Light induced degradation of testosterone in waters.

The degradation of testosterone under simulated irradiations was studied in phosphate buffers and in natural waters at various excitation wavelengths. The quantum yield of photolysis was significantly lower at 313 nm (2.4 x 10(-3)) than at 254 nm (0.225). The formation of several photoproducts was observed, some of them being rapidly transformed in turn while others show higher stability towards subsequent irradiations. The nature of the main products was tentatively identified, both deduced from their spectral and spectrometric data and by comparison with synthesised standard compounds. Among the obtained photoproducts, the main one is possibly a spiro-compound, hydroxylated derivative of testosterone originating from the photohydratation of the enone group. The photodegradation pathway includes also photorearrangements. One of them leads to (1,5,10)-cyclopropyl-17beta-hydroxyandrostane-2-one. The pH of the water does not seem to affect the rate of phototransformation and the nature of the by-products.

Effect of positional isomerism on the abiotic degradation of pesticides: Case of m- and p-imazamethabenz-methyl.

The effect of positional isomerism on chemical and photochemical degradations of the Imazamethabenz-methyl (IMBM), a pesticide of the imidazolinone family, has been studied. IMBM is proposed in the form of a mixture of the two positional isomers: meta and para. The development of an effective HPLC method (resolution factor R=1.3) allows us to follow either the abiotic disappearance of the meta and para IMBM and the formation of their breakdown products. The abiotic degradation studies include the chemical hydrolysis, as well as the direct and the indirect photodecomposition. We used TiO(2), a well-known initiator of hydroxyl radicals, to highlight the role of *OH in the indirect photodegradation. This work confirms the different behaviours of positional isomers in the environment. Indeed the chemical or direct photochemical degradation is faster for the meta isomer than for the para. Whereas, concerning IMBM, there is not any prevalent influence of this type of isomerism on the indirect photochemical degradation. The degradation products were tentatively identified by LC-MS, NMR and IR and a degradation pathway was proposed.

Influence of metal salts on the photodegradation of imazapyr, an imidazolinone pesticide.

The behaviour of imazapyr (2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)nicotinic acid), a broad spectrum herbicide of the imidazolinone family, has been studied under UV radiation in the presence of metal salts. Complexation interactions between imazapyr and metal ions decreased imazapyr photolysis. A chemometric study compared the photodegradation of imazapyr in aqueous solutions in the presence of Na+, Ca2+ or Cu2+ and their concomitant anionic species (Cl-, NO3-) at various pesticide/metal ion molar ratios. The study showed the major role of metal ions in the degradation of imazapyr and its main photoproducts. The molecules were strongly stabilised on complexation with metal ions, leading to an increase in persistence of the pesticide.

Photochemical degradation of imazamox in aqueous solution: influence of metal ions and anionic species on the ultraviolet photolysis.

Imazamox [5-methoxymethyl-2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid] is one of the later pesticides of the imidazolinone family. The fate of imazamox has been studied upon UV irradiation. The degradation of a 10 mg L(-1) imazamox solution leads to pyridine derivatives, which remain in solution for 50-100 h. Most of the photoproducts occurring during the photodegradation have been characterized by means of liquid chromatography coupled with mass spectrometry. The degradation scheme is very similar to that observed for the analogous imazapyr pesticide [2-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl) nicotinic acid]. Nevertheless, imazamox shows a greater stability than imazapyr. More, complexation interactions between imazamox and metal ions such as Cu2+ or Ca2+ increase the persistence of the pesticide.