Fast simultaneous determination of traces of Cu(II) and Co(II) in soils and sediments with the luminol/perborate chemiluminescent system.

A flow injection analysis method based on ion chromatography and luminol chemiluminescence detection was used for the simultaneous determination of copper (II) and cobalt (II) trace levels in soils and sediments following microwave-assisted acid digestion. Detection was based on chemiluminescence (CL) of the luminol-perborate system in an alkaline medium, which is catalyzed by both transition metals. The concentration and pH of the eluent (oxalic acid) was found to affect CL intensities and retention times, both of which were inversely proportional to the oxalic acid concentration. The calibration curves for both metal ions were linear and allowed a limit of detection of 0.003 µg l(-1) for cobalt (II) and 0.014 µg l(-1) for cooper (II) to be calculated. The proposed method was successfully used to determine both metal ions in certified reference materials of stream and river sediments and soil samples. Based on the results, the determination is free of interferences from the usual concomitant ions.

Kinetic-spectrometric three-dimensional chemiluminescence as an effective analytical tool. Application to the determination of benzo(a)pyrene.

Kinetic and spectroscopic methods were used in combination in this work to develop a new analytical tool for use in chemiluminescence detection processes. Specifically, time-resolved chemiluminescence was used jointly with a stopped-flow assembly in order to monitor the chemiluminescence produced in the oxidation of bis(2,4-dinitrophenyl)oxalate (DNPO) by hydrogen peroxide in the presence of a polycyclic aromatic hydrocarbon. Recording of successive two-dimensional spectra during the emission process and treating the acquired spectral data with dedicated software allows the obtainment of three-dimensional chemiluminescence spectra, a result of the joint use of two analytical techniques. Thus, using a flow cell specifically designed for direct coupling to the charge-coupled device (CCD) detector increases the emission intensity without the need for fibre optics. Also, using dedicated software to process the acquired two-dimensional spectra affords a comprehensive kinetic and spectroscopic characterization of the chemiluminescence signal via the three-dimensional spectrum previously obtained. The analytical potential of this new tool was assessed by application to the chemiluminescent reaction between a peroxyoxalate and an oxidant (hydrogen peroxide); the reaction is induced by benzo(a)pyrene, which was used to determine this polycyclic aromatic hydrocarbon in an organic solvent. A linear calibration graph was obtained between 0.5 and 20 mg L(-1). The limit of detection found to be 3.97 µg L(-1) and a relative standard error of 0.64% and a relative standard deviation of 1.87% were obtained. The results reached testify to the usefulness of the proposed analytical tool for simple determinations and its potential for the resolution of complex mixtures or determinations in complex matrices.