Polycationic oxides as potential electrode materials for aqueous-based electrochemical capacitors

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Preparation of candidate certified reference materials for the quality control of EDTA-and acetic acid-extractable trace metal determinations in sewage sludge-amended soil and terra rossa soil

The determination of extractable trace metal contents in soil using single extraction procedures is currently performed in many laboratories to assess the bioavailable metal fraction (and related phytotoxic effects) and the accessability to the environment (e.g. contamination of ground waters). Owing to the need for validation of the extraction schemes used and of the analytical techniques, the EC Measurements and Testing Programme (formerly BCR) has organized a project for improving the quality of determination of extractable trace metal contents in soil, the first step being an interlaboratory study to adopt common extraction procedures and the second being a certification campaign to certify two soils for their extractable trace element contents following these procedures. This paper gives a brief overview of the project organisation and describes the preparation, homogeneity and stability studies of two soil candidate reference materials (sewage sludge-amended and terra rossa soils).     

Selection of reference methods for the determination of selenium in biological materials

Summary Over the period 1985–1989 the European Community Bureau of Reference (BCR) has certified 7 biological reference materials for selenium with concentrations ranging from 0.03 to 10 mg/kg. Certification analyses were carried out by the most experienced laboratories in the Member States, using Fluorimetry, Hydride formation, combined with ICP or AAS, Electrothermal AAS with or without Zeeman-background correction, Instrumental or radiochemical NAA. Results from these exercises are available in a form suitable for estimating the experimental precision of the various methods as a function of concentration. With the same number of replicates for all analyses the logarithm of the observed standard deviations have constant variance, independent of concentration; for each method the absolute and relative standard deviations can therefore be estimated by means of non-linear regression. Analytical bias was monitored plotting results and their estimated standard deviations from individual laboratories versus certified confidence intervals. For concentrations of Se <0.3 mg/kg fluorimetry was selected as a reference method; above this level INAA is recommended; both are capable of producing unbiased results.     

Certified reference materials for validating spectroscopic methods and experimental data

Summary Chemical laboratories frequently obtain significantly different results when analyzing the same homogeneous material. The different results may be caused by poor methodology, improper instrument calibration, faulty experimental techniques, impure reagents, or a combination of these factors. For trace constituent determinations, the magnitude and evaluation of the method blank are often the main limitations toward obtaining accurate results.One approach towards improving the accuracy of analytical determinations is by the use of Certified Reference Materials (CRMs) issued by organizations throughout the world. A CRM is a homogeneous, stable material with certified chemical and/or physical properties used in calibrating instruments, validating experimental data, developing methods of known reliability, and referring data from different laboratories to a common base. In the United States, the National Bureau of Standards (NBS) has legal authority to issue CRMs, which for historical reasons are called Standard Reference Materials (SRMs). There are more than 900 SRMs listed in the current NBS SRM catalog, the greatest number of these SRMs are certified for chemical composition. Chemical composition SRMs, which comprise a variety of matrices and constituents, inorganic and organic, are of greatest interest to spectrochemists. These SRMs have applications in such diverse areas as clinical, environmental, nutritional, agricultural, and industrial analytical chemistry. Instrument-performance SRMs, such as the one developed for validating the performance of gas chromatograph-mass spectrometers, will also be of interest to spectrochemists.

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Zertifizierte Referenzmaterialien für die Bewertung spektroskopischer Methoden und experimenteller Daten

Zusammenfassung Chemische Laboratorien erhalten häufig signifikant verschiedene Ergebnisse, wenn sie das gleiche homogene Material untersuchen. Die unterschiedlichen Ergebnisse können verursacht sein durch ungeeignete Methoden, falsche Geräteeichung, fehlerhafte experimentelle Techniken, unreine Reagentien oder eine Kombination dieser Faktoren. Für die Spurenbestimmung sind Größe und Auswertung des Blindwertes der Methode oft die Hauptbeschränkungen bei der Erzielung genauer Ergebnisse.Ein Schritt in Richtung auf Verbesserung der Genauigkeit von analytischen Bestimmungen ist die Benutzung zertifizierter Referenzmaterialien (CRMs), die von Organisationen überall in der Welt ausgegeben werden. Ein CRM ist ein homogenes, stabiles Material mit zertifizierten chemischen und/oder physikalischen Eigenschaften, das benutzt wird, um Geräte zu eichen, experimentelle Daten zu bewerten, zuverlässige Methoden zu entwickeln und Daten verschiedener Laboratorien auf eine gemeinsame Basis zu beziehen. In den Vereinigten Staaten ist das National Bureau of Standards (NBS) gesetzlich autorisiert, CRMs auszugeben, die aus historischen Gründen Standardreferenzmaterialien (SRMs) genannt werden. In dem heute gültigen NBS-Katalog sind mehr als 900 SRMs aufgelistet, wovon die meisten in bezug auf ihre chemische Zusammensetzung zertifiziert sind. Sie umfassen eine Vielzahl von Matrices mit Bestandteilen anorganischer und organischer Art und sind von großem Interesse für Spektrochemiker. Diese SRMs finden Anwendung auf derart verschiedenen Gebieten wie klinische analytische Chemie, Umweltanalytik, Nahrungsmittelchemie, landwirtschaftliche und industrielle analytische Chemie. Auch SRMs zur Beurteilung der Leistungsfähigkeit von Geräten, wie die, die entwickelt wurden, um die Leistungsfähigkeit von Gas-Chromatograph-Massenspektrometern zu bewerten, sind für Spektrochemiker von Interesse.

     

Certification of reference materials for the quality control of major element determinations in groundwater Part 2: Certification

The quality control of groundwater monitoring requires the availability of representative CRMs. This paper describes the preparation of two artificial groundwater reference materials, CRM 616 (high carbonate content) and CRM 617 (low carbonate content), the homogeneity and stability studies and the analytical work performed for the certification of a range of major elements (Ca, Cl, Fe, K, Mg, Mn, Na, NO₃, PO₄ and SO₄).     

Certification of reference materials for the quality control of major element determinations in groundwater Part 2: Certification

The quality control of groundwater monitoring requires the availability of representative CRMs. This paper describes the preparation of two artificial groundwater reference materials, CRM 616 (high carbonate content) and CRM 617 (low carbonate content), the homogeneity and stability studies and the analytical work performed for the certification of a range of major elements (Ca, Cl, Fe, K, Mg, Mn, Na, NO₃, PO₄ and SO₄). Received: 15 May 1998 / Revised: 25 June 1998 / Accepted: 1 July 1998     

Evaluation of an ultrasonic digestion procedure for total metal determination in sediment reference materials

In this work the possibility to use a simple and easily available laboratory device—routine ultrasonic bath—has been evaluated for total metal determination in sediments from different origin. The investigated instrumental parameters were time and temperature, whereas power was maintained constant set at 100% of nominal power. Four different sets of parameters were applied on a lake sediment reference material (RM), the results obtained for five elements—Cd, Cr, Cu, Ni and Zn—were statistically compared with those obtained by a previously optimised microwave acid digestion procedure on the same material. The optimal set of parameters—30 min sonication at ambient temperature—was chosen, and then applied to other five sediment RMs from different origin. In this case four additional elements—As, Pb, V and Fe—were also determined and the results were compared with reference and microwave values.The results obtained by the ultrasound digestion procedure were higher than 80% of the reference and/or microwave values in 40 out of 44 cases. In any case, the results obtained by ultrasonic procedure were statistically comparable to reference values (mean of means of interlaboratory exercises or certified values) in the 84% of the cases.     

The NIH analytical methods and reference materials program for dietary supplements

Quality of botanical products is a great uncertainty that consumers, clinicians, regulators, and researchers face. Definitions of quality abound, and include specifications for sanitation, adventitious agents (pesticides, metals, weeds), and content of natural chemicals. Because dietary supplements (DS) are often complex mixtures, they pose analytical challenges and method validation may be difficult. In response to product quality concerns and the need for validated and publicly available methods for DS analysis, the US Congress directed the Office of Dietary Supplements (ODS) at the National Institutes of Health (NIH) to accelerate an ongoing methods validation process, and the Dietary Supplements Methods and Reference Materials Program was created. The program was constructed from stakeholder input and incorporates several federal procurement and granting mechanisms in a coordinated and interlocking framework. The framework facilitates validation of analytical methods, analytical standards, and reference materials.     

Certification of reference materials for the quality control of major element determinations in groundwater Part 1: Feasibility study

 Analyses of groundwater are routinely performed by control laboratories within the European Union to monitor the levels of major elements. The quality control of such determinations requires the use of certified reference materials which are representative of natural samples. However, the preparation and stabilisation of natural groundwater for their major element composition is difficult to achieve and materials simulating the mean composition of real samples often represent the best alternative. In order to investigate the feasibility of preparation and stabilisation of simulated groundwater samples, various tests were necessary prior to the production of a large batch of candidate reference materials. This paper presents the preparation of simulated groundwater reference materials and the different stabilisation procedures tested. Received: 9 September 1996/Revised: 4 December 1996/Accepted: 14 December 1996     

Matching reference materials with AOAC International methods of analysis

Proper implementation and use of validated analytical methodology with use of appropriate reference materials (RM) is a preferred means of helping to ensure equivalent analytical method performance in diverse laboratories. Choice of an appropriate RM that not only matches the analyte and matrix of the required determination, but also has been demonstrated to be within the applicability of a specific analytical method, are key factors. In response to numerous requests since its founding in 1993, the Technical Division on Reference Materials (TDRM), AOAC International is implementing a program for recognizing the matching of specific reference materials to specific AOAC methods of analysis. This recognition is accomplished by means of a thorough peer-reviewed selection system, under the auspices of the AOAC official methods board and the executive committee of the TDRM. Potential RM/method matching (RM/MM) proposals will be submitted to an RM/MM committee. After technical review of the suitability of the proposed RM by the RM/MM committee, acceptable matches are recommended for review by the current AOAC process responsible for review and recognition of new methods and modifications to existing AOAC methods of analysis. Several trial matches have been used to develop and test this system. The end product of this effort will ultimately be made available as either a stand-alone document, a section of the AOAC Official Methods of Analysis, or a site within the AOAC web site listing recognized matches.     

Size-selective poorly soluble particulate reference materials for evaluation of quantitative analytical methods

Owing to the absence of readily available certified particulate reference materials (RMs), most analytical methods used to determine particulate contaminant levels in workplace or other environments are validated using solution RMs, which do not assess the robustness of the digestion step for all forms and sizes of particles in a sample. A library of particulate RMs having a range of chemical forms and particle sizes is needed to support a shift in method evaluation strategies to include both solution and particulate RMs. In support of creating this library, we characterized bulk and physically size separated fractions of beryllium oxide (BeO) particles recovered from the machining fluid sludge of an industrial ceramic products grinding operation. Particles were large agglomerates of compact, crystalline BeO primary particles having diameters on the order of several micrometers. As expected, the particle surface area was independent of sieve size, with a range from 3.61 m(2)/g (53-63-microm fraction) to 4.82 m(2)/g (355-600-microm fraction). The density was near the theoretical value (3.01 g/cm(3)). The data support more detailed characterization of the sludge materials for use as size-selective RMs. This work illustrates an approach that can be used to develop RMs that are difficult to digest.     

Present status and potential of group contribution methods for process development

The development of chemical processes can be performed with the help process simulators. However, for the simulation, besides kinetic data, a reliable knowledge of the pure component and mixture properties is required. Since often 60–80% of the total costs arise in the separation step, a reliable knowledge of the phase equilibrium behaviour of the system to be separated is of special importance.The models for excess Gibbs energy g^E and equations of state allow the calculation of the phase equilibrium behaviour of multicomponent systems using binary information alone. But often, the required binary experimental data are missing. For these systems, a reliable predictive thermodynamic model with a large range of applicabilities would be most desirable.With a view to the development of a powerful predictive method, work on the development of a group contribution method was started in Dortmund 1973. A prerequisite for this work is a large database. Therefore, all published pure component properties, phase equilibrium data, and excess properties were stored in a computerized form. At the same time, experimental techniques for the systematic measurements were built up to measure the missing values.The information stored was used for the development of the group contribution method UNIFAC. The weaknesses of this method were removed with the development of modified UNIFAC. With the introduction of g^E-mixing rules in equations of state, the usage of the “solution of groups”-concept lead to group contribution equations of state. In combination with electrolyte models, the influence of strong electrolytes on the phase equilibrium behaviour can be taken into account.In this paper, the continuous development, present status, and potential of group contribution methods for the development of chemical processes will be shown.     

An interlaboratory study to evaluate potential matrix reference materials for herbicides in water

Matrix reference materials (MRM) are essential tools for the validation of analytical protocols. Nowadays, there are no such materials for the determination of herbicides in water. Pesticides stored in acetonitrile and stored on solid phase extraction (SPE) cartridges previously percolated with a water sample spiked with triazines and phenylureas have proven to be good candidates for reference materials because of their satisfactory stability under appropriate temperature conditions. To evaluate the behaviors of these materials containing pesticides and to be analyzed by liquid chromatography, a collaborative study including 15 laboratories has been organized. Observed reproducibility on candidate materials after the removal of extreme results was 16.1% for the vials with pesticides in acetonitrile (at around 0.125 mg/L) directly analyzed, 29.2% for a water sample spiked with the pesticides (at around 0.5 microg/L) analyzed after preconcentration on a cartridge and 26.7% for the cartridges previously percolated with a water containing the pesticides (250 mL at around 0.5 microg/L for each pesticide) analyzed after elution. Such dispersion values are quite compatible with the requirement of a further certification for such materials.     

Radiochemical separation methods for the determination of some toxic elements in biological reference materials

The present paper describes radiochemical separation procedures developed for the determination of the elements As, Cr, Hg, Sb and Se in biological reference materials. The methods chosen utilize ion exchange, retention on inorganic exchangers and solvent extraction techniques for the isolation of the elements of interest. These procedures are more rapid than previously used methods, such as distillation and precipitation. As to the sample dissolution, the following procedures were tested using radioactive tracers and reference materials: treatment of the materials in teflon bombs with a mixture of HNO₃+H₂SO₄ or HNO₃ only in a normal oven, and with HNO₃ in a microwave oven using specially designed digestion bombs.     

Present status and future trends in biological and environmental reference materials in China

Summary The present status of biological and environmental reference materials (BERMs) is summarized, including the institutions involved in the preparation, certification and approval of BERMs, types, analysis, homogeneity, stability and role in analytical practice. The future perspectives on the BERMs in China are also briefly discussed.     

Controlling the conductance of atomically thin metal wires with electrochemical potential

We report on the study of quantum transport in atomically thin Au wires suspended between two Au electrodes by modulating the electrochemical potential of the wires in various electrolytes. The potential modulation induces a conductance modulation with a phase shift that is always approximately 180 degrees, meaning that an increase in the potential always causes a decrease in the conductance. The amplitude of the induced conductance modulation, however, depends on several parameters. First, it depends on the atomic configurations of the individual wires. Second, the relative amplitude, defined as the ratio of the conductance modulation amplitude to the conductance, decreases as the diameter of the wire increases. Third, it depends on whether anion adsorption is present. In the absence of anion adsorption, it is approximately 0.55G(0) (G(0) = 2e(2)/h) per V of potential modulation, for a wire with conductance quantized near 1G(0). This double layer charging-induced conductance modulation can be attributed to a change in the effective diameter of the wire. In the presence of anion adsorption, the amplitude is much larger (e.g., approximately 1.6G(0)/V when I(-) adsorption takes place) and correlates well with the strength of the adsorption, which is due to the scattering of conduction electrons by the adsorbed anions.     

Availability of reference materials: COMAR the database for certified reference materials

COMAR is the international database for certified reference materials. A new user-friendly web-based version, COMAR², has been developed by BAM and CONET Consulting AG which will be available in December 2002. The advantages of COMAR² are briefly explained.Presented at the International ILAC/IAF Conference on Accreditation in Global Trade, 23-25 September 2002, Berlin, Germany