Ecotoxicity of ammonium chlorophenoxyacetate derivatives towards aquatic organisms: Unexpected enhanced toxicity upon oxygen by sulfur replacement

Phenoxyacetate herbicides, such as 2,4-D and MCPA, having a high toxicity to non-target organisms are commonly used for controlling broadleaf weeds in agriculture. However, novel and environmentally friendly analogs are constantly sought after. For this purpose, various substituents at the phenyl group have been tested to find the optimal balance between the potent herbicidal activity and safety for non-target species. In this work, we investigated the influence of the oxygen by sulfur replacement in the phenoxy moiety of ammonium chlorophenoxyacetates on the toxicity towards aquatic organisms, such as bacteria (Vibrio fischen), water flea (Daphnia magna) and freshwater fish (Pimephales promelas) by determining experimental (Microtox (R) test - V. fischen) and predicted (ACD lab Percepta software - D. magna, P. promelas) EC50/LC50 values. The achieved results showed that in contrary to the literature observations, where O-compounds were more toxic than their S-analogs (urea/thiourea), the O/S replacement in chlorophenoxyacetate significantly increased ecotoxicity of the S-analogs (up to 11 times). Moreover, one- and two-substituted phenoxyacetates in the form of ammonium salts were less toxic to V. fischeri than the commercially available phenoxy herbicides in the acid form. The logP/logD values were also calculated to understand hydro/ lipophilic nature of the investigated compounds and differences in their toxicity.