Environmental fate of rice paddy pesticides in a model ecosystem.

The distribution and metabolic fate of several rice paddy pesticides were evaluated in a modified model ecosystem. Among the three BHC isomers, beta-isomer was the most stable and bioconcentrated in all of the organisms. Alpha- and gamma-isomers were moderately persistent and degraded to some extent during the 33 day period. Disulfoton was relatively persistent due to the transformation to its oxidation products. Pyridaphenthion was fairly biodegradable. N-Phenyl maleic hydrazide derived from the hydrolysis of pyridaphenthion was not detected in the organisms though it was found in the aquarium water after 33 days. Cartap and edifenphos were considerably biodegradable, and the ratio of the conversion to water soluble metabolites was very high. There was a distinct difference in the persistence of Kitazin P and edifenphos in the aquarium water. It appeared that the hydrolysis rate of the pesticides affected their fate in the organisms. PCP appeared to be moderately biodegradable. CNP was considerably stable and stored in the organisms though the concentration in the aquarium water was relatively low. The persistence and distribution of the pesticides in the model ecosystem were dependent on their chemical structures. In spite of the limitation derived from short experimental period, the model ecosystem may be applicable for predicting the environmental fate of pesticides.

Movement and metabolism of S-benzyl O,O-diisopropyl phosphorothiolate (Kitazin P) and O-ethyl S,S-diphenyl phosphorodithiolate (edifenphos) in various types of soils.

Movement and Metabolism of 32P and 35S-double labeled Kitazin P (S-benzyl O,O-diisopropyl phosphorothiolate) and 35S-labeled edifenphos (O-ethyl S,S-diphenyl phosphorodithiolate) were examined with three types of soils, sandy loam, alluvial clay loam, and volcanic ash loam. Vertical movement of both the compounds in soil column was different with soil types, and the order of mobility in soil column was as follows: sandy loam greater than alluvial clay loam greater than volcanic ash loam. Persistence of edifenphos in soil was shorter than that of Kitazin P. Main degradation products at the initial stage of metabolism were S,S,S-triphenyl phosphorotrithiolate, O,O-diethyl S-phenyl phosphorothiolate, S-phenyl dihydrogen phosphorothiolate and diphenyl disulfide in edifenphos and O,O-diisopropyl hydorgen phosphorothioate in Kitazin P. Sulfur atom of Kitazin P was found in sulfuric acid at a minor level through dibenzyl disulfide and toluene-alpha-sulfonic acid, and that of edifenphos was converted to sulfuric acid through diphenyl disulfide and benzenesulfonic acid. Kitazin P under flooded condition of alluvial clay loam was slightly more persistent as compared with upland condition. Sterilized condition of Kitazin P did not cause any appreciable degradation throughout the experimental period, but such condition did not necessarily prevent the degradation of edifenphos.

Chemical transformation of S-benzyl O-ethyl phenylphosphonothiolate (Inezin) by ultraviolet light.

The photodecomposition of Inezin (S-benzyl O-ethyl phenylphosphonothiolate) in n-hexane under the ultraviiolet irradiation was investigated by gas liquid chromatography, thin layer chromatography, mass spectrometry, and infrared spectroscopy. Two main steps of photodecomposition were observed at the initial stage of irradiation. One was the cleavage of P-S bond to produce O-ethyl phenylphosphinate and dibenzyl disulfide, the latter of which was degraded rather rapidly to produce sulfuric acid and benzoic acid through toluene-alpha-sulfonic acid by oxidation. The other step was the isomerization to the thionate, O-benzyl O-ethyl phenylphosphonothionate, which was gradually oxidized to itx oxygen analogue, O-benzyl O-ethyl phenylphosphate. O-ethyl phenylphosphinate, O-benzyl O-ethyl phenylphosphonate and O-benzyl O-ethyl phenylphosphonthionate were fairly stable under the ultraviolet light, as compared with Inezin. As hydrolysis products of the parent compound, phenylphosphonic acid, O-ethyl hydrogen phenylphosphonate, O-ethyl hydrogen phenylphosphonothioate and benzyl alcohol were detected.

Degradation of organophosphorus pesticides in soils with special reference to unaerobic soil conditions.

Organophosphorus pesticides are generally transformed by the reactions including oxidation, reduction, hydrolysis, hydroxylation, dehydrochlorination, dealkylation, methylation, isomerization, and conjugate formation. Although the degradation process of pesticides in soils is complicated, main factors may be soil constituents, soil microflora, and chemical structures of pesticides. Chemical structures are especially important for soil metabolism of organophosphorus pesticides, because the priority of the reactions mentioned above is decided. Although organophosphorus pesticides are generally hydrolyzable, the order of hydrolysis varies with chemical structures. It might be said that the slower the hydrolysis rate of the molecule, the more the possibility to be attacked by reactions other than hydrolysis. In such cases, oxidation and reduction are primarily important for the degradation of organophosphorus pesticides. Flooded soils in paddy fields give a favourable environment for the reduction of organophosphorus pesticides having labile substituents such as nitro groups. The threshold of reduction in-flooded soil is expressed as redox potential. Eh, the Eh of paddy soil fluctuates to a great extent, depending on seasons and soil types, especially organic matter content. The result of laboratory experiments with fenthion, disulfoton, Kitazin P (0,0-diisopropyl S-benzyl phosphorothiolate), edifenphos (0-ethyl S,S-diphenyl phosphorodithiolate) and amiprophos (0-ethyl 0-(2-nitro-p-tolyl) N-isopropyl phosphoramidothionate) suggested the participation of several factors mentioned above in the degradation of organophosphorus pesticides.