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).     

Extraction method for arsenic speciation in marine organisms

Three extraction systems have been assayed to extract arsenic species from biological marine sample, using methanol, methanol-chloroform (1:1) and methanol-water (1:1) as solvents. From a comparative study methanol-water 1:1 was chosen. A clean-up of the raw extract using C₁₈ cartridges is proposed. The results obtained from flounder (Pleuronectes platessa), sole (Solea solea), mussel (Mytilus edulis) and cockle (Cardium edule) are reported.     

Germanium speciation by LC-HG-ICP/OES

Liquid chromatography-hydride generation-inductively coupled plasma optical emission spectroscopy (LC-HG-ICP/OES) has been used to determine inorganic and organometallic species of germanium. In recent studies these coupled systems has been applied successfully to the speciation of arsenic. To establish separation conditions for germanium two reversed stationary phases and different solvent mixtures for elution, in isocratic or gradient mode have been tested. The reduction of germanium species to the corresponding volatile hydride is a critical step, especially for acidity control, thus the conditions for reduction using different concentrations of acid have been studied systematically. For the conditions established quality parameters as limit of detection (at the g l^–1 level), precision and recovery have been determined for the germanium species considered in a saline matrix.     

Determination of styrene in olive oil by an automatic purge-and-trap system coupled to gas chromatography-mass spectrometry

Summary A new gas chromatographic method using an automatic purge-and-trap system coupled to a GC with mass selective detection to analyze styrene at the parts-per-trillions (ng kg^–1) level is described. The method shows a good sensitivity and the detection limit is 10 ng kg^–1 with a relative standard deviation (RSD) of 4.7% for 164 ng kg^–1 styrene in olive oil. This analytical method has been successfully applied to the analysis of styrene in extra-virgin olive oil from the European market.     

Variable-angle scanning fluorescence spectrometry for the determination of closely overlapped pesticide mixtures

The application of a program written in BASIC for an IBM/PC interfaced with a commercial spectrofluorimeter enables variable-angle scanning fluorescence spectra to be obtained, without modification of the instrument. The technique is effective for determinations of the components of mixtures of carbaryl, fuberidazol and warfarin, all of which are pesticides with intrinsic fluorescence and closely overlapping profiles. The proposed method permitted simultaneous determinations with RSD of less than 2.5% and recoveries of 99–110%.     

Fluorimetric determination of beryllium with pyridoxal-5-phosphate

A simple, rapid and selective method for the determination of beryllium with pyridoxal-5-phosphate has been developed. The system is only fluorescent (lambda(ex) 360, lambda(em) 460 nm) in the presence of a nitrogenous base such as ammonia, ethylenediamine or pyridine, owing to the possible formation of a ternary complex. The calibration graph is linear over the range 8-60 ng ml . The high selectivity of the method permits the determination of beryllium in various types of alloys.     

Fluorimetric determination of sulphate by ternary complex formation with zirconium and biacetylmonoxime nicotinylhydrazone

A fluorimetric procedure for the determination of sulphate (0.5-6 mug ml ) based on the formation of a ternary complex with biacetylmonoxime nicotinylhydrazone and zirconium(IV) is described. The excitation and fluorescence maxima are at 415 and 505 nm, respectively. The method is rapid and the procedure reproducible. The precision is +/- 2% near to the middle range of the calibration curves. There is no interference from most common ions. Phosphate and fluoride are tolerated at 100-fold molar ratio to sulphate. The method has been applied to the determination of sulphate in a variety of water samples.     

Simultaneous determination of histamine and spermidine by second-derivative synchronous fluorescence spectrometry

The method is based on formation of the fluorescent condensation products with o-phthaldialdehyde; 0.5–2000 ng ml^?1 histamine and 3–700 ng ml^?1 spermidine can be quantified, with relative standard deviations of 2–3%. Histamine/spermidine ratios of 2.5:1–1:30 can be handled. A selectivity study is reported.     

Synthesis of 1,2-di-(4-pyridyl)ethylenediamine and related compounds

Hydrolysis of N,N'-diacyl-1,2-di(4-pyridyl)ethylenediamines 1 in aqueous sulfuric acid gave the corresponding imidazolines 3. 1,2-Di-(4-pyridyl)ethylenediamine 2 was prepared in 61 % yield by treating N,N'-di-t-butyl-oxycarbonyl-1,2-di(4-pyridyl)ethylenediamine 4 with trifluoroacetic acid or in 94% yield by the hydrolysis under basic conditions of N,N'-diphthaloylglycyl-1,2-di(4-pyridy)ethylenediamine 13.     

Excess enthalpies of ethylbenzene + alkane systems at 25°C. An interpretation in terms of the Prigogine-Flory-Patterson model

The molar excess enthalpies for the ethylbenzene + n-decane and ethylbenzene + n-tetradecane systems have been measured at 25°C over the complete concentration range. These results and others from the literature for alkanes + ethylbenzene, and alkanes + toluene have been discussed in terms of the Prigogine-Flory-Patterson theory.