Photodegradation kinetics, mechanism and aquatic toxicity of deltamethrin, permethrin and dihaloacetylated heterocyclic pyrethroids

Abstract

Photochemical methods attracted much research interests for their high-efficiency and low secondary pollution. Decomposition of synthetic pyrethroids, the fourth major group of insecticides in use worldwide, was also of great significance due to their possible environmental risks. The photodegradation of deltamethrin, permethrin and dihaloacetylated heterocyclic pyrethroids in methanol/acetone = 9/1 (by volume) by a 400 W mercury lamp was examined. The t1/2 of tested pyrethroids was less than 25 min, except for cis-permethrin with a t1/2 of up to 50 min. The trans-isomer of permethrin and compound DCA-01 with a smaller t1/2 might be more susceptible to degradation than their cis-isomer. Besides, the photodegradation of pyrethroids was divided into twelve pathways including isomerization, ester hydrolysis, ester bond cleavage, CO bond cleavage, 3,3-dimethylacrylate formation, double bond break, C1-C3 bond cleavage in cyclopropyl, reductive dehalogenation, decarboxylation, nucleophilic reagents attack on lone pair electrons on oxygen atoms in the phenyl ether, cyano hydrolysis, and halogenated hydrocarbon hydrolysis. The ECOSAR program displayed that pyrethroids and most of their photodegradation products were toxic to fish, daphnid, green algae. Particularly, some photodegradation products were more harmful to aquatic organisms than their parents.