Possibilities of ED-XRF with radionuclide sources for analysis of plants

A comparative evaluation of the applicability of different radionuclide sources for the determination of toxic elements in plants by ED-XRF is presented.²³⁸Pu or¹⁰⁹Cd are suggested as most suitable single excitation sources in ED-XRF for monitoring investigations. More elements are determined with a combination of⁵⁵F/¹⁰⁹Cd(²³⁸Pu)/²⁴¹Am. The results obtained by radionuclide ED-XRF analysis of different plants show that the method permits the reliable determination of Br, Ca, Fe, K, Mn, Rb, Sr and Zn in plant bioindicators. For toxic elements like As, Cd, Cu Cr, Hg, Ni, Se and Pb the detection limits of the method are not low enough.     

Heavy metals and some other elements in medicinal plants. Determined by X-ray fluorescence analysis

Determination of Mn, Fe, Cu, Zn, Hg, Pb, Br, Se, Rb, Sr and Cd in the medicinal plants by radionuclide X-ray fluorescence analysis (using²³⁸Pu,²⁴¹Am/Ag and¹²⁵I) is described.     

Evaluation of strontium isotope abundance ratios in combination with multi-elemental analysis as a possible tool to study the geographical origin of ciders

In order to evaluate alternative analytical methodologies to study the geographical origin of ciders, both multi-elemental analysis and Sr isotope abundance ratios in combination with multivariate statistical analysis were estimated in 67 samples from England, Switzerland, France and two Spanish regions (Asturias and the Basque Country). A methodology for the precise and accurate determination of the ⁸⁷Sr/⁸⁶Sr isotope abundance ratio in ciders by multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) was developed. Major elements (Na, K, Ca and Mg) were measured by ICP-AES and minor and trace elements (Li, Be, B, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Mo, Cd, Sn, Sb, Cs, Ba, La, Ce, W, Tl, Pb, Bi, Th and U) were measured by ICP-MS using a collision cell instrument operated in multitune mode. An analysis of variance (ANOVA test) indicated that group means for B, Cr, Fe, Ni, Cu, Se, Cd, Cs, Ce, W, Pb, Bi and U did not show any significant differences at the 95% confidence level, so these elements were rejected for further statistical analysis. Another group of elements (Li, Be, Sc, Co, Ga, Y, Sn, Sb, La, Tl, Th) was removed from the data set because concentrations were close to the limits of detection for many samples. Therefore, the remaining elements (Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba) together with ⁸⁷Sr/⁸⁶Sr isotope abundance ratio were considered for principal component analysis (PCA) and linear discriminant analysis (LDA). Finally, LDA was able to classify correctly 100% of cider samples coming from different Spanish regions, France, England and Switzerland when considering Na, Mg, Al, K, Ca, Ti, V, Mn, Zn, As, Rb, Sr, Mo, Ba and ⁸⁷Sr/⁸⁶Sr isotope abundance ratio as original variables.     

Ion chromatographic determination of alkaline earth metals and some heavy metals

The method is described for ion chromatographic determination of Ba, Ca, Cd, Cu, Mn, Ni, Sr, Pb and Zn. Ethylenediammonium chloride or tartrate solutions are used as eluents with a suppressor column. The detection limits for the listed elements are (in μg l^?1): Ba 1.4, Ca 0.045, Cd 0.6, Cu 0.3, Mn 0.8, Ni 0.5, Pb 6.3, Sr 0.3, Zn 1.2. Relative standard deviations are 0.015–0.050 ar the 20 mg l^?1 level (n = 5, p = 0.95). Interferences are considered.     

Application of multivariate optimization in the development of an ultrasound-assisted extraction procedure for multielemental determination in bean seeds samples using ICP OES

In this paper, multivariate optimization was applied for the development of an ultrasound-assisted multielemental extraction procedure for analysis of bean samples by inductively coupled plasma optical emission spectrometry. For this procedure, powdered samples were treated with an acid mixture and submitted to ultrasound energy for extracting the target elements (Ba, Ca, Cu, Fe, K, Mg, Mn, Sr and Zn). Centroid simplex mixture design was used for optimize the acid proportions (nitric, acetic and chloride acid) and Box Behnken design was applied for optimize the process variables (particle size, final concentration of extracting solution and sonication time) after mixture optimization. Iron had not presented quantitative extractions and it was excluded from final samples analysis. The developed method presents the follow limits of quantification in μg g^{− 1}: Ba (0.90); Ca (5.2); Cu (4.0); K (0.90); Mg (1.4); Mn (0.22); Sr (0.25) and Zn (4.0). Accuracy was accessed by comparison of determined concentration with the values obtained by the microwave digestion procedure. The proposed method was applied toward the determination of elemental composition in bean samples collected in the country zone from Jequié city located on the Bahia State, Brazil. The trace elements content ranged from 0.21 to 3.04, 3.84 to 10.8, 0.60 to 5.23, 31.0 to 46.5 and 10.8 to 19.6 μg g^{− 1} Ba, Cu, Sr, Zn, Mn, respectively. The major elements content ranged from 0.0418 to 0.0877, 0.109 to 0.153 and 1.30 to 1.56% (w/w) Ca, Mg and K, respectively.     

Multielemental evaluation of garbage bags by EDXRF

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.     

Multielement determination in river water by neutron activation analysis

Concentrations of Al, Br, Ca, Ce, Co, Cr, Eu, Fe, Hf, La, Lu, Mg, Mn, Na, Rb, Sc, Sm, Sr, Tb, Th, Ti, V, Yb, Zn, and Zr have been measured in Tigris and Euphrates river water, using neutron activation analysis in combination with preconcentration technique. River water samples were preconcentrated by evaporation at 70°C under atmospheric pressure. The samples with standard reference materials were irradiated with a neutron flux of 2.3·10¹³ n·cm^–2·s^–1.     

Neutron activation analysis of ivory of African elephants

Instrumental neutron activation analysis was applied to 61 ivory samples of which origin countries are known. 12 elements such as Br, Ca, Cl, Co, Cs, Fe, Mg, Mn, Na, Sc, Sr and Zn, were determined in all samples. The factor score of each sample was calculated for each factor by making use of principal component analysis in order to determine their origins. The results were compared with those by stable isotope analysis (¹³C and¹⁵N).     

Determination of metal impurities in ultrapure CaCl2 and MgCl2 by ICP OES

An effective, rapid and simple analytical method for the determination of Na, K, Ca, Mg, Cd, Pb, Ba, Fe, Mn, Sr, Zr, Cu, Zn and Al at mg kg⁻¹ levels in the ultrapure salts MgCl₂ and CaCl₂ using optical emission spectrometry was developed. Optimisation of the operation conditions was performed with real samples of ultrapure MgCl₂ and CaCl₂. The results of the determination with multi-elemental water standards were compared to the internal standardisation, the standard addition method, and the maximum allowable content of the above mentioned elements in pure chemicals. The method was shown to be very sensitive with the following limits of detection: Na 1.01, K 3.12, Ca 0.263, Mg 0.275, Cd 0.0832, Pb 0.482, Ba 0.0153, Fe 0.0528, Mn 0.0473, Sr 0.0203, Zr 0.638, Cu 0.0732, Zn 0.0686 and Al 0.459 (all in mg kg⁻¹). The method exhibited satisfactory precision, high analytical recoveries, linear responses of an accuracy of at least 4 orders of magnitude and low contamination susceptibility.     

Trace element distribution in geochemical environment of the island Krk and its influence on the local population

Samples of soil, plant material and water collected on the Croatian island Krk in northern Adriatic sea were analyzed for a number of elements (Ca, Ti, Mn, Fe, Ni, Cu, Zn, As, Br, Rb, Sr, Zr, Pb) by using energy dispersive X-ray fluorescence (EDXRF) as an analytical tool. Some of these data have been previously used to produce geochemical map of the island.¹ In addition, trace element contents of hair from children, attending elementary and secondary schools, has been investigated using the same analytical method for Mg, S, Ca, Cr, Mn, Fe, Ni, Cu, Zn, As, Hg and Pb elements. Concentrations of the twelve elements and nine variables from the questionnaire, i.e., age, sex, living place, transportation, medication, hair colour, hair type, type of shampoo used and hair treatment, were considered in the statistical analysis. The observed differences for the seven island's communes have also been discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Excretion of biotrace elements using the multitracer technique in mice

A radioactive multitracer solution obtained from the nuclear reaction of selenium with 25 MeV/nucleon⁴⁰Ar ions was applied to the investigation of the trace elements behavior in feces and urine of mouse. The excretion rates of 23 elements, Na, K, Rb, Mg, Ca, Sr, Ga, As, Sc, V, Cr, Mn, Co, Fe, Zn, Y, Zr, Mo, Nb, Tc, Ru, Ag and In were simultaneously detected under strictly identical experimental conditions, in order to clarify the excretion behavior of the elements in mice. Fecal and urinary excretion rates of the elements in mice reached the highest value separately at 48 and 24 hours. The total excretion of Mo, Tc and Co within 96 hours were all larger, more than 60%. Accumulative excretion rates of Ca, Nb, Mg, Sr, V, Sc, Na, Cr, Fe, Ag, Mn and Zr were 60-30%. The total rates of Ru, K, As, Zn, Rb, Y, Ga and In were less than 30%, and low excretion. The main excretion pathway of Mo, Co, Mg, Fe and Ag was through urine, and Na, K, As and Rb were eliminated from the body also in urine. But fecal excretion of Tc, Nb, Sr, Y, Ru, and In were larger than urinary excretion, and Ca, Sc, Mn, Zr, Zn were eliminated from the body in feces.     

Ionen-chromatographische Analyse von Mg, Ca, Mn und Zn mit Anwendungsbeispielen zur Ca-/Mg-Bestimmung

Zusammenfassung Es werden die Trennmöglichkeiten für Ca, Mg, Sr, Mn, Zn, Ni und Pb an einem kommerziell erhältlichen Kationenaustauscher geringer Kapazität mit einem Gemisch aus Ethylendiamin und Citronensäure sowie anderen organischen Säuren als mobile Phasen ermittelt. Die Abhängigkeiten der Retentionszeiten von der Konzentration an Ethylendiamin und Citronensäure sowie vom pH-Wert werden untersucht. Die quantitativen Analysen erfolgen mittels eines Leitfähigkeits-Detektors. Für Ca und Mg ergeben sich Nachweisgrenzen von 20 bzw. 10 ppb (0,4 bzw. 0,2 ng in der Meßzelle). Anwendungsbeispiele für Wasser, Boden und Gestein mit Vergleichen zur komplexometrischen Titration werden vorgestellt.

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Ion-chromatographic analysis of Mg, Ca, Mn and Zn together with application examples for Ca/Mg determination

Summary The possibilities were found out for the separation of Ca, Mg, Sr, Mn, Zn, Ni and Pb on a commercial cation-exchanger column of low capacity by ethylendiamine and citric acid and other organic acids mixtures as eluents. The dependences of retention times on concentrations of ethylendiamine and citric acid as well as on the pH value were investigated. Quantitative analyses were carried out by means of a conductivity detector. For Ca and Mg the detection limits are 20 and 10 ppb resp. (0.4 and 0.2 ng resp. in the detector cell). Application examples for water, soil and rock with comparisons to the complexometric titrations are presented.

     

A new approach for determination of crustal and trace elements in airborne particulate matter

An ICP-OES procedure was developed for fast and accurate determination of various crustal (Al, Ca, Fe, Mg, Si) and trace elements (Ba, Cu, Mn, Na, K, Sr, Ti, Zn) in airborne particulate matter. The method is based on a preliminary treatment of the aerosol samples with a mixture of nitric acid and hydrogen peroxide at elevated temperature leading to a mineralization of the organic sampling substrate, dissolution of soluble material and homogeneous suspension of the remaining non-soluble fraction. After dilution the derived slurry solutions were measured using ICP-OES. The reproducibility of analysis given as the relative standard deviation (% RSD) varied between 3.2 and 6.8% for bulk constituents such as Al, Ca, Fe, Mg and Si whereas values ranging from 3.5 to 9.1% were obtained for trace metals present with distinctly lower abundance in PM10 (e.g. Ba, Cu, Mn, Sr, Zn). The limits of detection (LOD) calculated as three times the standard deviation (3σ) of the signal derived from filter blank samples ranged from approximately 1?ng?m^?3 (Sr) to 71?ng?m^?3(Ca). The developed procedure was evaluated by comparing the obtained results with the findings derived for the same set of aerosol samples analyzed using a microwave procedure for sample dissolution with subsequent ICP-OES analysis. Finally the developed procedure was applied for the analysis of crustal and trace elements in PM10 samples collected at an urban site (Getreidemarkt, Vienna) and a rural site (Hartberg, Styria), in Austria. The concentrations of the investigated crustal elements varied between some hundred ng?m^?3 and few µg?m^?3 with highest concentrations for Fe and Si, distinctly reduced concentrations ranging from some ng?m^?3 (Sr) to more than hundred ng?m^?3 (K) were found for trace elements. Observed PM10 concentrations were found to be in accordance to literature findings from urban sites in central Europe.     

The behaviour of precipitating systems of Mg,Ca, Sr,Ba, Mn and Zn-oxalates in aqueous and in the ethanol medium at the room temperature

Summary The behaviour of precipitating systems of Mg, Ca, Sr, Ba, Mn and Zn oxalates in statu nascendi from the electrolytic solutions in water and in ethanol were determined by tyndallometric technique. PDs (diagrams by plotting of logarithms of concentrations of cationic component against anionic one) show the limits of liquid/solid phase. According to the PDs, the solubility of oxalates in water increases in the following order: Ca < Sr < Zn < Ba < Mg < Mn. In the alcohol medium, the complexes disappear, the limits approach to the ionic solubility products.

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Zusammenfassung Die Reihe der Mg, Ca, Sr, Ba, Mn und Zn-Oxalate wird tyndallometrisch in wässeriger und wässerigäthanolischer Base untersucht. Die Ergebnisse werden in sog. Fällungsdiagrammen dargestellt. Nach diesen steigt die Löslichkeit der Oxalate in der Reihe: Ca < Sr < Zn < Ba < Mg < Mn.

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With 3 figures     

Multielement determination in water by instrumental neutron activation analysis

Instrumental neutron activation analysis /INAA/ technique has been applied to a water sample to determine the elemental concentrations. The sample was irradiated with a neutron flux of 1.2×10¹² n cm^–2 s^–1 for two different periods followed by counting at three different decay times, using two coaxial type high-resolution Ge/Li/ detectors. The dominant elements determined in the water sample are Ca, Cl, Na, Mg, and K present in ppm-level while Co, I, Mn, Sm, and Sb are present in smaller amounts, approximately on the average 0.01 ppm. Only traces of other elements such as the rare-earth elements, Ag, As, Ba, Cu, Cd, Fe, Sr, W, Zn, seem to be present in the water sample.     

INAA of cortical and trabecular bone samples from animals

Instrumental neutron activation analysis (INAA) was applied to determine Ba, Br, Ca, Cl, Fe, K, Mg, Mn, Na, P, Sr and Zn in bovine and porcine rib bones. Precise results were obtained in analyses of freeze-dried cortical and trabecular bones separately, and also of whole bone ashes. Cortical tissues presented higher concentrations of Ba, Ca, Mg, Mn, Na, P, Sr and Zn than those obtained in trabecular ones. Comparisons were also made between the results obtained for bovine and porcine rib bones. This revised version was published online in August 2006 with corrections to the Cover Date.     

Multielemental determination in water by neutron activation analysis

Instrumental neutron activation analysis (INAA) technique has been applied to a water sample to determine the elemental concentrations. The sample was irradiated at a neutron flux of 1.2·10¹² n·cm^–2·s^–1 for two different periods followed by counting at three different decay times, using two coaxial type high-resolution Ge(Li) detectors. The dominant elements detected in the water sample are Ca, Cl, Na, Mg, and K present in levels while Co, I, Mn, Sm, and Sb are present in smaller amounts approximately on the average 0.01 ppm. Only traces of other elements such as rare-earth elements, Ag, As, Ba, Cu, Cd, Fe, Sr, W, Zn, seem to be present in the water samples.     

Neutron activation analysis of ivory of African elephants

Instrumental neutron activation analysis was applied to 80 samples from various African countries and 81 samples from the Kruger National Park in the Republic of South Africa. Twelve elements such as Br, Ca, Cl, Co, Cs, Fe, Mg, Mn, Na, Sc, Sr, and Zn, were determined in all samples. The factor scores of each sample were calculated from those elemental concentrations for the first and second factors to clarify the differences of samples from various African countries with those from Kruger Park. The results were compared with those by stable isotope analysis (¹³C and¹⁵N).     

Three-filament and toroidal microwave induced plasmas as radiation sources for emission spectrometric analysis of solutions and gaseous samples—II: Analytical performance

The generation of two new types of the Ar-MIP and their analytical performance as radiation sources for atomic emission spectrometry in the extreme trace analysis of elements is described. A stable 3-filament Ar-MIP, and a toroidal Ar-MIP can be generated in a cylindrical TM₀₁₀ cavity with special mountings and adjustment devices for the discharge tube. The first was found to be suitable for the determination of volatile elements or compounds and the latter for the analysis of solutions subsequent to pneumatic nebulization. The influence of different plasma parameters, e.g. microwave power and argon gas flow was investigated. The detection limits for the elements Be, Ca, Cd, Co, Cr, Cu, Ga, Hg, Mg, Mn, Sr, Tl and Zn were found to be in the range of 1–50 ng ml^?1. As an example for the application of the toroidal MIP, analyses of natural water samples (drinking water, glacial ice and snow) were performed.