Comparative abiotic or biotic degradation of carboxin by two Entisols with different surface properties or Pseudomonas aeruginosa strain: A toxicity study using the crustacean Thamnocephalus platyurus

The microcrustacean Thamnocephalus platyurus was used to detect the toxicity reduction of carboxin in abiotic degradation compared to biotic degradation. The abiotic degradation was obtained using two sterilized Entisols with different surface properties while the biotic degradation by Pseudomonas aeruginosa was obtained using the fungicide as the only C source. The results showed that the highest toxicity reduction rates for the abiotic degradation were achieved in 20 days with 49.2% for the coarser soil, 60.7% for the soil with a finer texture, whereas for the biotic degradation, 60.6%. Analysis (¹H NMR) showed that the soils transformed carboxin to produce sulfoxide and enol in different concentrations depending on the soil properties, while P. aeruginosa metabolized the fungicide to produce inorganic compounds such as ammonium and nitrite, minor degradation pathways were oxidized to sulfoxide and hydrolytic ring-opening to 2-[(2-hydroxyethyl)thio]acetoacetanilide enol. These results indicated that the degradation of carboxin occurred via abiotic catalytic processes as well as via biotic transformation leading to less toxic derivatives and such phenomena are caused by exchange/surface features of soils, rather than by the mere content of clay or organic matter fractions.     

Effects of sensitizers on the photodegradation of the systemic fungicide triadimenol

The photochemical behaviour of triadimenol (1) under various conditions has been examined. Significant degradation is obtained only in the presence of electron-acceptor sensitizers as 9,10-dicyanoanthracene or 2,4,6-triphenylpyrylium tetrafluoroborate, and long irradiation times are required. 1H-1,2,4-Triazole (2), 4-chlorophenyl formate (3), 4-chlorophenol (4), 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one (5), 4-chlorophenyl 2,2-dimethylpropanoate (6) and 4-chlorobenzoic acid (7) were identified as photoproducts by NMR and GC-MS.     

A mild photochemical approach to the degradation of phenols from olive oil mill wastewater

Photooxidation of cathecol (1) is carried out in aqueous solution at lambda > 300 nm using different sensitizers: rose bengal (RB), 9,10-dicyanoanthracene (DCA), 2,4,6-triphenylpyrylium tetrafluoroborate (Pyryl). The highest degradation is observed in the UV/RB-sensitized reaction (66% after 15 h of irradiation), mineralization and formation of dimers are the final events. This procedure has been extended to tyrosol (2), caffeic acid (3), vanillic acid (4), 4-hydroxycinnamic acid (5) and 4-hydroxybenzoic acid (6) as well as to a mixture of all phenols. A reduced toxicity of the UV/RB-irradiated solutions of cathecol and tyrosol towards alga Ankistrodesmus braunii is also verified.     

Photochemical behaviour of the systemic fungicide carboxin

Irradiation of carboxin (1) with a 500 W UV lamp (filter Pyrex) in CH3CN leads to the products 3, 5-8, 12-14 depending upon the reaction conditions. All photo-products were isolated and characterized. Photooxidation occurred even if unsensitized, while photoalteration was very slow in the absence of oxygen. The main oxygenated-products 3 and 13 were also recovered under biomimetic conditions by exposure of an aqueous solution of 1 to sunlight.     

Transformation and Ecotoxicity of Carbamic Pesticides in Water (5 pp)

Background N-methylcarbamate insecticides are widely used chemicals for crop protection. This study examines the hydrolytic and photolytic cleavage of benfuracarb, carbosulfan and carbofuran under natural conditions. Their toxicity and that of the corresponding main degradation products toward aquatic organisms were evaluated. Methods Suspensions of benfuracarb, carbosulfan and carbofuran in water were exposed to sunlight, with one set of dark controls, for 6 days, and analyzed by 1H-NMR and HPLC. Acute toxicity tests were performed on Brachionus calyciflorus, Daphnia magna, and Thamnocefalus platyurus. Chronic tests were performed on Pseudokirchneriella subcapitata, and Ceriodaphnia dubia. Results and Discussion Under sunlight irradiation, benfuracarb and carbosulfan gave off carbofuran and carbofuran-phenol, while only carbofuran was detected in the dark experiments. The latter was degraded to phenol by exposure to sunlight. Effects of pH, humic acid and KNO3 were evaluated by kinetics on dilute solutions in the dark and by UV irradiation, which evidenced the lability of the pesticide at pH 9. All three pesticides and phenol exhibited acute and higher chronic toxicity towards the aquatic organisms tested. Conclusion Investigation on the hydrolysis and photolysis of benfuracarb and carbosulfan under natural conditions provides evidence concerning the selective decay to carbofuran and/or phenol. Carbofuran is found to be more persistent and toxic. Recommendations and Outlook The decay of benfuracarb and carbosulfan to carbofuran and the relative stability of this latter pesticide account for many papers that report the detection of carbofuran in water, fruits and vegetables.     

Phototransformation of fibrate drugs in aqueous media

The photochemical conversion of bezafibrate, gemfibrozil, fenofibrate and fenofibric acid has been examined in aqueous media. Irradiation with a solar simulator in distilled water caused about 10% degradation for the first three drugs after 200 hr, while fenofibric acid was completely degraded after 100 hr. Experiments have also been performed in the presence of nitrates or humic acids, considered as environmental photosensitizers, and only for gemfibrozil a reduction of degradation has been observed. Photoproducts have been characterized and the mechanistic pathways discussed on the basis of experimental and literature data.     

Sensitized photooxygenation of the fungicide furalaxyl

BACKGROUND: The photolysis of pesticides is of high current interest since light is one of the most important abiotic factors which are responsible for the environmental fate of these substances and may induce their conversion into noxious products. The action of light can also be mediated by oxygen and synthetic or naturally occurring substances which act as sensitizers. Our objective in this study was to investigate the photochemical behaviour of the systemic fungicide furalaxyl in the presence of oxygen and various sensitizers, and to compare the toxicity of the main photoproduct(s) to that of the parent compound. Previous reports on the direct photolysis of the pesticide demonstrated a very slow degradation and the only identified photoproducts were N-2,6-xylyl-D,L-alaninare and 2,6-dimethylaniline. METHODS: Solutions of furalaxyl in CH3CN were photooxygenate using a 500W high-pressure mercury lamp (through a Pyrex glass filter, lambda>300 nm) or a 650W halogen lamp or sunlight and the proper sensitizer. When sunlight was used, aqueous solutions were employed. The photodegradation was checked by NMR and/or GC-MS. The photoproducts were spectroscopically evidenced and, when possible, isolated chromatographically. Acute toxicity tests were performed on the rotifer Brachionus calyciflorus, the crustacean cladoceran Daphnia magna and the anostracan Thamnocephalus platyurus, while chronic toxicity tests (sublethal endpoints) comprised a producer, the alga Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia, as a consumer. RESULTS AND DISCUSSION: In the presence of both oxygen and sensitizer, furalaxyl underwent rapid photochemical transformations mainly to N-disubstituted formamide, maleic anhydride and a 2(5H)-furanone derivative. The formation of these products was rationalized in terms of a furan endoperoxide intermediate derived from the reaction of furalaxyl with active dioxygenated species (singlet oxygen, superoxide anion or ground state oxygen). The 2(5H)-furanone exhibited a higher toxicity than the parent compound. CONCLUSION: This work reports the first data on the photosensitized oxygenation of furalaxyl with evidence of the high tendency of the pesticide to undergo photodegradation under these conditions leading, among other things, to a 2(5H)-furanone, which is more toxic than the starting furalaxyl towards aquatic organisms. RECOMMENDATIONS AND OUTLOOK: Investigation highlights that the photolytic fate of a pesticide, although quite stable to direct photoreaction due to its low absorption of solar radiation at ground level, can be significantly influenced in the environment by the presence of substances with energy or electron-transfer properties as natural dyes, e.g. chlorophyll, or synthetic pollutants, e.g. polycyclic aromatic hydrocarbons (PAH).