Pesticide Encapsulation at the Nanoscale Drives Changes to the Hydrophobic Partitioning and Toxicity of an Active Ingredient

Given the costs associated with designing novel active ingredients, new formulations focus on the use of other ingredients to modify existing formulations. Nanosized encapsulated pesticides offer a variety of enhanced features including controlled release and improved efficacy. Despite the presence of nanosized capsules in current-use pesticide formulations, the analytical and toxicological implications of encapsulation are uncertain. To explore this issue quantitatively, we fractionated the capsules of a commercially available encapsulated insecticide formulation (gamma-cyhalothrin active ingredient) into two size ranges: a large fraction (LF), with an average hydrodynamic diameter (HDD) of 758 nm, and a small fraction (SF), with an average HDD of 449 nm. We developed a novel extraction method demonstrating a time-dependent inhibition of gamma-cyhalothrin from capsules for up to 48 h. An acute immobilization test with a freshwater macroinvertebrate (Ceriodaphnia dubia) revealed that the SF was significantly more toxic than both the LF and the free gamma-cyhalothrin treatment (EC50 = 0.18 mu g/L, 0.57 mu g/L, and 0.65 mu g/L, respectively). These findings highlight that encapsulation of gamma-cyhalothrin mitigates hydrophobic partitioning in a time-dependent manner and influences toxicity in a size-dependent manner. Recognizing the analytical and toxicological nuances of various nanosized capsules can contribute to innovation in pesticide formulations and may lead to more comprehensive pesticide regulation.