With one exception, the structures proposed for the photoproducts on the basis of mass spectra interpretation have not been reported in previous studies. In silico toxicity predictions showed that two photoproducts are potentially more toxic than the parent compound considering oral rat LD50 while five photoproducts may induce mutagenic toxicity. With the exception of one compound, all photoproducts may potentially induce developmental toxicity.

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Ultraviolet (UV)-visible irradiation of fludioxonil was investigated with two photoreactors using either a mercury or xenon vapor lamp. In both cases, it led to the formation of only one photoproduct in significant amount: 2-(2,2-difluorobenzo[d][1,3]dioxol-4-yl)-2-(nitrosomethylene)-4-oxobutanenitrile, which has been characterized using Liquid Chromatography - High Resolution - Tandem Mass Spectrometry (LC-HR-MS/MS) coupling. A photolysis pathway has been proposed to rationalize its formation in degassed water. In vitro bioassays on Vibrio fischeri bacteria showed that UV-vis irradiation of an aqueous solution of fludioxonil significantly increases its toxicity. Because no other by-product was detected in significant amount, the photoproduct mentioned above may be considered mainly responsible for this increase in toxicity. Grape berries treated with a 50 ppm aqueous solution of fludioxonil were submitted to UV-visible irradiation under laboratory conditions. The fungicide and photoproduct were detected in both skin and flesh of berries, even after they have been rinsed with water. The ability of the photoproduct to pass through the fruit skin is comparable with that of fludioxonil. These results are of concern for consumers because they mean that water tap rinsing does not lead to efficient removing of both compounds.

UV-visible irradiation of fenbuconazole in aqueous solution and on grapes leads to the formation of isomers, all of which being potentially much more toxic than the parent fungicide.

Abstract:In this work, the low cost synthesis of polydimethylsiloxane (PDMS) rods is described, and the performances of this new passive sampling device (in laboratory and in situ) are compared to the passive stir bar sorptive extraction (SBSE) for the monitoring of pesticides from different classes (herbicides, insecticides and fungicides) in surface waters. The influence of synthesis parameters of PDMS rods (i.e., heating temperature, heating time and relative amount of curing agent) were assessed regarding their efficiency for the extraction of the target pesticides through a Hadamard's experimental design. This allowed the determination of the effect of the three parameters on the sorption of pesticides within four experiments. Thus, specific conditions were selected for the synthesis of the PDMS rods (heating at 80 °C for 2 h with 10% of curing agent). Laboratory experiments led to similar to lower extraction recovery in the PDMS rods in comparison with passive SBSE, depending on the pesticide. The in situ application demonstrated the efficiency of the PDMS rods for the passive sampling of the target pesticides in river water, although lower amounts of pesticides were recovered in comparison with passive SBSE. So, these very low cost PDMS rods could be used as an alternative to passive SBSE for large-scale monitoring campaigns. OPEN ACCESSWater 2013, 5 1367

Hydrophilic interaction LC was investigated in hydro-organic and nonaqueous elution modes on a titania column by using a set of N-methyl xanthines as neutral polar probes. To get information regarding the mechanisms that are behind the discrimination of these analytes in hydrophilic interaction, we focused our study on the type and amount of organic modifier as a critical yet rarely explored mobile phase parameter. Several alcohols such as methanol, ethanol, and isopropanol were studied as substitutes to acetonitrile in hydro-organic elution mode. Compared to silica, the investigation of the eluotropic series of these alcohols on titania highlighted a different implication in the retention mechanism of the xanthine derivatives. At low amounts of protic solvents, the adsorption mainly characterized the retention of analytes on bare silica; whereas mixed interactions including adsorption and ligand exchange were identified on native titania. To investigate the peculiar behavior of alcohols on the metal oxide, methanol, ethanol, and ethylene glycol were tested in replacement of water in polar-organic elution mode. Distinctive effects on the chromatographic retention and selectivity of xanthines were noticed for the dihydric alcohol, which was found to be a stronger eluting component than water on titania.