs semiconductor were determined by reactor neutron activation analysis after removal of As by evaporation of AsCl₃. The retentions of the elements of interest were measured using radiotracers. The concentrations of doping elements (Te, Cr and Zn) in commercial GaAs samples were compared to the limit of detection of these elements to analyze the possibility to use NAA for concentration depth profiling measurements. The NAA results were compared with those of electrical measurements and SIMS and the discrepancies found are discussed.     

Activation analysis: A basis for chemical similarity and classification

It is shown that activation analysis is especially suited to serve as a basis for determining the chemical similarity between samples defined by their trace element concentration patterns. The general problem of classification and identification is discussed. The nature of possible classification structures and their approriate clustering strategies is considered. A practical computer method is suggested and its application as well as the graphical representation of classification results are given. The possibility for classification using information theory is mentioned. Classification of chemical elements is discussed and practically realized after Hadamard transformation of the concerntration variation patterns in a series of samples.     

Copper content of vineyard soils at Sremski Karlovci (Vojvodina Province,Serbia) as affected by the use of copper-based fungicides

The present study investigated the copper content of nine vineyard plots soils and four control plots as affected by the application of copper-based fungicides. The study was carried out at the site of Sremski Karlovci in the Serbian province of Vojvodina. The results showed that Cu soil concentrations are increased at the site and that there is a tendency towards soil contamination by this element. Of the 27 total samples studied, only one had Cu concentration above the maximum allowable concentration of 100?mg?kg^?1. That sample's concentration was 111.7?mg?kg^?1. All the samples from the 0–15?cm layer had copper levels that were above the critical value of 60?mg?kg^?1. The mean value of the samples was 79.4?mg?kg^?1, contrasting with the background concentration of 19.8?mg?kg^?1. The results obtained for the studied vineyard soils indicate that these soils are potentially at risk and call for reduced application of Cu-based fungicides along with soil monitoring.     

X-ray fluorescence raw intensities vs. concentration data for multivariate classification of hungarian coal

A set of coal samples was examined by routine methods of coal analysis (density, calorific value, sulfur content, etc.) and by trace element determinations on the coal ash. Both data sets gave satisfactory clustering of samples from similar geological zones. X-ray fluorescence spectra were evaluated in order to identify the significant data-reduction steps in the sequence raw spectra/net intensities/trace element concentrations that is commonly used in x-ray spectrometry. The deconvolution yielding net intensities from spectra was identified as the most significant step. This was explained by the decorrelation effect of geochemically dissimilar elements.     

Trace elements in Australian opals using neutron activation analysis

Neutron activation analysis was used to determine the concentration of trace elements in 42 samples of black, grey and white opals taken from a number of recognised Australian field. The results were evaluated to determine if a relationship existed between trace element content and opal colour.     

Hochdisperse kieselsäure als spurenfänger zur multi-elementanreicherung: Highly dispersed silicic acid as a trace collector for multi-element preconcentration

Highly dispersed silicic acid as a trace collector for multi-element preconcentrationThe purity and sorption properties of commercially available, highly dispersed silicic acid are investigated and compared with those of pure activated carbon for use as trace collectors. For a series of elements, the blanks and their fluctuations caused by silicic acid are significantly smaller, so that detection limits are improved. Activated carbon, however, is the better adsorbent for preconcentration of chelate complexes; in general, recoveries are much higher than are obtainable under similar conditions with the silicic acid. As examples of the applicability of hydrophobic silicic acid as a trace collector, about ten trace elements are preconcentrated from the pure aluminium, gallium and magnesium metals.     

Determination of chromium,manganese, lead and cadmium in biological samples including hair using direct electrothermal atomic absorption spectrometry

Direct analysis of solid samples employing a laboratory assembled electrothermal atomic absorption spectrometer is demonstrated to be a feasible approach for determination of trace elements in plant tissue and hair samples for special applications in plant physiology and biomedical research. As an example, the kinetics of Cr uptake by cabbage and its distribution have been measured as a function of chromium speciation in the nutrient solution. Further, longitudinal concentration gradients of Cr, Pb and Cd have been measured in hair of various population groups exposed to different levels of these elements in ambient and/or occupational environments. The techniques are validated for the determination of these trace elements by neutron activation analysis, dissolution atomic absorption spectrometry and by analysis of certified reference materials. Slurry sample introduction is found appropriate for routine trace element determination and in homogeneity testing. Direct sample introduction is indispensable in the analysis of very small (< 1 mg) tissue biopsy samples in the determination of trace element distributions.     

Analysis of elemental concentration censored distributions in breast malignant and breast benign neoplasm tissues

The total reflection X-ray fluorescence method was applied to study the trace element concentrations in human breast malignant and breast benign neoplasm tissues taken from the women who were patients of Holycross Cancer Centre in Kielce (Poland). These investigations were mainly focused on the development of new possibilities of cancer diagnosis and therapy monitoring. This systematic comparative study was based on relatively large (∼ 100) population studied, namely 26 samples of breast malignant and 68 samples of breast benign neoplasm tissues. The concentrations, being in the range from a few ppb to 0.1%, were determined for thirteen elements (from P to Pb). The results were carefully analysed to investigate the concentration distribution of trace elements in the studied samples. The measurements of concentration of trace elements by total reflection X-ray fluorescence were limited, however, by the detection limit of the method. It was observed that for more than 50% of elements determined, the concentrations were not measured in all samples. These incomplete measurements were treated within the statistical concept called left-random censoring and for the estimation of the mean value and median of censored concentration distributions, the Kaplan–Meier estimator was used. For comparison of concentrations in two populations, the log-rank test was applied, which allows to compare the censored total reflection X-ray fluorescence data. Found statistically significant differences are discussed in more details. It is noted that described data analysis procedures should be the standard tool to analyze the censored concentrations of trace elements analysed by X-ray fluorescence methods.     

Trace elements in coloured opals using neutron activation analysis

Neutron activation analysis was used to determine the concentration of trace elements in 50 samples of orange, yellow, honey, green, blue and pink opals as well as 18 samples of colourless opals taken from a number of recognised fields in Australia, Peru, Mexico and USA. The results were evaluated to determine the relationship between trace element content and opal colour.     

青藏高原3种秦艽组植物微量元素比较分析

利用全谱直读等离子体发射光谱法(ICP-AES)测定了3种秦艽组植物10种微量元素(Cu,Zn,Fe,Mn,Ni,Co,Sn,V,Al,Ti)的含量,并进行了比较分析。结果表明,所测定元素在3个不同物种内的含量排列顺序基本一致,显示了三者在元素富集方面的相似性。就同一种元素在3个物种内的富集水平而言,以麻花艽根部具有较高含量的元素Cu,Zn,Co,Al和Ti,管花秦艽根部则大量富集了其余5种微量元素,达乌里秦艽对元素的吸收积累能力居中,揭示了不同物种对同一元素富集能力的差异。该研究可为秦艽类植物资源的深入开发利用提供参考。     

Trace elements in precious and common opals using neutron activation analysis

Neutron activation analysis (NAA) was used to determine the concentration of trace elements in 44 precious and 52 common opals sampled from a number of recognised fields within Australia. The purpose of this study was to determine if precious and common opals of the same colour and location have the same or a different trace element profile. Similar numbers of black, white and grey samples were studied in each case. In most cases common opals had a significantly higher concentrationof certain trace elements when compared with precious opals.     

最近十年中国头发微量元素研究进展

2006—2015年,是中国头发微量元素研究继续取得重要成果的10年,也是该项研究量质转变的10年。概述了10年内中国头发微量元素研究的进展、现状和发展方向,高通量微量元素组学研究和微量微区分析技术的发展将引领头发微量元素研究领域走向新的高度。