Direct Spectrofluorimetric Method for the Analysis of Carbofuran and Fluometuron in Senegalese Natural Waters.

In this work, analytical study of carbofuran (CAF) and fluometuron (FLM) pesticides was carried out using direct spectrofluorimetric method in various solvents. Results showed that CAF and FLM are naturally fluorescent in all solvents under study including organic (MeOH, MeCN, DMF) and aqueous micellar one (CTAC, SDS, Brij-700). For the analysis of FLM, CTAC give the best fluorescence signal enhancement. Analytical performances, such as limit of detection (LOD) and quantification (LOQ) was evaluated after solvent optimization and were found to vary, respectively, between 0.1 and 11 ng mL- 1 and between 0.3 and 36.6 ng mL- 1. Analytical application in various environmental aqueous samples matrices (sea, tap, runoff and well waters) give satisfactory recovery rates in the limits of 73.7-113.7% for both pesticides. This method is described for its simplicity for routine analysis.

A spectrofluorimetric method for the determination of pindolol in natural waters using various organic and cyclodextrin media.

A simple, sensitive, and rapid spectrofluorimetric method was developed for the determination of the ß-blocker pindolol. The native fluorescence of pindolol was measured in different organic solvents and in cyclodextrin aqueous media. The highest fluorescence signal was obtained in 2-propanol at λem = 303 nm with λex = 260 nm. Analytical figures of merit for the spectrofluorimetric determination of pindolol were satisfactory, with wide linear dynamic range (LDR) values of two orders of magnitude, and rather low limit of detection (LOD) values between 0.2 and 8.7 ng/mL. Moreover, the addition of cyclodextrins (HP-ß-CD and ß-CD) in aqueous media enhanced the fluorescence of pindolol. In addition, the inclusion complexes of pindolol with cyclodextrins were investigated and the stability constants of complexes were calculated by means of the method of nonlinear regression (NLR). The method was successfully applied to the analysis of tap water and natural water samples, spiked with pindolol.

Micellar enhanced photo-induced fluorescence and absorbance for the development of an on-site early warning water quality monitoring system for pesticides.

This paper describes two prototypes of an on-site Early Warning Water Quality Monitoring System (EWWQMS) for pesticide quantification in natural waters. As many pesticides are non-fluorescent, the EWWQMS setup uses UV photoconversion to form highly fluorescent photoproducts. To enhance sensitivity, the two prototypes use micellar-enhanced fluorescence with surfactant (cetyl trimethyl ammonium chloride) in aqueous solution. To improve specificity, four UV LEDs at different wavelengths then excite the fluorescent photoproducts. The EWWQMS prototypes also employ UV absorption for quantification of non-photosensitive pesticides. The first prototype detects the pesticides via a diode array spectrometer. The second system is developed with higher resolution spectrometer and an intensified CCD camera detection to improve the sensitivity of the method. These experimental set-ups are described, explained and tested. Analytical applications were carried out online in CTAC aqueous solution, for the determination of isoproturon, flufenoxuron and profenofos. The calibration curves obtained are linear over one order of magnitude, and the detection limits are in the ng mL-1 range. The analytical performances of these new methods are good compared with other published classical micellar enhanced photo-induced fluorescence methods for the determination of pesticides in aqueous solutions. Our results show that these EWWQMS prototypes can be used as a warning system to protect against pesticide contamination exceeding the threshold of treatment capabilities at industrial facilities using natural waters.

Alternative to High Pressure Mercury Vapor Lamp for Photo Induced Fluorescence Analytical Methods; Application to the Determination of Pesticides in Water.

The photo-induced fluorescence method is often applied to determine non-native fluorescent compounds. It typically uses UV irradiation from a high pressure mercury vapor discharge lamp to create photo-induced fluorescent compounds, which are then quantified by fluorescence spectroscopy. However, these mercury lamps require a high-voltage power supply and may accidentally induce electric shocks and the release of mercury vapors. As an alternative, we have evaluated in this technical note new UV-C germicidal lamps. These lamps exhibit a higher power at 254 nm and allowed us to obtain a far greater amount of photo-induced compounds in a shorter time. For the first time, this new irradiation system has been applied for the determination of pesticides in water and has shown a significant increase in the method sensitivity. These good results allowed us to conclude that the new UV-C lamps are a relevant alternative to high pressure mercury vapor discharge lamps for use with photo induced fluorescent methods.

Development of an on-site early warning water quality monitoring system for pesticide detection by absorption and photo-induced fluorescence.

This paper describes prototypes of an on-site early warning water quality monitoring system (EWWQMS) for pesticide quantification in natural waters by fluorescence and absorbance. As many pesticides are not naturally fluorescent, this EWWQMS uses UV irradiation to transform these compounds into highly fluorescent photoproducts and obtain sufficient sensitivity. To obtain a better specificity, the system uses four UV LEDs at different wavelengths to excite the fluorescent photoproducts. For pesticides that are not sensitive to photoconversion, the EWWQMS prototypes also use UV absorption for their quantification, thus offering a wider application range. A first system uses a diode array spectrometer for detection. A second system uses a higher resolution spectrometer and an intensified CCD camera detection to increase sensitivity. Analytical applications were conducted for the determination of fipronil, acetamipride, cyprodinil, trifluraline and pendimethaline in water using both the EWWQMS prototypes. The analytical performances of these new systems are good compared with other photo-induced fluorescence methods already published. Limits of detection without pre-concentration are in the range of 0.2 to 3 ng mL-1 and the recovery values range from 95 to 108%. These results show that the EWWQMS prototypes can be used as an alert system to protect industrial plants from pesticide contaminations that exceed the capabilities of their cleaning processes.

Analysis of Oxadiazon Herbicide in Natural Water Samples by a Micellar-enhanced Photo-induced Fluorescence.

A micellar-enhanced photo-induced fluorescence (ME-PIF) method was developed to analyze, for the first time, oxadiazole herbicide (namely oxadiazon) in natural water samples. Photo-conversion under UV irradiation of the herbicide into strongly fluorescent photoproducts was performed in aqueous solution and in the presence of two surfactants, cetyltrimethylammonium chloride (CTAC) or Tween 20, at micellar concentrations. The ME-PIF parameters were optimized. The ME-PIF method gave very good results with satisfactory analytical performance for the determination of a selected pesticide with concentration linear dynamic ranges of over one to two orders of magnitude. It yielded good reproducibility (RSD values of between 3.6 and 9.6%) in tap, river and sea water spiked samples, and the limits of detection were in the ng mL-1 range.

Fluorescence Quenching of Two Coumarin-3-carboxylic Acids by Trivalent Lanthanide Ions.

The effects of various trivalent lanthanide ions (acetates of Ce3+, Er3+, Eu3+, Nd3+) on the electronic absorption and fluorescence spectra of un-substituted coumarin-3-carboxylic acid (CCA) and 7-N,N-diethylamino-coumarin-3-carboxylic acid (DECCA) have been investigated in dimethylsulfoxide (DMSO) at room temperature. Depending on the lanthanide ion nature and concentration, significant spectral changes of absorption bands occurred for both coumarin derivatives. These spectral changes were attributed to the formation of ground-state complexes between the coumarin carboxylate derivatives and lanthanide ions. The fluorescence quenching of CCA and DECCA upon increasing the lanthanide ion concentration was studied. Different quantitative treatments, including the Stern-Volmer equation, the Perrin equation and a polynomial equation, were applied and compared in order to determine the nature of the quenching mechanisms for both coumarin derivatives. The results suggested the contribution of both dynamic and static quenching. Significant differences of CCA and DECCA fluorescence quenching efficiency were also observed, depending on the lanthanide ion. DECCA fluorescence lifetime measurements, performed in the absence and in the presence of Ln3+, confirmed a contribution of static quenching.

Spectrofluorometric Determination of Putrescine: Optimization of the Putrescine-Orthophthaldehyde Complex Using Spectrofluorometry.

In alkaline medium, the complex formed between putrescine and orthophthalaldehyde was studied using spectrofluorescence. The derivative is kinetically stable 24 h after complexation. The stoichiometry of the complex is 1:1 at maximum fluorescence intensity, also 24 h after complexation.

Spectrofluorometric Determination of Putrescine Using Orthophthaldehyde as a Fluorophore: A Novel Method.

This paper concerns spectrofluorometric analysis of putrescine using orthophthaladehyde as a fluorophore in aqueous alkaline medium. Wavelengths of excitation and emission in acid, neutral, and alkaline media were different. There is a maximum intensity of fluorescence in alkaline medium 24 h after complexation compared with other media. Putrescine and orthophthaladehyde are used at an equimolar ratio, and the product is kinetically stable in alkaline medium. Calibration curves obtained gave limits of detection and quantification of 39 and 65 ng/mL, respectively. The correlation coefficient obtained in alkaline medium was 0.992 at pH 12. Results obtained largely showed a good reproducibility of our method.

Revisiting the photophysical properties and excited singlet-state dipole moments of several coumarin derivatives.

The solvent effects on the electronic absorption and fluorescence emission spectra of several coumarins derivatives, containing amino, N,N-dimethyl-amino, N,N-diethyl-amino, hydroxyl, methyl, carboxyl, or halogen substituents at the positions 7, 4, or 3, were investigated in eight solvents with various polarities. The first excited singlet-state dipole moments of these coumarins were determined by various solvatochromic methods, using the theoretical ground-state dipole moments which were calculated by the AM1 method. The first excited singlet-state dipole moment values were obtained by the Bakhshiev, Kawski-Chamma-Viallet, Lippert-Mataga, and Reichardt-Dimroth equations, and were compared to the ground-state dipole moments. In all cases, the dipole moments were found to be higher in the excited singlet-state than in the ground state because of the different electron densities in both states. The red-shifts of the absorption and fluorescence emission bands, observed for most compounds upon increasing the solvent polarity, indicated that the electronic transitions were of π-π* nature.

Mass Spectrometry Study of Coumarins: Correlation Between Charges of Atoms and Fragmentation Processes.

The mass spectrometry of a number of 6-substituted coumarins was studied in the context of correlating fragmentation pathways and electronic charges of atoms performed by AM1 semiempirical method. The atomic charges of atoms are found to be good predictors of the fragmentation pathways.