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X-ray fluorescence (XRF) allows multielement analysis to be performed on a variety of solid matrices, including powders and grains. To obtain reliable results, the sample must meet certain criteria related to its thickness, surface flatness, homogeneity and particle size. Heterogeneous solid samples to be measured must be pulverized, homogenized, and prepared as loose powder, pressed powders (pellets) or fused beads, if accurate and reproducible measurements are sought. The measurement conditions are defined by the analytical depth of the fluorescent X-rays of the analytes, and can be estimated from the relationship between the absorption of each beam and its respective energy, and the composition and density of the sample. Furthermore, in purpose of assuring the validity of the results, the measurement method must be validated to confirm that it fulfills the purpose for which it was developed. This review is focused on the preparation of solid samples, the quantitative analysis, which includes the validation of the methods involved in XRF spectrometry measurements, and on the main applications of the technique. [ABSTRACT FROM AUTHOR]

Background and objectives: Determining the geographical origin of durum wheat is an important and emerging challenge because consumers perceive added value of final products (e.g., pasta) depending on the origin. Declaration of geographical origin is also an emerging requirement of specific national regulations. Among analytical strategies for determining geographical origins of samples, isotopic techniques based on both light and radiogenic isotope targets stand out, despite limitations of applicability, validation and assessment of interyear variability. Findings: In this study, 87Sr/86Sr isotopic analysis was successfully used to discriminate Italian (ITA) samples versus rest‐of‐the world (RoW) samples and subsequently integrated with an elemental analysis (ICP‒MS) on 75 elements. A tiered approach was finally adopted in which the results of the 87Sr/86Sr analysis were input to a second step of support vector machine classification modeling (SVMC) based on the Al, Mn, Mo, P, S, Ti, Y, and Zn percentages in each sample. This model was tested against a blind group of samples with overall satisfactory performance. Conclusion: Valuable information from multielemental and stable isotope ratio analyses was collected for authentic samples from different Italian, European, and non‐European regions harvested during different years. Significance and novelty: This study demonstrates the potential and validity of an innovative combined multielemental and strontium isotope ratio approach for the geographic discrimination of durum wheat on a global scale: the developed predictive model has already been routinely employed to control industrial lots. [ABSTRACT FROM AUTHOR]

In this paper, the effect of the extraction method on the concentrations of selected elements in yerba mate (Ilex paraguariensis) infusions is presented. Seven pure yerba mate samples (without additives) were selected, representing various types and countries of origin. An extensive sample preparation procedure was proposed: ultrasound-assisted extraction using two types of extractants (deionized and tap water) at two different temperatures (room and 80 °C). In parallel, the above extractants and temperatures were carried out for all samples by the classical brewing method (without ultrasound). In addition, microwave-assisted acid mineralization was carried out to determine the total content. All the proposed procedures were thoroughly investigated with certified reference material (tea leaves, INCT–TL–1). For the total content of all the determined elements, acceptable recoveries (80–116%) were obtained. All digests and extracts were analyzed by simultaneous ICP OES. For the first time, it was assessed how tap water extraction affects the percentage of extracted element concentrations. [ABSTRACT FROM AUTHOR]

In this study, benchtop micro-X-ray fluorescence spectrometry (µXRF) was evaluated as a green and cost-effective multielemental analytical technique for P. vittata. Here, we compare the arsenic (As) content values obtained from the same samples by µXRF and inductively coupled plasma-optical emissions spectrometry (ICP–OES). To obtain samples with different As concentrations, fronds at different growth time points were collected from P. vittata plants grown on two natural As-rich soils with either high or moderate As (750 and 58 mg/kg). Dried samples were evaluated using multielement-µXRF analysis and processed by PCA. The same samples were then analysed for multielement concentrations by ICP–OES. We show that As concentrations detected by ICP–OES, ranging from 0 to 3300 mg/kg, were comparable to those obtained by µXRF. Similar reliability was obtained for micro- and macronutrient concentrations. A positive correlation between As and potassium (K) contents and a negative correlation between As and iron (Fe), calcium (Ca) and manganese (Mn) contents were found at both high and moderate As. In conclusion, we demonstrate that this methodological approach based on μXRF analysis is suitable for monitoring the As and element contents in dried plant tissues without any chemical treatment of samples and that changes in most nutrient concentrations can be strictly related to the As content in plant tissue. [ABSTRACT FROM AUTHOR]

In this paper, the effect of the extraction method on the concentrations of selected elements in yerba mate (Ilex paraguariensis) infusions is presented. Seven pure yerba mate samples (without additives) were selected, representing various types and countries of origin. An extensive sample preparation procedure was proposed: ultrasound-assisted extraction using two types of extractants (deionized and tap water) at two different temperatures (room and 80 °C). In parallel, the above extractants and temperatures were carried out for all samples by the classical brewing method (without ultrasound). In addition, microwave-assisted acid mineralization was carried out to determine the total content. All the proposed procedures were thoroughly investigated with certified reference material (tea leaves, INCT–TL–1). For the total content of all the determined elements, acceptable recoveries (80–116%) were obtained. All digests and extracts were analyzed by simultaneous ICP OES. For the first time, it was assessed how tap water extraction affects the percentage of extracted element concentrations.

Seventy-three samples of alcoholic beverages and juices that were purchased on the Polish market and home-made were analyzed for their elemental profiles. The levels of 23 metals were determined by ICP-MS (Ag, Ba, Bi, Cd, Co, Cr, Li, Mn, Ni, Pb, Sr and Tl), ICP-OES (Al, B, Ca, Cu, Fe, K, Mg, Na, Ti and Zn) and CVAAS (Hg) techniques in twenty-five samples of ciders widely available on the Polish market; six samples of home-made ciders; two samples of juices used in the production of these ciders; and forty samples of low-percentage, flavored alcoholic beverages based on beer. The gathered analytical data confirmed that the final elemental fingerprint of a product is affected by the elemental fingerprint of the ingredients used (apple variety) as well as the technology and equipment used by the producer, and in the case of commercial ciders, also the impact of type of the packaging used was proven. These factors are specific to each producer and the influence of the mentioned above parameters was revealed as a result of the performed analysis. Additionally, the inclusion of the home-made ciders in the data set helped us to understand the potential origin of some elements, from the raw materials to the final products. The applied statistical tests revealed (Kruskal–Wallis and ANOVA) the existence of statistically significant differences in the concentration of the following metals: Ag, Al, B, Bi, Co, Cr, Cu, Fe, K, Li, Mg, Na, Ni, Ti and Zn in terms of the type of cider origin (commercial and home-made). In turn, for different packaging (can or bottle) within one brand of commercial cider, the existence of statistically significant differences for Cu, Mn and Na was proved. The concentrations of all determined elements in the commercial cider from the Polish market and home-made cider samples can be considered as nontoxic, because the measured levels of elements indicated in the regulations were lower than the allowable limits. Moreover, the obtained results can be treated as preliminary for the potential authentication of products in order to distinguish the home-made (fake) from the authentic products, especially for premium-class alcoholic beverages.

Beehive products possess nutritional value and health-promoting properties and are recommended as so-called “superfoods”. However, because of their natural origin, they may contain relevant elemental contaminants. Therefore, to assess the quality of bee products, we examined concentrations of a broad range of 24 selected elements in propolis, bee pollen, and royal jelly. The quantitative analyses were performed with inductively coupled plasma-mass spectrometry (ICP-MS) and inductively coupled plasma optical emission spectrometry (ICP-OES) techniques. The results of our research indicate that bee products contain essential macronutrients (i.e., K, P, and S) and micronutrients (i.e., Zn and Fe) in concentrations depending on the products’ type. However, the presence of toxic heavy metals makes it necessary to test the quality of bee products before using them as dietary supplements. Bearing in mind that bee products are highly heterogenous and, depending on the environmental factors, differ in their elemental content, it is necessary to develop standards regulating the acceptable levels of inorganic pollutants. Furthermore, since bees and their products are considered to be an effective biomonitoring tool, our results may reflect the environment’s condition in west-central Poland, affecting the health and well-being of both humans and bees.

The main goal of this research is to define reference values of elemental concentration in human urine. The second topic is to develop a fast analytical method for multielemental analysis of human urine by means of a low-power benchtop total reflection X-ray fluorescence system. For this purpose a set of certified human urine and real samples was employed. All of the parameters affecting sample preparation and measurement conditions were carefully evaluated, and finally, the procedure for optimal urine preparation and optimal measurement conditions is defined. The accuracy and precision of the measurements were verified using an internal standardization approach for quantification. As results, the reference values of concentration of several elements (K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb and Sr) were defined on the basis of the analysis of 100 urine samples. Donors were presumably healthy volunteers from the Świętokrzyskie Province in Poland: 62 women and 38 men. Because of the strong asymmetry of elemental concentration distributions, the median and the 1st and 3rd quartiles reflect features of the distributions better than the mean value and standard deviation (which are proper for symmetric distributions). Finally, the 1st and 3rd quartiles were accepted as the initial and final values of the concentration reference range. For measurements, in which the concentration is below the detection limit of the method used (i.e. for Cr, Mn, Cu, Se), the well-known random-left censoring approach was applied for the statistical analysis of the results. [ABSTRACT FROM AUTHOR]

We have examined the potential of discriminant inorganic constituents (trace-, ultra-trace elements and Sr isotope ratios) to assess the origin of world famous brands of European dry-cured hams. The variation of the multielemental composition with principal component analysis allowed to discriminate the origin of Bayonne hams. Determined ratio 87 Sr/ 86 Sr was recognized as a strong additional distinctive parameter. The ratio 87 Sr/ 86 Sr allowed to better separate all the different categories of hams in addition to the multi-elemental detection. The major contribution of the value 87 Sr/ 86 Sr for the Bayonne ham is directly related to its curing due to the salt used in process coming from the nearby salt mine Salies-de-Béarn. Since the salt represents around 4% of the final product, it will therefore strongly influence the elemental and isotopic composition of hams. The overall discrimination potential of strontium isotope ratio is evidenced in the final statistical discrimination of the origin of hams. [ABSTRACT FROM AUTHOR]

Whisky (whiskey) consists of many trace elements coming from the raw materials used in its fermentation, distillation and maturation processes. These ingredients assure the exceptional organoleptic characteristics of the beverage. Their analysis is important to better control the stages of fermentation, distillation, taste repeatability and for product quality assurance as well as from the brand protection point of view. This article presents the usefulness of modern analytical techniques based on elemental analysis. ICP mass spectrometry and CV atomic absorption spectroscopy were applied to distinguish whisky produced in Scotland from whisky coming from Ireland and the United States. The collected semi-quantitative data were used for multivariate analysis performed using the Statistica 10.0 software. The results showed that Irish whiskey is characterized by quite a high amount of Ba and Ti compared with other samples, which made it possible to distinguish this sample from the others. No strict correlation was found between the type of whisky and the amount of trace elements, however, the projection of objects on the first two components revealed that single malt samples created one cluster.

The composition of Spanish natural mineral waters has been determined by means of inductively coupled plasma-mass spectrometry, inductively coupled plasma-atomic emission spectrometry, ionic chromatography and other routine techniques. Methods were applied to samples of bottled water from springs situated in five different mountain systems such as Cordillera Costero-Catalana, Macizo Galaico, Sistemas Béticos, Sistema Central and Sistema Ibérico. Pattern recognition techniques have been applied to differentiate the origin of samples. Data were initially studied by using nonparametric multiple comparison techniques and principal component analysis to highlight data trends. Classification models based on linear discriminant analysis and multilayer perceptron artificial neural networks have been built and validated by means of a stratified jackknifing methodology. An iterative approach has been used to build an artificial neural network model based on the variables selected by linear discriminant analysis. The prediction ability of the constructed model was 94 %. [ABSTRACT FROM AUTHOR]

High throughput analytical methodologies entailing low-cost multielemental analysis are attractive for identifying and quantitating elements in medicinal herb infusions. The aim of the present research was to develop a cost-effective and fast method for multielemental analysis of black tea and mint infusions by low-power TXRF instrumentation. The developed methodology was applied to study how infusion time, water temperature and type of water used to prepare infusions (tap, mineral and high purity water) affect element content in the resulting tea and mint beverages. Additionally, pH, conductivity, hardness and anionic composition of infusions and the different water types used to prepare the infusions were also considered. The elemental composition (K, Ca, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr) of different preparations, as well as infusions from different commercial tea brands available in Jamaican and Spanish markets is reported. It is expected that the TXRF method developed as well as the information derived from this study may be useful in the fields of nutrition and health. [ABSTRACT FROM AUTHOR]

Amniotic fluid is the substantial factor in the development of an embryo and fetus due to the fact that water and solutes contained in it penetrate the fetal membranes in an hydrostatic and osmotic way as well as being swallowed by the fetus. Elemental composition of amniotic fluid influences the growth and health of the fetus, therefore, an analysis of amniotic fluid is important because the results would indicate abnormal levels of minerals or toxic elements. Inductively coupled plasma mass spectroscopy (ICP-MS) is often used for determination of trace and ultra-trace level elements in a wide range of matrices including biological samples because of its unique analytical capabilities. In the case of trace and ultra-trace level analysis detailed characteristics of analytical procedure as well as properties of the analytical result are particularly important. The purpose of this study was to develop a new analytical procedure for multielemental analysis of 18 elements (Al, As, Ba, Ca, Cd, Co, Cr, Cu, Mg, Mn, Ni, Pb, Sb, Se, Sr, U, V and Zn) in amniotic fluid samples using ICP-MS. Dynamic reaction cell (DRC) with two reaction gases, ammonia and oxygen, was involved in the experiment to eliminate spectral interferences. Detailed validation was conducted using 3 certified reference mterials (CRMs) and real amniotic fluid samples collected from patients. Repeatability for all analyzed analytes was found to range from 0.70% to 8.0% and for intermediate precision results varied from 1.3% to 15%. Trueness expressed as recovery ranged from 80% to 125%. Traceability was assured through the analyses of CRMs. Uncertainty of the results was also evaluated using single-laboratory validation approach. The obtained expanded uncertainty ( U ) results for CRMs, expressed as a percentage of the concentration of an analyte, were found to be between 8.3% for V and 45% for Cd. Standard uncertainty of the precision was found to have a greater influence on the combined standard uncertainty than on trueness factor. [ABSTRACT FROM AUTHOR]

An approach for high throughput reliable multielemental analysis of trace elements in a large number of horse hair samples was designed. Suitability of time-of-flight mass spectrometer (oaTOF-ICP-MS) for fast determination of unlimited numbers of isotopes in the low volume samples was demonstrated. Due to quasi-simultaneous capability of the oaTOF-ICP-MS the large number of highly valuated data with unaffected isotopic ratio in a very short time could be obtained. The choice of horse hair was obvious because of easy reachability and clear conception about horse nutritional habits and stabling. Such large data set with preserved isotopic ratios is ideal for statistical evaluation which could reveal some interesting interconnection between elemental composition of horse hair and the way of stabling, feeding, etc. Statistical treatment of the data is not a part of this study and will be presented later. We collected one hundred horse hair samples from horse stables through Czech Republic. Samples were washed by optimized washing process to eliminate exogenic contamination prior to digestion and following analysis. A determination of 36 elements (As, Au, B, Be, Cd, Ce, Co, Cr, Dy, Er, Eu, Ga, Gd, Ge, Ho, La, Li, Lu, Nd, Ni, Pb, Pd, Pr, Pt, Rb, Sb, Sc, Sm, Ta, Tb, Te, Tm, U, V, Y, Yb) in horse hair by oaTOF-ICP-MS was optimized. A throughput of 100 samples with unlimited numbers of isotopes per 6 h was achieved. Proposed very fast multielemental method preserves isotopic ratios, and therefore, is undoubtedly highly suitable for statistical studies. Detection limits of the proposed method ranged from 0.13 μg kg (Eu, Gd, Tm) to 27.9 μg kg (Au), except for Ni (48.5 μg kg) that is probably affected by contamination raised from nickel cones. [ABSTRACT FROM AUTHOR]

In the present contribution, benchtop total reflection X-ray fluorescence spectrometry (TXRF) has been evaluated as a cost-effective multielemental analytical technique for human placenta analysis. An easy and rapid sample preparation consisting of suspending 50 mg of sample in 1 mL of a Triton 1% solution in deionized water showed to be the most suitable for this kind of samples. However, for comparison purposes, an acidic microwave acidic digestion procedure was also applied. For both sample treatment methodologies, limits of detection for most elements were in the low mg/kg level. Accurate and precise results were obtained using internal standardization as quantification approach and applying a correction factor to compensate for absorption effects. The correction factor was based on the proportional ratio between the slurry preparation results and those obtained for the analysis of a set of human placenta samples analysed by microwave acidic digestion and ICP-AES analysis. As a study case, the developed TXRF methodology was applied for multielemental analysis (K, Ca, Fe, Cu, Zn, As, Se, Br, Rb and Sr) of several healthy women's placenta samples from two regions in Jamaica. [ABSTRACT FROM AUTHOR]

The aim of this paper is to present the validation of inductively coupled plasma optical emission spectrometry (ICP-OES) method used for metals determination from several perennial plant samples. The suitability of two digestion procedures using wet digestion with mineral acids mixture on hot plate and microwave digestion was investigated to determine As, Cd, Cu, Fe, Mn, Pb and Zn in plants samples. The LOD of the seven analysed elements in solid samples varied between 0.20µg g-1 for Mn and 0.55µg g-1 for Pb. The found values for metals determined by ICP-OES in a vegetable certified reference material digested using the two procedures were compared with the certified values and good agreements between these values were obtained. The proposed method indicated satisfactory recovery, detection limits and standard deviations for trace metal determination in perennial plants samples.

In this work, a method of recalculation of results of X-ray fluorescence (XRF) technique to Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) method was elaborated for biosorption studies. Equations that calibrate XRF to ICP-OES were determined, as a biosorbent strawberry, blackcurrant and raspberry seeds after supercritical CO2 extraction were used. ICP-OES showed a better precision and lower detection limits than XRF. The latter technique is cheaper, requires minimal sample preparation and gives faster results. Linear regression of the data gave almost 1:1 correlations without additional correction (for Cu r2 = 0.9998, Mn r2 = 0.807, Zn r2 = 0.979). Calibration and quantification of intensities of XRF was obtained using ICP-OES measurements after samples digestion with HNO3 in a microwave system. High positive correlations were estimated for Cu, Mn, Zn. It was demonstrated that XRF technique can be used together with other well established techniques (ICP-OES) to produce quantitative data from biosorption studies. Elaboration of cheap and quick analytical methodology is an important aspect in development of new processes and products based on biosorption process.

In this work, a rapid and simple ultrasound-assisted pretreatment for maize samples is proposed. Also, the performance of microwave plasma atomic emission spectrometry (MPAES) for the analysis of Ag, Al, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Mo, Na, Ni, Pb, Tl, V and Zn in maize seeds, was evaluated. Instrumental parameters optimization, as well as validation and application of the MPAES are presented. The obtained limits of detection were ranged between 0.7 μg g − 1 (for Mo and Fe) and 4.3 μg g − 1 (for Ca). Validation assays were carried out by standard addition and internal standard, showing good recovery performances, over 96% in all cases. The developed method was applied to trace elements determination of Argentinean maize samples, improving the productivity performance due the reducing costs — by the use of atmospheric nitrogen as plasma source for MPAES — and time analysis, which could be trustworthy for routine analysis, quality control and traceability of maize. [ABSTRACT FROM AUTHOR]

This paper introduces a calibration procedure and provides the data achieved for accuracy, precision, reproducibility and the detection limits for major (Si, Al, Fe, Mn, Mg, Ca, Na, K, Ti, P) and trace (Ba, Cr, Cu, Hf, La, Nb, Ni, Pb, Rb, Sr, Ta, Th, U, Y, Zn, Zr) elements in the routine analysis of geological and environmental samples. Forty-two rock and soil reference materials were used to calibrate and evaluate the analytical method using a sequential wavelength dispersive X-ray fluorescence spectrometer. Samples were prepared as fused glass discs and analysis performed with a total measuring time of thirty-one minutes. Another set of twelve independent reference materials were analyzed for the evaluation of accuracy. The detection limits and accuracy obtained for the trace elements (1–2 mg/kg) are adequate both for geochemical exploration and environmental studies. The fitness for purpose of the results was also evaluated by the quality criteria test proposed by the International Global Geochemical Mapping Program (IGCP) from which it can be deduced that the method is adequate considering geochemical mapping application and accuracy obtained is within the expected interval of certified values in most cases. [ABSTRACT FROM AUTHOR]

Recent technological improvements have led to a widespread adoption of benchtop total reflection X-ray fluorescence systems (TXRF) for analysis of liquid samples. However, benchtop TXRF systems usually present limited sensitivity compared with high-scale instrumentation which can restrict its application in some fields. The aim of the present work was to evaluate and compare the analytical capabilities of two TXRF systems, equipped with low power Mo and W target X-ray tubes, for multielemental analysis of wine samples. Using the Mo-TXRF system, the detection limits for most elements were one order of magnitude lower than those attained using the W-TXRF system. For the detection of high Z elements like Cd and Ag, however, W-TXRF remains a very good option due to the possibility of K-Lines detection. Accuracy and precision of the obtained results have been evaluated analyzing spiked real wine samples and comparing the TXRF results with those obtained by inductively coupled plasma emission spectroscopy (ICP-OES). In general, good agreement was obtained between ICP-OES and TXRF results for the analysis of both red and white wine samples except for light elements (i.e., K) which TXRF concentrations were underestimated. However, a further achievement of analytical quality of TXRF results can be achieved if wine analysis is performed after dilution of the sample with de-ionized water. [ABSTRACT FROM AUTHOR]

In order to obtain a value-added product from the removal and processing of waste algal biomass, it is essential to elaborate on cost-effective methods of their utilization. Composting appears to be one of the methods of obtaining a natural fertilizer. This paper demonstrates the results of a study where the biomass of seaweed (Fucus sp.) has been co-composted with ecological hay, grass, sawdust, and spent mushroom substrate for three months. The utilitarian properties of the new natural products (compost and compost extract) were examined in germination tests on Lepidium sativum. Three groups were compared: the control group treated with distilled water, and two experimental groups: one treated with seaweed extract and the other fertilized with algal compost. Results showed that the addition of compost and compost extract contributed to the increase in plant length and mass. Moreover, the biomass fertilized with new products was rich in micro- and macroelements (in particular B, Fe, Cu, Zn, Ca, K, S). Utilization of algal biomass for agricultural and horticultural purposes could be beneficial for environmental protection in that it might help remove waste biomass from coastal areas and from the point of view of the economy by resulting in the production of value-added natural fertilizers and biostimulants (extracts). The latter could help reduce the use of chemical fertilizers and could help to improve physicochemical properties of the soil, thus producing an enhanced seed yield. [ABSTRACT FROM AUTHOR]

Elemental content plays an important role in biological processes, and so, the multielemental analysis of human tissue samples is required in biomedical research. Still, the small amount of available biological samples and the adipose content of the samples can be major setbacks for the accurate determination of elemental content. In this study, we explored the potential of several analytical approaches combined with total reflection X-ray fluorescence spectrometry (TXRF) for multielemental analysis of human tissues with different adipose content (colon, heart, liver, lung, muscle, intestine, skin, stomach, uterus, bladder and aorta). The capabilities and limitations of different sample treatment procedures (suspension and acidic digestion) and two TXRF systems with different anode configurations (Mo and W X-ray tubes) have been evaluated for such purpose. Results showed that for tissues with a higher fat content (e.g., skin, and intestine) the best strategy was the acidic digestion of the sample before TXRF analysis. However, for other tissues, acceptable results were obtained by suspending 20 mg of powdered material in 1 mL of 2 M nitric acid. A further enhancement of the limits of detection and accuracy of the results was achieved if using Mo-TXRF systems, especially for the determination of low Z elements (e.g., K, and Ca) and of elements present at low concentrations (e.g., Cu) in the human tissues. Finally, results by TXRF analysis were compared with those obtained with μ-EDXRF and ICP-OES, and a good agreement was obtained. [Display omitted] • Good quantitative compromise between techniques for medium-Z elements. • Gauging adipose content through EDXRF for decision-making in TXRF sample preparation. • Tissues with high adipose content require sample digestion procedures. [ABSTRACT FROM AUTHOR]

A study of the optical emission as a function of concentration of laser-ablated yttrium (Y) and of six rare earth elements, europium (Eu), gadolinium (Gd), lanthanum (La), praseodymium (Pr), neodymium (Nd), and samarium (Sm), has been evaluated using the laser-induced breakdown spectroscopy (LIBS) technique. Statistical methodology using multivariate analysis has been used to obtain the sampling errors, coefficient of regression, calibration, and cross-validation of measurements as they relate to the LIBS analysis in graphite-matrix pellets that were doped with elements at several concentrations. Each element (in oxide form) was mixed in the graphite matrix in percentages ranging from 1% to 50% by weight and the LIBS spectra obtained for each composition as well as for pure oxide samples. Finally, a single pellet was mixed with all the elements in equal oxide masses to determine if we can identify the elemental peaks in a mixed pellet. This dataset is relevant for future application to studies of fission product content and distribution in irradiated nuclear fuels. These results demonstrate that LIBS technique is inherently well suited for the future challenge of in situ analysis of nuclear materials. These studies also show that LIBS spectral analysis using statistical methodology can provide quantitative results and suggest an approach in future to the far more challenging multielemental analysis of ~ 20 primary elements in high-burnup nuclear reactor fuel. [ABSTRACT FROM AUTHOR]

The main objective of this study is to assess the level of contamination from mercury and other elements in the Sarajevo area. The soil and lichen samples (Hypogymnia physodes) were collected from selected areas there were nine soil sites and four sites for lichens. Validated and standardized analytical procedures were used in order to compare the obtained results with data from other countries in Europe. The accuracy of the results obtained by cold vapour atomic absorption spectrometry (CVAAS) for total mercury and instrumental neutron activation analysis (INAA) for other elements (Ag, As, Au, Ba, Br, Ca, Cd, Ce, Co, Cr, Cs, Eu, Fe, Ga, Hf, Ho, In, K, La, Mo, Na, Nd, Pd, Pr, Rb, Ru, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Te, Th, Tm, U, W, Yb, Zn, and Zr) was verified by the use of certified reference materials. Results obtained for mercury showed that at three sites (Butmir, PMF, and Blekin potok) the mercury concentrations in the soil were much higher, 5 to 10 times higher, than the allowed values. All lichens samples examined contained low mercury concentrations that cannot be correlated with the mercury contents in the soil. Comparison of the multielemental analysis of the lichen H. physodes and surface soils samples is also presented. Keywords: Lichen, multielemental analysis, pollution, Sarajevo, soil. [ABSTRACT FROM AUTHOR]

The article presents the optimisation, validation and application of the microwave induced plasma optical emission spectrometry (MIP–OES) dedicated for a routine determination of Ag, Al, B, Ba, Bi, Ca, Cd, Cr, Cu, Fe, Ga, In, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Sr, Tl, Zn, in the geological samples. The three procedures of sample preparation has been proposed: sample digestion with the use of hydrofluoric acid for determination of total concentration of elements, extraction by aqua regia for determination of the quasi-total element concentration and extraction by hydrochloric acid solution to determine contents of the elements in acid leachable fraction. The detection limits were on the level 0.001–0.121 mg L −1 (from 0.010–0.10 to 1.2–12 mg kg −1 depend on the samples preparation procedure); the precision: 0.20–1.37%; accuracy 85–115% (for recovery for certified standards materials analysis and parallel analysis by independent analytical techniques: X-ray fluorescence (XRF) and flame absorption spectrometry (FAAS)). The conformity of the results obtained by MIP–OES analytical procedures with the results obtained by XRF and FAAS analysis allows to propose the procedures for studies of elemental composition of the fraction of the geological samples. Additionally, the MIP–OES technique is much less expensive than ICP techniques and much less time-consuming than AAS techniques. [ABSTRACT FROM AUTHOR]

A combined procedure has been developed for the analysis of high-purity silicon with preliminary vapor-phase digestion and preconcentration in a microwave oven using inductively coupled plasma atomic emission spectrometry ( ICP-AES). Liners for high-pressure vessels of microwave oven ensuring the simultaneous distillation of matrices from 3-4 samples without their contact with the acid solution have been designed and manufactured. The procedure ensures the determination of up to 30 elements: Ag, Al, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hf, In, K, Li, Mn, Mo, Na, Nb, Ni, P, Rb, Sb, Sn, Sr, Ta, V, W, Zn, and Zr with the limits of detection 10 −10 wt %. [ABSTRACT FROM AUTHOR]

A low power and low argon consumption (13.56 MHz, 15 W, 150 ml min-1) capacitively coupled plasma microtorch interfaced with a low-resolution microspectrometer and a small-sized electrothermal vaporization Rh coiled-filament as liquid microsample introduction device into the plasma was investigated for the simultaneous determination of several volatile elements of interest for environment. Constructive details, spectral and analytical characteristics, and optimum operating conditions of the laboratory equipment for the simultaneous determination of Ag, Cd, Cu, Pb and Zn requiring low vaporization power are provided. The method involves drying of 10 µl sample at 100 °C, vaporization at 1500 °C and emission measurement by capture of 20 successive spectral episodes each at an integration time of 500 ms. Experiments showed that emission of elements and plasma background were disturbed by the presence of complex matrix and hot Ar flow transporting the microsample into plasma. The emission spectrum of elements is simple, dominated by the resonance lines. The analytical system provided detection limits in the ng ml-1 range: 0.5(Ag); 1.5(Cd); 5.6(Cu); 20(Pb) and 3(Zn) and absolute detection limits of the order of pg: 5(Ag); 15(Cd); 56(Cu); 200(Pb) and 30(Zn). It was demonstrated the utility and capability of the miniaturized analytical system in the simultaneous determination of elements in soil and water sediment using the standard addition method to compensate for the non-spectral effects of alkali and earth alkaline elements. The analysis of eight certified reference materials exhibited reliable results with recovery in the range of 95-108% and precision of 0.5-9.0% for the five examined elements. The proposed miniaturized analytical system is attractive due to the simple construction of the electrothermal vaporization device and microtorch, low costs associated to plasma generation, high analytical sensitivity and easy-to-run for simultaneous multielemental analysis of liquid microsamples. [ABSTRACT FROM AUTHOR]

Garbage bags have been broadly used for collecting household waste in Brazil and worldwide. Many of these bags are made from recycled polymers, and the presence of harmful elements is a matter of concern. In this study, an energy dispersive X-ray fluorescence (EDXRF) approach for direct analysis of garbage bags is proposed. The concentrations of K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr and Pb were determined in 14 garbage bags of different brands purchased from local markets in Piracicaba, São Paulo State, Brazil. The EDXRF technique proved to be an effective technique for multielemental, environmentally friendly and direct garbage bag monitoring. For most samples, Ca and Ti presented at minor concentration ranges and K, Cr, Mn, Fe, Ni, Cu, Zn and Pb at minor and trace levels. The EDXRF limits of quantification were K: 220; Ca: 112; Ti: 42; Cr: 19; Mn: 13; Fe: 9.2; Ni: 5.7; Cu: 5.3; Zn: 5.2; Br: 12; Rb: 20; Sr: 28 and Pb:17 μg g–1. The samples had variable thicknesses, with a superficial density variation of 1.5 to 23% among the triplicates. The trueness of the method was checked by analysing the National Institute of Standards and Technology standard reference material SRM2783. [ABSTRACT FROM PUBLISHER]

Abstract: In the last years, there has been a revival of total reflection X-ray fluorescence spectrometry (TXRF), which was firstly applied for analytical purposes in the late 80s. The aim of this work is to discuss and compare the current approaches for sample pretreatment including in situ microdigestion, slurry preparation, acid digestion, extraction, etc. prior to TXRF analysis. Advantages and drawbacks inherent to each of those procedures are considered. A comprehensive revision in the period January 2008–July 2013 about different sample preparation strategies prior to TXRF analysis apart from early pioneering reports dealing with sample pretreatment are included in the review. Non-conventional sample pretreatment approaches such as microflow online preconcentration, lab-on-a-chip, etc., are also discussed. Finally, future prospects in sample preparation prior to TXRF analysis are outlined. [Copyright &y& Elsevier]

Highlights: [•] Mineral profile established by inductively coupled plasma optical emission. [•] Protected designation of origin cherries characterized by linear discriminant analysis. [•] Mineral content of the edible parts is more informative that the stone composition. [•] Data about 23 elements of 28 different Spanish cherries have been provided. [Copyright &y& Elsevier]

Abstract: Fast and reliable analytical methodologies are required for quality control of plants in order to assure human health. Ultrasound-assisted extraction in combination with total reflection X-ray fluorescence is proposed as a fast and simple method for multielemental analysis of plants on a routine basis. For this purpose, five certified reference materials have been analysed for the determination of P, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn and Pb. Different extractant media (acids and oxidants) were tried. A mixture of diluted HNO3 +HCl+HF, was selected as the best option for the achievement of complete extractions. Accurate and precise results can be reached in most cases along with a high sample throughput. Different plants (i.e., herbs, spices and medicinal plants) were analysed. Linear discriminant analysis together with the elemental concentrations allowed the differentiation of commercial preparations corresponding to flower, fruit and leaf. [Copyright &y& Elsevier]

Abstract: A method for multielemental (Ca, Cr, Cu, Fe, K, Mg, Mn, Na, P and Zn) determination in multimineral/multivitamins by atomic emission spectrometry in a medium power radiofrequency capacitively coupled plasma (275W) and low Ar consumption (0.4Lmin−1) is proposed. Determinations were performed on commercially available tablets and a standard reference material after acidic high-pressure microwave assisted digestion and using the standard additions procedure. The detection limits (mgg−1) were in the range 0.003 (Na)–1.5 (P) and were not depreciated by the non-spectral interference of mineral matrices of K, Ca, Mg and Na excepting Zn and P. Found concentrations corresponded generally to the labelled contents with recovery in the range of 90–107% and 1.0–13.0% repeatability. The proposed technique could be an advantageous alternative to the more expensive inductively coupled plasma atomic emission spectrometry in the quality control of multimineral/multivitamin preparations. [Copyright &y& Elsevier]

In this work the intralaboratory precision for the simultaneous determination of Al, Si, Fe, Mg, Ni, Co, Cr and Mn in lateritic ores employing coupled plasma atomic emission spectrometry is evaluated. The task was realized in the Laboratory of Minerals from Geominera Orient Company and the standard deviations of the relative differences obtained from 58600 duplicates determinations at 15 levels of concentration were determinate. The value obtained was ± 2,8 % independently of the analyzed element or its concentration level in the sample. This result is agree with the values reported by specialized literature for this type of analysis, but contradicts in part the quality control system established in the laboratory, which utilize different precisions according to the element and concentration level. It is recommended that the laboratory modifies the form which evaluate the quality of the analytical results when the simultaneous quantification is employed, in order to avoid reject correct results with precisions not reached by the analytical system and will be originate a increasing in the total of samples to be controlled, with the unnecessary spent of humans and materials recourses. [ABSTRACT FROM AUTHOR]

Abstract: In this work, two ultrasound-based procedures are developed for sample preparation prior to determination of P, K, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Se and Sr in biological tissues by total reflection X-ray fluorescence spectrometry. Ultrasound-assisted extraction by means of a cup-horn sonoreactor and ultrasonic-probe slurry sampling were compared with a well-established procedure such as magnetic agitation slurry sampling. For that purpose, seven certified reference materials and different real samples of animal tissue were used. Similar accuracy and precision is obtained with the three sample preparation approaches tried. Limits of detection were dependent on both the sample matrix and the sample pre-treatment used, best values being achieved with ultrasound-assisted extraction. Advantages of ultrasound-assisted extraction include reduced sample handling, decreased contamination risks (neither addition of surfactants nor use of foreign objects inside the extraction vial), simpler background (no solid particles onto the sample carrier) and improved recovery for some elements such as P. A mixture of 10% v/v HNO3 +20–40% v/v HCl was suitable for extraction from biological tissues. [Copyright &y& Elsevier]

In this study, we analysed the tree-ring metal concentrations and isotope ratios of five stands located in three contrasted settings to infer the diffuse air pollution history of the northern part of the Windsor-Québec City Corridor in eastern Canada. Tree-ring series show that the Cd and Zn accumulation rates were higher between 1960 and 1986 and that the long-term acidification of the soil (Ca/Al series) was likely induced by NOx and SOx deposition (δ15N and δ13C trends as proxy). The Pb concentrations and 206Pb/207Pb ratios indicate that the dominant source of lead from 1880 to the 1920s was the combustion of north-eastern American coal, which was succeeded by the combustion of leaded gasoline from the 1920s to the end of the 1980s. Our modelling approach allows separating the climatic and anthropogenic effects on the tree-ring δ13C and δ18O responses. Diffuse air pollution caused an enrichment in 13C in all stands and a decrease of the δ18O values only in three of the stands. This study indicates that dendrogeochemistry can show contrasted responses to environmental changes and that the combination of several independent indicators constitutes a powerful tool to reconstruct the air pollution history in the complex context of peri-urban regions. [ABSTRACT FROM AUTHOR]

The aim of this paper is to present the validation of inductively coupled plasma optical emission spectrometry (ICP-OES) method used for metals determination from several perennial plant samples. The suitability of two digestion procedures using wet digestion with mineral acids mixture on hot plate and microwave digestion was investigated to determine As, Cd, Cu, Fe, Mn, Pb and Zn in plants samples. The LOD of the seven analysed elements in solid samples varied between 0.20μg g-1 for Mn and 0.55μg g-1 for Pb. The found values for metals determined by ICP-OES in a vegetable certified reference material digested using the two procedures were compared with the certified values and good agreements between these values were obtained. The proposed method indicated satisfactory recovery, detection limits and standard deviations for trace metal determination in perennial plants samples. [ABSTRACT FROM AUTHOR]

The characterization and accurate determination of the chloride content in cement/concrete is very important for the assessment of the durability and safety of a concrete structure. The available analytical techniques are relatively expensive and time consuming. In this study, a laser-induced breakdown spectroscopy (LIBS) system was used for determination of elemental composition in three different types of cement samples. The plasma was generated by focusing a pulsed Nd: YAG laser at 1064 nm on the cement samples. The concentrations of different elements of significance for structural stability in cement samples were determined. The evaluation of the potential and the capabilities of LIBS as a rapid tool for characterization of cement samples is discussed. The optimum LIBS setup and experimental conditions to detect and measure chloride in building materials are reported. The LIBS results were compared with the results obtained using a standard analytical technique such as inductively coupled plasma emission spectroscopy (ICP-ES). The limits of detection were determined, and calibration curves were measured. The results of this investigation indicate the reliability of LIBS to characterize different cement samples and to assess the chloride content in these cements. [ABSTRACT FROM AUTHOR]

In this study, the elemental concentrations of some spice plants gathered from Mut-Mersin in Turkey were analyzed by polarized energy dispersive x-ray fluorescence (PEDXRF) spectrometry. The analyzed spices are peppermint (Mentha piperita), thyme (Thymus vulgaris), and sumac (Rhus glabra). These samples are very often used in the preparation of Turkish foods. The spice samples are indispensable in foods for Turkish people. The results of the analysis show that each sample has different compositions, and some of these elements have a great benefit in human health. The spice samples results reveal that the PEDXRF method is more reasonably sensitive in the determination of the elemental composition of the plants. [ABSTRACT FROM AUTHOR]

Concentrations of Cd, Cr, Cu, Mn, Mo, Ni, Pb, Se, TI and Zn were analyzed by ICP-MS in the scalp hair of male subjects from an urban area, three different quarters of Krakow, Poland, and from a rural area as control, which were assumed to differ in ambient pollution by metals. A questionnaire on personal data, nutritional habits, socio-economic, occupation and health status was completed by the subjects. Significant differences (p<0.05) were found in the levels of Cd, Cu, Mn and Ni between the locations. Using statistical methods of principal components analysis, the relationships were found between metals in the scalp hair as follows: Mn-Ni, Cr-TI and Cd-Pb. Two separated clusters of smokers were revealed in the principal components, space suggesting other factors like environmental contamination could confound the values of parameters and relationships between them. [ABSTRACT FROM AUTHOR]

During our study a procedure of hair (62 samples) and teeth (38 samples) preparation for the XRF analysis was worked out. The samples were collected from the inhabitants of Katowice, Gliwice, Pysko-wice and Tychy (Silesia, Poland). In hair samples S, Ca, Na, Mg, P, K, Mn, Fe, Cu, Zn, Sr, Pb content was determined and in teeth samples Ca, P, Na, Mg, Al, S, K, Fe, Ni, Cu, Zn, Sr, Pb content was determined. Conformity between the XRF and ICP results was obtained. Several correlations between the concentration of some elements and personal features (sex, age, smoking related) and environmental contamination were indicated. There were differences in the content of Al, Pb and Fe in women's teeth and men's teeth. A positive correlation between age and Mg, Fe, Cu, Sr and Pb content in teeth samples was noticed. Zn, S and Pb content depended on the level of pollution in the environment the samples came from. There were high levels of Zn and Pb concentration in teeth samples from smokers. In hair, positive correlations between the content of Ca, Fe and P and age were observed. Differences in Na, K and S content between women's and men's hair were noticed. Ca and Pb levels were different in samples obtained from different cities in Silesia. No correlation for Ba, Zn, Cu, Mn, Si was observed. [ABSTRACT FROM AUTHOR]