The interlaboratory comparison "IMEP-19 trace elements in rice"—a new approach for measurement performance evaluation

The aim of IMEP is to present objectively the quality of chemical measurements. Participants in IMEP compare their reported measurement results with independent external certified reference values with demonstrated traceability and uncertainty, as evaluated according to international guidelines. IMEP-19 focused on measurements of trace elements in rice aiming to support the Commission Regulation (EC) No. 466/2001 on maximum levels for certain contaminants in foodstuff. Measurement results for the elements Cd, Cu, Pb and Zn were reported by 267 field laboratories involved in food analysis from 43 countries. Performance criteria for the evaluation of the reported measurement results in IMEP-19 are suggested. The chosen performance indicators not only take into account the deviation of the reported measurement value from the certified reference value, but also set criteria for maximum and minimum acceptable uncertainty. The IMEP-19 participants' performance is reviewed by means of using new simple graphical tools, called "Naji plots".     

Co3O4@Cu-Based Conductive Metal–Organic Framework Core–Shell Nanowire Electrocatalysts Enable Efficient Low-Overall-Potential Water Splitting

In the work reported herein, the electrocatalytic properties of Co₃O₄ in hydrogen and oxygen evolution reactions have been significantly enhanced by coating a shell layer of a copper-based metal–organic framework on Co₃O₄ porous nanowire arrays and using the products as high-performance bifunctional electrocatalysts for overall water splitting. The coating of the copper-based metal–organic framework resulted in the hybridization of the copper-embedded protective carbon shell layer with Co₃O₄ to create a strong Cu−O−Co bonding interaction for efficient hydrogen adsorption. The hybridization also led to electronically induced oxygen defects and nitrogen doping to effectively enhance the electrical conductivity of Co₃O₄. The optimal as-prepared core–shell hybrid material displayed excellent overall-water-splitting catalytic activity that required overall voltages of 1.45 and 1.57 V to reach onset and a current density of 10 mA cm⁻², respectively. This is the first report to highlight the relevance of hybridizing MOF-based co-catalysts to boost the electrocatalytic performance of nonprecious transition-metal oxides.     

The use of multiple correspondence analysis for the evaluation of inter-laboratory comparisons

Participation in inter-laboratory comparisons (ILC) is one of the recommended means of external quality control according to ISO/IEC 17025:2005. Providers of ILC or proficiency test (PT) schemes collect, besides the measurement results on the test samples, information on the sample treatment and measurement procedure. The objective of this paper is to evaluate in a non-traditional way, using numerical and non-numerical data provided by the participants in IMEP-20 (trace elements in tuna fish), the additional information concerning the applied analytical methods and the accreditation/nomination status. Arsenic was taken as an example. The basic statistical procedure for the evaluation of questionnaire information was the multiple correspondence analysis (MCA). Univariate clustering techniques were applied for the categorization of the numerical data (measurement values). The methodology of the evaluation of supplementary non-numeric information used in this paper might serve (a) to providers of ILC (PT) schemes to modify/improve their questionnaires and (b) to give laboratories better guidance in the methods used for the determination of various analytes in different matrices. This paper is meant serve as a guide for the possible interpretation of the questionnaires accompanying ILC schemas. Presented at the 3rd International Conference on Metrology, November 2006, Tel Aviv, Israel     

Surface waves generated by a line load on a half-space with depth-dependent properties

The reciprocity theorem of elastodynamics is used in this paper to determine the surface waves that are radiated from a time-harmonic line load applied at the surface of a solid body, whose elastic moduli and mass density depend on the distance from the surface. In a high-frequency approximation, the surface wave velocity and expressions for the displacement and stresses of free surface waves are employed in the reciprocity theorem. The general expressions for the surface wave radiated by the oscillating line load, together with a virtual free surface wave, when employed in the reciprocity theorem, yield relatively simple expressions for the amplitude factor of the radiated surface wave. Results show the amplitude factor as a function of the wavenumber.     

A Water-Soluble Polymer-Lumefantrine Conjugate for the Intravenous Treatment of Severe Malaria

Uncomplicated malaria is effectively treated with oral artemisinin-based combination therapy (ACT). Yet, there is an unmet clinical need for the intravenous treatment of the more fatal severe malaria. There is no combination intravenous therapy for uncomplicated due to the nonavailability of a water-soluble partner drug for the artemisinin, artesunate. The currently available treatment is a two-part regimen split into an intravenous artesunate followed by the conventional oral ACT . In a novel application of polymer therapeutics, the aqueous insoluble antimalarial lumefantrine is conjugated to a carrier polymer to create a new water-soluble chemical entity suitable for intravenous administration in a clinically relevant formulation . The conjugate is characterized by spectroscopic and analytical techniques, and the aqueous solubility of lumefantrine is determined to have increased by three orders of magnitude. Pharmacokinetic studies in mice indicate that there is a significant plasma release of lumefantrine and production its metabolite desbutyl-lumefantrine (area under the curve of metabolite is ≈10% that of the parent). In a Plasmodium falciparum malaria mouse model, parasitemia clearance is 50% higher than that of reference unconjugated lumefantrine. The polymer-lumefantrine shows potential for entering the clinic to meet the need for a one-course combination treatment for severe malaria.     

Kinetics of thermal decomposition of 4-carboxyl-2,6-dinitrobenzenediazonium ion (CDNBD)

The kinetics of thermal decomposition of 4-carboxyl-2,6-dinitrobenzenediazonium ion (CDNBD), an arenediazonium ion newly developed as a derivatizing reagent for drug analysis, are described. The arenediazonium ion, in an optimized concentrated sulfuric acid/orthophosphoric acid medium, was incubated for various time intervals at 30 degrees, 45 degrees, 55 degrees , 65 degrees , 75 degrees, and 85 degrees C. The amount of ion left after each time interval was quantified selectively by colorimetric assay at 490 nm, using mefenamic acid as a model diazo-coupling component. The rate constants for the decomposition were determined graphically. An Arrhenius plot was used to delineate the dependence of the rate constant on temperature and to predict the half-life at 25 degrees C and lower temperatures. The diazonium ion decomposed by first-order kinetics. The rate constants of decomposition, which increased progressively with temperature, were 3.18 +/- 0.41 x 10(-5), 1.19 +/- 0.07 x 10(-4), 4.87 +/- 0.15 x 10(-4), 12.88 +/- 0.73 x 10(-4), and 21.32 +/- 2.74 x 10(-4) (s(-1)) with corresponding half-lives of 363, 97.06, 23.72, 8.97, and 5.42 min at 30 degrees, 45 degrees, 55 degrees, 65 degrees, and 75 degrees C, respectively. CDNBD is highly stable in concentrated acid medium, with half-life values of about 10 h, 10 days, and 7.3 months at 25 degrees, 0 degrees, and -20 degrees C, respectively. The reagent stability profile shows that it could be readily adapted for routine applications in instrumental chemical analysis.     

Contribution of an interlaboratory comparison to the certification of the STAM/IRMM-0243 243Am reference material

Following the expression of the need for an americium (Am) standard and particularly for one with a certified americium-243 (²⁴³Am) content, the Commissariat à l’Energie Atomique et aux Energies Alternatives (CEA)/Direction de l’Energie Nucléaire of Marcoule and the European Commission Joint Research Center in Geel carried out a collaborative project for the production of a certified reference material enriched in ²⁴³Am. CEA’s Commission d’ETAblissement des Méthodes d’Analyse organized an interlaboratory comparison on this material prior to the issuing of its certificate. The usefulness of an interlaboratory comparison to assess the measurement capabilities in the field and to confirm the provisional certified values for the amount contents of ²⁴³Am, ²⁴¹Am, total Am, the isotopic composition and the molar mass of Am has been demonstrated. Furthermore this interlaboratory comparison enabled to derive an indicative value for the n(^242mAm)/n(²⁴³Am) isotope amount ratio.

     

Occurrence of natural radionuclides and fallout cesium-137 in dry-season agricultural land of South Western Nigeria

The radioactivity of the Opa river — irrigated farmlands in the south western Nigeria was determined using an HpGe based, low-level passive gamma-counting system. With the exception of two isotopes, the main radionuclides analysed in the sample were the progenies of²³⁸U and²³²Th. The other two isotopes were the naturally occurring⁴⁰K and the anthropogenic¹³⁷Cs. The result obtained showed elevated levels of radioactivity from all detected radionuclides compared to the published data for this area. Enhanced levels of naturally occurring radionuclides is attributed to the use of phosphatic fertilizers for dry season vegetable cultivation along this river banks. The presence of the fission product¹³⁷Cs could be traced to the fallouts occasioned by the various French nuclear tests in the Sahara desert, and probably, some effect of the more recent nuclear reactor accident at Chernobyl in 1986.     

TL response of a natural fluorite

A batch of a naturally occurring fluorite (CaF₂) from the Middle Benue Valley region of Nigeria has been studied in some detail for its thermoluminescence (TL) properties. TL glow peaks are observed at 119, 144 and 224°C at a heating rate of 10°C s⁻¹. The TL response is observed to increase with increasing dose, as expected, over the dose range examined. Variations are observed in the decay curves of the various glow peaks with storage at room temperature. While the lower temperature peaks are observed to decay, enhancement of the TL signal is observed for the 224°C glow peak when stored for four weeks. A low-level radioactivity measurement showed no evidence of self-irradiation from naturally occurring radionuclides. UV exposure was suppressed by storage in a black sealed container to exclude sunlight contribution to the observed TL response. A scheme involving the formation of large defect complexes, from smaller ones, during storage, as possible route leading to loss of signal in low temperature glow peaks and a corresponding enhancement at higher temperature, is suggested.