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.     

Elemental content in deionized water by total-reflection X-ray fluorescence spectrometry

This study aimed to evaluate minor and trace elements in the water during different water purification steps of a deionized water production plant, located at CENA, by total-reflection X-ray fluorescence (TXRF) technique, using Ga as internal standard for elemental quantification. This approach was capable of determining Cr, Mn, Fe, Co, Ni, Cu, Zn, Ge, As, Se, Br, Rb at concentrations higher than 40–100 μg L⁻¹, and for K, Ca, Sc, Ti, V and Sr at concentrations higher than sub mg L⁻¹ in the water samples. TXRF spectrometer encompasses an X-ray tube with a Mo target with a Zr filter. The elemental characteristic X-rays were recorded by a Si(Li) semiconductor detector and the X-ray spectra deconvoluted by AXIL software.     

Evaluation of the bioaccumulation of trace elements in tuna species by correlation analysis between their concentrations in muscle and first dorsal spine using microwave-assisted digestion and ICP-MS

Environmental pollution by metals is a recognized problem worldwide. As a result of the exposure to this pollution, marine species may bioaccumulate metals in both muscle and fishbone, as has been demonstrated in some species of tuna. The objective of this study has been the development and optimization of an inductively coupled plasma-mass spectrometry (ICP-MS) based method, which allows the quantification of 21 elements including priority pollutants and biologically essential elements (B, Mg, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Rb, Sr, Pd, Cd, Ba, La, Hg and Pb) in muscle and in the first spine of the first dorsal fin of albacore (Thunnus alalunga) and bluefin tuna (Thunnus thynnus). A microwave-assisted digestion has been developed for sample treatment, which has been evaluated using isotope dilution analysis (IDA) of Cr, Se, Cd, Ba and Pb. Evaluation of the analytical method in terms of sensitivity (LOQ between 0.002 and 1?mg?kg^?1), accuracy and precision within and between days (CV?<?11.3%) has also been conducted. The developed method has allowed information to be obtained on levels of these metals in both matrices. The correlation analyses performed for each of the metals in both matrices shows a positive linear relationship between the concentrations in muscle and fishbone for Zn, Se, Rb, Cd, As and Hg, which could be due to a higher bioaccumulation of these elements in muscle as it is concluded from the low spine/muscle ratios observed for these elements. The 34 specimens of tuna analyzed show that while the levels of Pb, Cd, Ni, Zn, Cu and Cr in muscle are below the limits set by the WHO/FAO, EC and the US-EPA, Hg shows higher concentration than the limits set by the EC in four samples, indicating a potential risk to human health.     

Trace Elements in Pleurotus Ostreatus,P. Eryngii,and P. Nebrodensis Mushrooms Cultivated on Various Agricultural By-Products

Abstract

Mushrooms are efficient accumulators of essential and toxic elements. Although oyster (Pleurotus spp.) mushrooms are widely commercialized and consumed, few data exist regarding trace elements content and bioaccumulation in cultivated P. ostreatus and P. eryngii, while no data are available for P. nebrodensis. The contents of Al, As, Ba, Cd, Co, Cr, Cs, Cu, Fe, K, Mn, Na, Ni, Pb, Rb, Sr, V, and Zn were monitored using inductively coupled plasma-mass spectrometry (ICP-MS) and atomic emission spectrometry (AES) in P. ostreatus, P. eryngii, and P. nebrodensis mushrooms and their cultivation substrates that include wheat straw (WHS), grape marc (GMC), olive leaves (OLV), and two-phase olive mill wastes (OMW), separately or in mixtures. Bioaccumulation factors (BAFs) less than 0.3 were obtained for Al, Ba, Co, Cr, Fe, Mn, Ni, Pb, Sr, and V; BAFs exceeding 1 for K?>?Zn?>?Cd?>?Cr?>?Rb?>?As, while the BAFs for Na were less 0.7. Mushrooms grown on OLV and OMW presented lower BAFs than those grown on WHS and GMC for all elements except for K, Cd, and Cu. P. ostreatus was an effective accumulator for Cr, Fe, and Zn; P. eryngii for Al, Cs, Ni, and V; and P. nebrodensis for As and Cd. The estimated daily intakes (μg kg^?1 body weight) from mushroom consumption were less than 0.010 for As, Cd, Co, Cs, Pb, and V, 0.010–0.10 for Ba, Cr, Ni, and Sr, 0.10–5.0 for Al, Cu, Fe, Mn, Rb, and Zn, 65–83 for Na, and 858–1030 for K. Overall, the mushrooms studied provide significant amounts of K, adequate amounts of Mn and Zn and low amounts of Na and toxic elements.     

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.     

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.     

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.     

Total reflection X-ray fluorescence analysis of fly ash from Bulgarian coal-fired power plants

The contents of Cl, Ca, K, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Rb, Sr, Ba and Pb in raw coal fly ash from five Bulgarian power plants were determined by total reflection X-ray fluorescence (TXRF), using gallium as the internal standard. The samples were analysed as in slurry form in Triton? X-114. The experimental parameters, such as grain size, concentrations of fly ash slurry and excitation time were optimised. For validation of the method, the certified reference material BCR-176R fly ash was used. The precision of the results obtained is characterised by a relative standard deviation of approximately 10%. The resulting data confirm the suitability of TXRF for the simultaneous determination of major, minor and trace elements in coal fly ash samples. Further advantages provided by TXRF are easy sample preparation (no sample dissolution) and the small sample amount required for analysis.     

Essential and trace element contents of some Nigerian medicinal plants

The energy-dispersive X-ray fluorescence (EDXRF) spectroscopy has been used for the determination of essential and trace elements" contents of some twenty Nigerian medicinal plants. The accuracy and precision of the technique were assured by analyzing the European Community Bureau Reference Standard BCR 62 (Olive Leaves). Fourteen elements, namely K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Se, Br, Rb, Sr were detected with toxic heavy metal such as Cd, As, Pb, Hg were detected in the samples. The ranges of elemental concentrations varied from 7.7^.10⁴ to 1.6 mg/kg in the herbs. The results show that many of these plants contain elements of vital importance for human metabolism and prevention and healing of diseases.     

XRF and TXRF techniques for multi-element determination of trace elements in whole blood and human hair samples

XRF and TXRF were established as useful techniques for multi-element analysis of whole blood and human head hair samples. Direct-XRF with different collimation units and different X-ray excitation modes was successfully used for the determination of S, P, K, Ca, Fe, and Br elements in blood samples and K, Ca, Mn, Fe elements in human hair samples. Direct analysis by TXRF was used for the determination of Rb and Sr in digested blood and human hair samples, respectively, while, the co-precipitation method using APDC for TXRF analysis was used for the determination of Ni, Cu, Zn, and Pb elements in both matrices. As a result, the improved XRF and TXRF methods were applied for multi-element determination of elements in whole blood and human hair samples in non-occupational exposed population living in Damascus city. The mean concentrations of analyzed elements in both matrices were on the reported range values for non-occupational population in other countries.     

Multielementanalyse von Aerosolen mit Hilfe der R?ntgenfluorescenzanalyse mit totalreflektierendem Probentr?ger (TRFA)

Zusammenfassung Für Aerosolproben auf Filterunterlage werden unter Benutzung der Röntgenfluorescenzanalyse mit totalreflektierendem Probenträger (TRFA) als Bestimmungsmethode Analysenverfahren aufgezeigt und charakterisiert.Bei dem Naßaufschluß des Probenmaterials im geschlossenen System mit HNO₃ mit anschließender Meßprobenpräparation durch Eintrocknung eines Aliquots der Lösung auf dem Probenträger werden Nachweisgrenzen bis zu 0,3 ng/cm² erhalten. Die Reduzierbarkeit der Messung beträgt für die Elemente K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Rb, Sr, Ba und Pb zwischen 5 und 25%. Bei Verwendung des Lowtemperature-Sauerstoffplasmas für die Veraschung von homogen belegten Membranfiltern auf dem Probenträger lassen sich ähnliche Reproduzierbarkeiten und Nachweisgrenzen erhalten. Beide Verfahren wurden inaktiv und mit Radiotracern hinsichtlich systematischer Elementverluste untersucht.Zur Bestimmung des Broms und zur schnellen Erfassung von Hauptbestandteilen wird eine Möglichkeit für die Vermessung von Membranfiltern unter Umgehung eines Veraschungsschritts aufgezeigt. Die Nachweisgrenzen betragen hier bis zu 3 ng/cm².Der Ergebnisvergleich mit den entsprechenden Werten der NNA, der AAS und der PIXE ergibt zumeist gute Übereinstimmungen der Resultate.

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Multielement analysis of aerosol samples by X-ray fluorescence analysis with totally reflecting sample holders

Summary Aerosole samples on filter support were analyzed using the X-ray flourescence analytical method (Mo excitation) with totally reflecting sample carrier (TXFA).Wet decomposition of the sample material with HNO₃ in an enclosed system and subsequent sample preparation by evaporating an aliquot of the solution on the sample carrier yields detection limits up to 0.3 ng/cm².The reproducibilities of the measurements of the elements K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Rb, Sr, Ba and Pb lie between 5 and 25%.Similar detection limits and reproducibilities are obtained, when low-temperature oxygen plasma is employed for the direct ashing of the homogenously covered filter on the sample carrier.For the systematic loss of elements both methods were investigated with radiotracers as well as with inactive techniques. A comparison of the results with those obtained by NAA, AAS and PIXE shows good agreement in most cases.For the bromine determination and the fast coverage of the main elements a possibility for measuring the filter membrane has been indicated, which neglects the ashing step. The corresponding detection limits are up to 3 ng/cm².

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Herrn Prof. Dr. W. Fresenius zum 70. Geburtstag gewidmet     

Cold plasma ashing improves the trace element detection of single Daphnia specimens by total reflection X-ray fluorescence spectrometry

The recently developed dry method for the element determination of single freshwater microcrustacean specimens (Daphnia) using total reflection X-ray fluorescence (TXRF) spectrometry showed that inhomogeneities of the biological material on the glass carriers resulted in some cases in high background and hampered the detection of certain trace elements (e.g. Cr, Ni). The aim of this study was to test how inhomogeneities of the biological material can be reduced using cold plasma ashing (CPA) techniques. For that, single specimens of the microcrustacean Daphnia pulex prepared according to the dry method were measured by TXRF before and after CPA. To determine the efficiency of the removal of organic matrix, the background and signal-to-background relationship of 28 samples were analyzed. The results showed (1) a highly significant reduction of the background by CPA fluctuating between 26 and 46% (all elements) and (2) a significant increase of the signal-to-background relationship by the factor 1.5–2.5 (all elements) and a much better detection of Cr, Pb, As and Se. The element concentrations (with exception of Cr, Ni and Pb) after ashing were in the same range or slightly higher than that before ashing. No significant differences between the two treatments were observed for Mn, As, Pb, Se (November), Sr (November), Cr (March) and Pb (March). The element concentration of P, K, Ca, Cu, Zn, Cr (November), Fe and Rb were significantly higher after ashing. In general, they increased by 1.5–13.6% and were highest for Rb (March) and P (November). In contrast, the element concentration of Ni and Cr (only March) decreased significantly after ashing (Ni: 91.6–92.1%, Cr: 91.3%). We recommend the use of CPA for biological material in the microgram-range as a routine method for TXRF analysis, especially when trace elements in minute concentrations are of interest.     

Major and Trace Element Accumulation in Coastal Sediments along Southeastern Baja California Studied by Instrumental Neutron Activation Analysis and 210Pb Age-Dating

The vertical distribution of K, Rb, Cs, Ca, Sr, Ba, Fe, Cr, Co, Ni, Zn, Sc, Zr, Sb, Se and As was studied by means of instrumental neutron activation analysis in four sediment cores collected from the eastern shelf of tectonically active Baja California peninsula accompanied by ²¹⁰Pb age-dating. ²¹⁰Pb analysis was performed by extraction chromatography with measuring the ingrowing daughter 210Bi radioactivity by liquid-scintillation spectrometry. It was found that concentration variations of Se, As, Sb, Zr and Zn are probably controlled by the intensity and composition of the material supplied from the drainage basin constituted by volcanic and sedimentary rocks.     

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.     

Trace,Alkaline and Alkaline-Earth Elements in Sea Water Samples from Terra Nova Bay - Ross Sea (ANTARCTICA): A Three-Year Period of Observation

Abstract

This report concerns the correlation of the analytical results relevant to some elements obtained in filtered sea water samples collected in Terra Nova Bay and the Ross Sea (Antarctica) during three Italian expeditions. The following ranges of variability of the medians of total concentrations (ng/l) - which include time effect among expeditions and bias effect among participant groups - were found for trace elements (single values refer to elements which were only determined once by one laboratory): Sb (260), As (1.2 10³), Cd (5–50), Cr (120), Co (4), Cu (110–230), Fe (435–445), Pb (6–52), Mn (15–88), Hg (3), Ni (185–580), Se (30) and Zn (242–265). Speciation studies pointed out that 10–40% of Cd, 15–60% of Cu and 20–50% of Pb were present in the samples as an ASV-labile fraction.

As for alkaline and alkaline-earth elements, the following concentration ranges in surface sea waters, expressed in mM, were found: Li ([1.4–3.0] 10^?2), Na (394–480), K(5.1–9.9), Ca (6.4–14.7), Mg (46.2–59.0) and Sr ([7.6–10] 10^?2).

Inter- and intra-laboratory data comparison, incorrect results, local variations of concentration, including pollution effects and pack melting effect, are discussed in detail.     

Solid phase extraction and diffusive gradients in thin films techniques for determination of total and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) in Black Sea water

Total dissolved and labile concentrations of Cd(II), Cu(II), Ni(II) and Pb(II) were determined at six locations of the Bourgas Gulf of the Bulgarian Black Sea coast. Solid phase extraction procedure based on monodisperse, submicrometer silica spheres modified with 3-aminopropyltrimethoxysilane followed by the electrothermal atomic absorption spectrometry (ETAAS) was developed and applied to quantify the total dissolved metal concentrations in sea water. Quantitative sorption of Cd, Cu, Ni and Pb was achieved in the pH range 7.5–8, for 30?min, adsorbed elements were easily eluted with 2?mL 2?mol?L^?1 HNO₃. Since the optimal pH for quantitative sorption coincides with typical pH of Black Sea water (7.9–8.2), on-site pre-concentration of the analytes without any additional treatment was possible. Detection limits achieved for total dissolved metal quantification were: Cd 0.002?µg?L^?1, Cu 0.005?µg?L^?1, Ni 0.03?µg?L^?1, Pb 0.02?µg?L^?1 and relative standard deviations varied from 5–13% for all studied elements (for typical Cd, Cu, Ni and Pb concentrations in Black Sea water). Open pore diffusive gradients in thin films (DGT) technique was employed for in-situ sampling and pre-concentration of the sea water and in combination with ETAAS was used to determine the proportion of dynamic (mobile and kinetically labile) species of Cd(II), Cu(II), Ni(II) and Pb(II) in the sea water. Obtained results showed strong complexation for Cu and Pb with sea water dissolved organic matter. The ratios between DGT-labile and total dissolved concentrations found for Cu(II) and Pb(II) were in the range 0.2–0.4. For Cd and Ni, these ratios varied from 0.6 to 0.8, suggesting higher degree of free and kinetically labile species of these metals in sea water.     

Identification of elements in plant drugs and their water infusion using X-ray fluorescence analysis

The present work gives preliminary results of analysis of drug mixtures (NEPHROSAL tea bag) and its water infusion. In a sample of dried drugs the elements K, Ca, Mn, Fe, Ni, Cu, Zn, Br, Rb, Sr, Pb were identified, whereas in their water infusion only Ca, Mn, Zn and Sr were found. The method applied was radionuclide X-ray fluorescence analysis using a radionuclide source¹⁰⁹Cd, a Si/Li semiconductor detector and a multichannel analyzer Canberra 8100.     

Determination of trace elements in Syrian medicinal plants and their infusions by energy dispersive X-ray fluorescence and total reflection X-ray fluorescence spectrometry

X-ray fluorescence (XRF) and total-reflection X-ray fluorescence (TXRF) techniques suited well for a multi-element determination of K, Ca, Mn, Fe, Cu, Zn, Rb, and Sr in some Syrian medicinal plant species. The accuracy and the precision of both techniques were verified by analyzing the Standard Reference Materials (SRM) peach-1547 and apple leaves-1515. A good agreement between the measured concentrations of the previously mentioned elements and the certified values were obtained with errors less than 10.7% for TXRF and 15.8% for XRF. The determination of Br was acceptable only by XRF with an error less than 24%. Furthermore, the XRF method showed a very good applicability for the determination of K, Ca, Mn, Fe, Cu, Zn, Rb, Sr, and Br in infusions of different Syrian medicinal plant species, namely anise (Anisum vulgare), licorice root (Glycyrrhiza glabra), and white wormwood (Artemisia herba-alba).     

The use of Si carriers for aerosol particle collection and subsequent elemental analysis by total-reflection X-ray fluorescence spectrometry

The adoption of polished Si carriers was studied for the sensitive elemental analysis of aerosol particles using total-reflection X-ray fluorescence (TXRF) spectrometry. The surface roughness of the Si carrier measured by atomic force microscopy was found to be smaller than those of glassy carbon and quartz glass carriers, which are commonly used for TXRF analysis. The detection limits of elements for the Si carrier were superior to those for the glassy carbon and the quartz glass carriers, presumably due to its smaller surface roughness. For example, the detection limit of Sr for the Si carrier was 9 pg, which was 100 times and 3 times lower than those for the glassy carbon and the quartz glass carriers, respectively. The Si carriers could be successfully applied to the direct aerosol particle collection by impaction and the subsequent elemental analysis by TXRF. From the results of the elemental analysis of aerosol particles, the variations in the concentrations of K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn Sr and Pb with time could be clarified.