Trace element characterization by INAA of three sediments to be certified as standard reference materials

Three environmental matrices proposed as Certified Reference Materials, issued by the EU Standards, Measurement and Testing Programme (SMTP) formerly Bureau Communautaire de Reference (BCR) have been characterized for their trace element contents.The materials are: BCR 277 R Estuarine Sediment, BCR 280 R Lake Sediment and BCR 320 R Channel Sediment.Several trace elements, including As, Co, Cr, Fe, Mn, Ni, Sb, Sc, Th, U and Zn have been determined by our laboratory using Instrumental Neutron Activation Analysis (INAA). Our contributed values are being considered for the final certification.     

A CRL–IRMM joint proficiency test for trace elements in fish tissue

The Community Reference Laboratory (CRL) for residues and contaminants in food of animal origin at the Istituto Superiore di Sanità (ISS) plans and undertakes on a regular basis Proficiency Tests Schemes (PTSs) focused on the residues under its responsibility, as prescribed by the Council Directive 96/23/EC of April 29, 1996. In consideration of the benefits ensuing from a constant monitoring of the daily activities of the National Reference Laboratories (NRLs) for residues in the Member States, the ISS–CRL frequently prepares test materials to promote comparability of data and support harmonisation of routine analytical procedures. When target values for the analytes are set, the PTSs also provide objective assessment and improvement of the analytical trueness in the daily work.In this context, an interlaboratory comparison for trace elements in tuna fish matrix was organised in cooperation with the Institute for Reference Materials and Measurements (IRMM), Joint Research Centre, European Commission. Freeze-dried tuna fish samples were sent out to the NRLs for chemical elements in the Member States. Participants were requested to carry out at least three independent measurements of the elements As, Cd, Cr, Cu, Fe, Hg, Pb and Zn. The assessment of the proficiency was based on the z-score approach and a relative bias better than or equal to 10% of the target value was deemed to be an acceptable performance for this kind of measurements. On this basis, more than 50% of the laboratories returned accurate results for As, Cu, Fe, Hg and Zn, whereas the analysis of Cd, Cr and Pb appeared to be more problematic.     

Ultra-trace nutritional and toxicological elements in Rome and Florence drinking waters determined by Instrumental Neutron Activation Analysis

In order to ascertain water quality for human consumption, the evaluation of trace and ultra-trace elements in drinking waters of two Italian cities, Rome and Florence, is investigated together with the potabilization processes involved and the relative human exposure to the contaminants. Through a multi-elemental detection with no chemical treatment using Instrumental Neutron Activation Analysis and Proton-Induced X-ray Emission the concentration of 40 elements is determined. Basically, the concentrations of the investigated parameters in drinking waters were within the permissible limits of the World Health Organization drinking water quality guidelines and the Water Pollution Control legislation of Italian authorities. The Rome drinking water shows a chemical water composition quite similar to uncontaminated natural water: potentially toxic elements (e.g., Cr, Hg, Ni, and Sb) are present at very low concentrations whereas the levels of nutritionally essential elements are adequate and low levels of I and Se cannot be considered a cause of deficiency diseases. A multivariate statistical approach was used to identify both the origins and correlations among elements and the six different apportionments contributing to the water supply in Rome. For the drinking waters distributed in Florence, the element levels show a sufficiently good situation, except for Al (range 103–267 μg/L) that is present at reasonable concentrations for almost the entire population due to the hard potabilization procedure involving aluminum salts. The values of Metal Index (MI), that helps to quickly evaluate the overall quality of drinking waters, show a good drinking water quality in Rome (Fe is the only element to be considered critical) whereas in Florence the situation is influenced by Al levels. No relevant differences are found among Rome and Florence water composition and other Italian and world potable waters.This study can be considered a useful reference for studies aimed to highlighting toxicological, nutritional and environmental disease patterns.     

IMEP-12: trace elements in water; objective evaluation of the performance of the laboratories when measuring quality parameters prescribed in the European Directive 98/83/EC

The International Measurement Evaluation Programme (IMEP) is an interlaboratory comparison scheme, founded, owned and co-ordinated by the Institute for Reference Materials and Measurements (IRMM) since 1988. IMEP-12, for the fourth time in the series, focused on trace elements in water and it was designed specifically to support European Commission directive 98/83/EC. Reference values for the concentration of ten elements were established with expanded uncertainties according to GUM. In total, 348 laboratories from 46 countries in five continents participated in the comparison and the degree of equivalence between the results of the laboratories and the reference values is presented graphically. Samples from the same batch were distributed to ten laboratories from European Countries, which represented their country in the framework of the EUROMET project 528. Participation in this comparison was offered to the European Co-operation for Accreditation (EA) for participation of accredited laboratories from all over Europe in the framework of the collaboration between IRMM and EA and to laboratories from the EU new member states and acceding countries in the frame of IRMM’s ‘Metrology in Chemistry support program for EU new member states and acceding countries.’     

Individuation of characteristic parameters of “glass paste” of Meridional Etruria by the use of scientific methodologies

The individuation of parameters that characterize decorations in “glass paste” of Etruscan jewels in Meridional Etruria area, by the use of scientific methodologies, has the aim to collocate this typology of manufacts in a historical and geographical context and to improve the knowledge of the technology connected with their realization. The term “glass paste” is widely used in humanistic literature to describe different materials, all based on a “glass like” composition, but its definition is lacking or confusing if the term is not referred to a scientific meaning.The glass analysis is difficult owing to the complexity of the elements that compose the various classes of vitreous materials. For this reason the interpretation of the composition table containing the values of the numerous glass elements, induces the use of statistical methods for the elaboration of the results. The multivariate analysis can be a valid tool for an immediate lecture of the common characteristics of the different typologies of vitreous materials.In this work, the application of the Principal Component Analysis (PCA), has been applied for the elaboration of chemical composition data obtained by electronic microanalysis (SEM-EDS) on findings coming from Etruscan archaeological sites of Nepi and Cerveteri, and on pearls of a necklace from Castellani's Collection. Besides, an attempt has been made to compare the chemical elements found in the vitreous materials of the jewelry with the elements of sands from probable sites along the rivers present in the Etruscan sites by following the indications reported by historical fonts.The obtained results furnished information in various directions, either for the characterization of each historical sample analyzed or the validation of the applied statistical methodology for the composition data elaboration, besides it has been possible to contribute in the knowledge of the possible existence of glass production sites in the Meridional Etruria, more specifically for the realization of decoration in glass paste.     

International Measurement Evaluation Programme: IMEP-9, trace elements in water

The International Measurement Evaluation Programme (IMEP) is an interlaboratory comparison scheme, founded, owned and coordinated by the Institute for Reference Materials and Measurements (IRMM) since 1988. IMEP-9 is the third round of trace elements in water evaluation following IMEP-3 and IMEP-6. Reference values for 15 elements stating total concentrations and combined uncertainties (according to GUM) were established. The reference values were established mainly by isotope dilution mass spectrometry (IDMS) as a primary method of measurement, and values traceable to the SI were obtained. The four elements that could not be certified by IDMS were assigned values by means of other measurement techniques. Results from 201 laboratories from 35 countries and four continents were evaluated against the reference values and the comparability between the laboratories is presented graphically.     

Certified sediment reference materials for trace element analysis from the National Metrology Institute of Japan (NMIJ)

Two types of sediment reference material (NMIJ 7302-a and 7303-a) for trace elements analysis have been prepared and certified by the National Metrology Institute of Japan in the National Institute of Advanced Industrial Science and Technology (NMIJ/AIST). The original materials were collected from a bay near industrial activity in Kyushu (NMIJ CRM 7302-a; marine sediment) and from Lake Biwa (NMIJ CRM 7303-a; lake sediment). The sediment materials were air-dried, sieved, homogenized, packaged in 1000 glass bottles (60 g each), and radiation sterilized. Certification of these CRM for trace elements was conducted by NMIJ, where each element was determined by at least two independent analytical techniques. Isotope-dilution inductively coupled plasma mass spectrometry (ICP–MS) was applied for certification of all the elements except mono-nuclide elements such as As and Co. Other techniques such as ICP–MS with quadrupole mass spectrometry and sector-field mass spectrometry, inductively coupled plasma atomic emission spectrometry (ICP–AES), and atomic absorption spectrometry (AAS), were also used. Certified values have been provided for 14 elements (Sb, As, Cd, Cr, Co, Cu, Pb, Hg, Mo, Ni, Se, Ag, Sn, and Zn) in both CRM.     

Human hair as a marker of pollution by chemical elements emitted by a thermoelectric power plant

A preliminary study was undertaken to assess the risk posed to the environment and health of residents by trace elements released by fuel combustion in the thermoelectric power plant of Pian de’ Gangani (Montalto di Castro, Latium, Italy). In this context, analysis of human hair can be considered as an advantageous approach to monitor the exposure of population to the adverse effects of the power plant, which is now fully operative. To this purpose 92 healthy children (aged 9–10 years) were selected from two primary schools of Montalto di Castro and Pescia Romana. The young age of the donors guarantees that the effects of cosmetic treatment and occupational exposure on the representativeness of data are minimized. Hair samples were collected, washed and digested as prescribed by already well-established procedures. Inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were employed for the determination of the trace and minor elements of interest (As, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, P, Pb, Sb, Se, Tl, V and Zn). The entire analytical procedure was checked for both measurement precision and accuracy by using the Certified Reference Material BCR No. 397 Human Hair. The mean values obtained were (in μg g⁻¹): As, 0.159±0.044; Ca, 393±187; Cd, 0.047±0.055; Co, 0.040±0.038; Cr, 0.704±0.208; Cu, 12.0±10.3; Fe, 12.1±10.8; Mg, 40.6±27.7; Mn, 0.383±0.296; Ni, 0.868±1.331; P, 141±138; Pb, 1.64±1.63; Sb, 0.041±0.058; Se, 0.430±0.135; Tl, 0.001±0.001; V, 0.185±0.158; and Zn, 177±173. These experimental figures can be assumed to be the baseline values prior to the full operation of the power plant. Within the next 4–5 years it is planned to conduct a similar study with a new group of subjects, comparable for age, sex, style of life and exposure mode, to the present ones so as to detect possible trends in the bioaccumulation of the above elements.     

Elemental analysis of a single-wall carbon nanotube candidate reference material

A material containing single-wall carbon nanotubes (SWCNTs) with other carbon species, catalyst residues, and trace element contaminants has been prepared by the National Institute of Standards and Technology for characterization and distribution as Standard Reference Material SRM 2483 Carbon Nanotube Soot. Neutron activation analysis (NAA) and inductively coupled plasma mass spectrometry (ICP–MS) were selected to characterize the elemental composition. Catalyst residues at percentage mass fraction level were determined with independent NAA procedures and a number of trace elements, including selected rare earth elements, were determined with NAA and ICP–MS procedures. The results of the investigated materials agreed well among the NAA and ICP–MS procedures and good agreement of measured values with certified values was found in selected SRMs included in the analyses. Based on this work mass fraction values for catalyst and trace elements were assigned to the candidate SRM.     

Characterization (certification) of Corn Bran (NIST RM 8433), Corn Starch (NIST RM 8432) and Microcrystalline Cellulose (NIST RM 8416) Reference Materials for essential and toxic major, minor and trace elemental constituents

Summary Corn Bran (NIST RM 8433), Corn Starch (NIST RM 8432) and Microcrystalline Cellulose (NIST RM 8416) Reference Materials were characterized for essential and toxic major, minor and trace elemental composition in an interlaboratory cooperative characterization campaign. Extensive application of widely varied analytical methods by analysts in cooperating laboratories yielded 10–29 best estimate and 1–16 informational concentration values for each of these materials. Two materials, Corn Starch and Microcrystalline Cellulose, contain particularly low levels of trace elements. These reference materials are intended for analytical quality control of elemental determinations in corn and plant products as well as other agricultural/food materials with related matrices.Contribution No. 92–146 from Centre for Land and Biological Resources Research     

Concentration Levels of Trace Elements in Carrots,Onions, and Potatoes Cultivated in Asopos Region,Central Greece

The objective of the work was to investigate the correlation between the environmental pollution of Asopos river area in Viotia, Greece and the concentration of Ni, Cr, Cd, Pb, Cu, and As in specific crops (carrots, onions, and potatoes) produced in this region. Samples of these crops from Asopos and other Greek areas (control) were collected. For method accuracy, the Certified Reference Material, CRM 281 (trace elements in rye grass) was measured. Simultaneous multi-element graphite furnace atomic absorption spectrometry was used after a microwave acid digestion. The levels of Ni in Asopos food were found up to 9 times higher than control (e.g., Asopos potatoes had an average Ni content of 800 µg/kg compared to 78 µg/kg in control, whereas Asopos carrots had an average Ni content of 474 µg/kg compared to 93 µg/kg in control). Likewise, the levels of Cr were found to be about 2 times higher than control (e.g., Asopos carrots were found to have an average Cr content of 43 µg/kg compared to 20 µg/kg in control). The levels of Cd and Pb had a high variance in the Asopos sourced food. Arsenic was not detected in any sample. Our results indicate that the mean intake of trace elements (Ni, Cr, Pb, Cd, and Cu) by adults through consumption of crops from Asopos, for an average consumption pattern, generally is well below the Allowable Daily Intakes (ADIs). Comparison was also made with data from literature from Greece.     

Novel disposable bismuth-sputtered electrodes for the determination of trace metals by stripping voltammetry

This work describes a novel type of bismuth electrode for stripping voltammetry based on coating a silicon substrate with a thin bismuth film by means of sputtering. The bismuth-based sensors were characterized by optical methods (scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray diffraction (XRD)) and as well as by linear sweep voltammetry. Subsequently, the electrodes were tested for the detection of low concentrations of trace metals (Cd(II), Pb(II) and Ni(II)) by stripping voltammetry. Well-formed stripping peaks were observed for trace concentrations of the target analytes demonstrating “proof-of-principle” for these sensors. This type of electrochemical device, utilizing thin-film technology for the formation of the bismuth film, holds promise for future applications in trace metal analysis.     

Reply to “Comments on the paper entitled ‘The formulation and modelling of the anodic dissolution of zinc through adsorbed intermediates’ ” by C. Cachet et al.

The points raised in the paper entitled “Comments on the paper entitled ‘The formulation and modelling of the anodic dissolution of zinc through adsorbed intermediates”’ have been discussed. It has been shown that, in contrast to the statements in the “Comments”, most of the papers concerning the reaction schemes suggested for the interpretation of the dissolution or deposition of metals, which were considered as a support for the opinion of the Authors of the “Comments”, support the views expressed in our original paper [J. Electroanal. Chem. 583 (2005) 148]. On the other hand, it has been stressed again that the criticism expressed in the original paper refers to dubious conclusions drawn on the basis of transient measurements.     

济南市健康孕妇必需微量元素含量的调查

应用ＤＣＰ－ＡＥＳ法对济南市１０１例健康孕妇及２５例育龄健康孕妇血清中９种元素进行了测定，结果表明，除钴外，所测不同年龄，职业，文化及胎次的孕妇，其必需微量元素营养状况良好，作者还本文孕妇缺钴的原因进行了探讨。     

Spectral interferences in the determination of traces of scandium, yttrium and rare earth elements in “pure” rare earth matrices by inductively coupled plasma atomic emission spectrometry: Part VII — Terbium, Dysprosium, Holmium and Thulium

This article is the seventh part of a series of papers discussing the spectral interferences of rare earth elements (REEs) in ICP-AES. Radial viewing 27.12 MHz inductively coupled plasma atomic emission spectrometry (ICP-AES) was used in the determination of scandium, yttrium and rare earth elements in Tb₂O₃, Dy₂O₃, Ho₂O₃ and Tm₂O₃ as “pure” rare earth matrices. The quantification of the interferences in terms of Q-values for line interference Q_I(_a) and wing background interference Q_W(Δλ_a) were used in accordance with Boumans and Vrakking [Spectrochim. Acta Part B 43 (1988) 69]. The “best” analysis lines from point of view of spectral interferences were selected. The true detection limits by using the “best” analysis lines were calculated.     

Benthic fluxes of trace metals in the lagoon of Venice

To assess the exchange and the mobility of trace metals between sediments and water and their geochemical behaviour, experiments were carried out within the sphere of the CORILA project for the safeguarding of the Venice lagoon. Trace element exchanges were examined for approximately 60 h at two sites in the central part of the Venice lagoon (Italy): the first one is located in front of the industrial area of Porto Marghera (Tresse) and the second one in front of Campalto, near the causeway (Campalto). The experiments were carried out using a benthic chamber monitored for pH, dissolved oxygen, salinity, and temperature. The temporal trend of metals inside the benthic chamber was examined in relation to changes of pH and dissolved oxygen. Diffusive metal fluxes were also assessed by determination of the vertical distribution of metals in pore water.Al, As, Cd, Cu, Fe, Mn, Mo, Sb, U, V and Zn were determined by ICP-SFMS. The metal concentrations for the lagoon samples were in agreement with expected values; the concentration ranges (min–max in ng/ml) were: Al 0.24–0.61, As 1.42–2.27, Cd 0.050–0.182, Cu 0.81–2.46, Fe 0.25–1.66, Mn 11.59–31.66, Mo 6.50–10.62, Sb 0.139–0.516, U 1.7–3.3, V 0.69–3.21, Zn 5.20–21.51.Positive fluxes for the Tresse and Campalto experiments were determined for Cd (0.21 and 0.18 pmol/cm²/h), Zn (62 and 67 pmol/cm²/h), Cu (0.29 and 0.50 pmol/cm²/h) and Mn (19 and 12 pmol/cm²/h), while negative fluxes were determined for iron (−3.5 and −6.3 pmol/cm²/h). Other elements showed differences in behaviour for the two experiments; the fluxes, for the Tresse and Campalto experiments, respectively, were 5.1 and −6.9 pmol/cm²/h for molybdenum, 0.25 and −0.18 pmol/cm²/h for arsenic and 1.3 and −8.4 pmol/cm²/h vanadium. Therefore, the different characteristics of the two areas affect the mobility of trace elements, which can derive from differences in the environmental characteristics of the two areas or seasonal difference in which the experiments were carried out.     

Characterization (certification) of Bovine Muscle Powder (NIST RM 8414), Whole Egg Powder (NIST RM 8415) and Whole Milk powder (NIST RM 8435) Reference Materials for essential and toxic major, minor and trace element constituents

Summary Bovine Muscle Powder (NIST RM 8414), Whole Egg Powder (NIST RM 8415) and Whole Milk Powder (NIST RM 8435) Reference Materials were characterized for essential and toxic major, minor and trace element composition in an interlaboratory cooperative characterization campaign. Extensive application of widely varied analytical methods yielded best estimate concentration values for 27, 23 and 21 elements, and informational concentration values for 5, 4 and 9 elements, respectively, in RM's 8414, 8415 and 8435. These Reference Materials are intended for analytical quality control of element determinations on meat, egg and milk-based products as well as agricultural/food materials with related matrices.Contribution no. 92–147 from Centre for Land and Biological Resources Research     

光疗对新生儿高胆红素血症患儿微量元素影响的临床观察

观察了４５例新生儿高胆红素血症患儿光疗（蓝光）前后血清１５种元素的变化。结果发现患儿在光疗后１２种元素含量较光疗前降低，尤其是Ｃｕ、Ｆｅ降低明显，ｔ值分别为２．０９，２．７３，Ｐ〈０．０５，Ｐ〈０．０１，有显著性差异，Ｚｎ、Ｃａ虽有所下降，但无统计学意义。推测Ｃｕ、Ｆｅ降低的原因与肠道、尿液及汗液排泄增加有关。提示对光疗后的高胆血症病人应注意及时补充Ｃｕ、Ｆｅ等微量元素，以保证小儿生长发育的需要。     

Determination of rare earth elements and other trace elements (Y, Mn, Co, Cr) in seawater using Tm addition and Mg(OH)₂ co-precipitation

This paper reports on a novel procedure for determining trace element abundances (REE and Y, Cr, Mn, Co) in seawater by inductively coupled plasma sector field mass spectrometry (ICP-SFMS). The procedure uses a combination of pre-concentration using co-precipitation onto magnesium hydroxides and addition of thulium spike. The validity of the method was assessed onto 25 ml volumes of certified reference materials (NASS- and CASS-4) and in house seawater standard. Procedural blanks were determined by applying the same procedure to aliquots of seawater previously depleted in trace elements by successive Mg(OH)₂ co-precipitations, yielding estimated contributions to the studied samples better than 1.1% for all elements, with the exception of Cr (<3.3%) and Co (up to 8%). The reproducibility of the method over the six month duration of the study was smaller than 11% RSD for all the studied elements. Results obtained for NASS-5 and CASS-4 agree well with published working values for trace elements.     

Structural and magnetic properties of “one-dimensional” barium vanadium triselenide

BaVSe₃ has been synthesized and its crystal structure determined at 293(2)°K. The structure was solved in the hexagonal space group P6₃/mmc (D⁴_6h), with a = 6.9990(11) and c = 5.8621(13) Å. Scans (2 Θ) of a polycrystalline sample revealed that BaVSe₃ undergoes a transition to an orthorhombic unit cell (b′ 3^1/2 a, a′ a, c′ c) at 303(5)°K. Magnetic susceptibility measurements between 4 and 300°K indicate that BaVSe₃ is paramagnetic down to 41(1)°K, where magnetic ordering occurs, with a magnetic moment in the ordered phase of 0.2 μ_B per vanadium atom. The orthorhombic lattice distortion may be caused by the “freezing in” of “soft” vibrational modes.