A simple approach for the ultrasensitive detection of paraquat residue in adzuki beans by surface-enhanced Raman scattering

Paraquat (PQ), a broad-spectrum contact herbicide, has been used in many countries for controlling weed growth in agriculture because of its quick-acting and nonselective contact with green plant tissue. PQ is also toxic to humans, and even contributes to the development of neurodegenerative diseases. However, PQ is generally excluded from pesticide residue monitoring programs due to the lack of suitable determination methods. Thus, this study developed a detection method combined with simple extraction and surface-enhanced Raman spectroscopy (SERS) to rapidly determine and quantify the PQ residue on legumes without destructive procedures and high-cost instruments. Following the extraction procedure of the QuPPe-method, however, we took whole adzuki beans (Vigna angularis) extracted via a mixture of methanol and 1% formic acid at room temperature and followed by a 1 min cleanup by SPE. The PQ values for adzuki beans determined by LC/MSMS showed that regardless of whether extraction was followed by the QuPPe-method or the method we proposed, a consistent and low relative standard deviation (RSD) below <22% was found. In this study, we proposed to extract PQ on the surface of the beans by shaking briefly with solvent, and then the PQ molecules were detected and quantified by depositing Ag nanoparticles (AgNPs) and performing SERS within 10 min. Using a coating of deposited Ag nanoparticles, SERS can achieve a limit of detection (LOD) for PQ on the order of 1 μg L-1 (∼4 × 10-9 M) and a method detection limit (MDL) for adzuki beans of 0.8 μg kg-1 (∼3.3 × 10-9 M). This sensitivity at the ppb level absolutely met the maximum residue limit (MRL) for PQ in dried beans as declared by most countries, including the US (0.3 mg kg-1), Australia (1.0 mg kg-1) and Taiwan (0.2 mg kg-1). Taiwan will ban the use of PQ as a defoliating agent for harvest in adzuki bean fields in 2019; therefore, developing a method for detecting PQ residues in the field or in import markets is necessary for consumer health and for authorities. This study provided an opportunity to utilize SERS in the field of on-site pesticide residue screening.