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.