L. Stephan

Molecular and atomic ultra trace analysis by laser induced fluorescence with OPO system and ICCD camera.

This paper presents a synthesis of some analytical potentialities of an equipment designed for both laser induced molecular and atomic fluorescence in the field of ultra-trace analysis (ng l(-1)). Excitation of fluorescence was performed with a pulsed Nd:Yag laser coupled to an optical parametric oscillator (OPO). Fluorescence spectra were recorded with a spectrograph and an intensified charge-coupled device (ICCD). The high energy and the tunability of the excitation combined with the sensitivity of the ICCD and the time-resolution provide better limit of detection (LOD) and selectivity. By molecular fluorescence, some major organic contaminants in the environment were studied, i.e. polycyclic aromatic hydrocarbons (PAHs) (benzo[a]pyrene and hydroxypyrene) and a pesticide (carbaryl). The LODs achieved by direct analysis were far below the restricted European values for tap water. Analysis was performed in water containing humic acids using time resolution to avoid the matrix fluorescence. By electro thermal atomisation-laser excited atomic fluorescence (ETA-LEAF), we detected traces of aluminium and lead in seawater. Some general considerations about the signal to noise ratio optimisation are reported. LODs reached the femtogram level.

Direct determination of aluminum content in seawater by electrothermal atomization-laser excited atomic fluorescence

Abstract The development of an analytical method for the direct determination of ultra trace content of aluminum in seawater by electrothermal atomization-laser excited atomic fluorescence (ETA-LEAF) using a pulsed Nd:Yag laser associated with an optical parametric oscillator (OPO) and an intensified CCD (ICCD) camera is described. The good temporal reproducibility of the device and the fairly long lifetime of the selected Al radiation allowed optimization of the temporal parameters in the nanosecond range. After optimizing thermal and optical parameters, this potentiality allowed to reach a 100 fg detection limit (5 ng l−1). The method was developed within a multidisciplinary program involving chemical and physical applications, thereby demonstrating the versatility of the apparatus.

Multicomponent Determination of a Polyaromatic Hydrocarbon Mixture by Direct Fluorescence Measurements

This study deals with an analysis of a mixture of five polyaromatic hydrocarbons (PAHs) with the aim of avoiding any preliminary treatment of the sample such as extraction or concentration, which are time-consuming procedures. To reach this goal we studied a direct multicomponent determination of the PAHs in mixture by applying principal-component analysis and principal-component regression techniques, which are briefly explained in this work. After a calibration procedure we were able to analyze each PAH of the mixture by a simple and direct fluorescence measurement. Moreover, the quantitative results obtained were assessed on some test samples. The results obtained and the further developments of this study will be also discussed.

Determination of phenylurea pesticides by direct laser photo-induced fluorescence

A direct Laser Photo-Induced Fluorescence (DL-PIF) method is developed for the determination of two phenylurea pesticides, namely fenuron and diflubenzuron. The DL-PIF method uses a tunable Nd:YAG-OPO Laser to obtain the photoproduct(s) and to simultaneously analyse their fluorescence in a short acquisition time on an intensified CCD camera. Compared to classical PIF methods, the use of a tunable laser improves the selectivity (by choosing the suitable excitation wavelength), increases the sensitivity (due to the high energy of the beam) and also reduces the time of analysis. The analytical performances of this method for the determination of both pesticides are satisfactory in comparison to other classical PIF methods published for the determination of phenylurea pesticides. The calibration curves were linear over one order of magnitude and the limits of detection were in the ng mL(-1) range. Satisfactory recoveries were obtained in the analysis of both pesticides in river and sea water spiked samples.

Enhanced metal adsorption on solid suspensions by organic molecules

This laboratory study mimicked the pollution of a suspension of silica beads, used as a crude model of sand, by naphthalene in mixture with carbofuran at first, and then by this mixture in association with a metal salt, Pb(NO(3))(2). The silica properties and the working conditions were such that they allowed us to only observe physisorption, which is the first and essential step of any adsorption mechanism. Naphthalene and carbofuran were, respectively, chosen as hydrocarbon and pesticide. Naphthalene adsorption from simple solutions is rather large compared to other organic adsorptions, and carbofuran seems to adsorb on a layer of naphthalene when the latter is mixed in solution with carbofuran. Like other organics, naphthalene favours the adsorption of lead ions, but ionic adsorption is considerably increased by the combination of naphthalene and carbofuran. The Wagner-Onsager-Samaras theory shows that the result implies a special organization of organic molecules at the interface. Conclusions about some environmental mechanisms of fixation, or release, of ions on sands in the case of simple physisorption are drawn from the study.

A new direct laser photo-induced fluorescence method coupled on-line with liquid chromatographic separation for the simultaneous determination of anilides pesticides

A new direct laser photo-induced fluorescence high performance liquid chromatography (DL-PIF-HPLC) method is developed for the simultaneous determination of three anilide pesticides, namely carboxin, monalide and propanil. DL-PIF-HPLC uses a tunable Nd:YAG-OPO laser to obtain fluorescent photoproduct(s) and to simultaneously analyze their fluorescence in a short acquisition time with an intensified CCD camera, which improves the selectivity (by choosing the suitable excitation wavelength), increases the sensitivity (due to the high energy of the laser beam) and reduces the time of analysis, relative to the classical PIF methods. However, one of the main drawbacks of PIF methods is the presence of interferences with other compounds, such as other pesticides from the same group yielding similar fluorescent photoproducts, which reduces their selectivity. The analytical interest of DL-PIF-HPLC to avoid these interferences is demonstrated. The DL-PIF spectra, chromatographic conditions and analytical performances of DL-PIF-HPLC are presented for the simultaneous determination of three anilide pesticides. The calibration curves are linear over one order of magnitude and the limits of detection are in the ng mL(-1) range. The new DL-PIF-HPLC system has the advantage to combine the performances of both techniques, DL-PIF and liquid chromatography, and to improve the analysis selectivity.