Green emulsive liquid-liquid microextraction with spontaneous emulsification and demulsification for the analysis of fungicides

Succinate dehydrogenase inhibitor fungicides (SFs) are emerging fungicides with unique mechanisms but raise concerns due to their persistence in foods. Reliable quantification of trace SF residues requires efficient and green pretreatment. Here, a green emulsive liquid–liquid microextraction (ELLME) method using cyclopentyl methyl ether and octyl glucoside was developed. The system enables spontaneous emulsification/demulsification without mixing or centrifugation, ensuring rapid mass transfer and phase separation. A semi-automated workflow allows high-throughput preparation. Coupled with high performance liquid chromatography-ultraviolet detector, recoveries were 85.4–102.8% with RSDs of 0.4–4.8%. Mechanistic studies based on density functional theory and molecular dynamics simulations revealed that van der Waals interactions predominantly drive the spontaneous extraction, while emulsion characterization confirmed the spontaneous phase-separation behavior. Multiple greenness assessment tools validated the sustainable nature of the workflow. In general, this ELLME strategy streamlines sample preparation, minimizes solvent and energy consumption, and provides a practical and sustainable platform for monitoring pesticide residues. Recovery experiments for triazole and strobilurin fungicides showed satisfactory extraction performance, suggesting that the proposed strategy can be extended to structurally diverse pesticides. Overall, the method reduces solvent and energy use and shows potential for broader pesticide analysis.