Rösch Andrea, Wettstein Felix E, Wächter Daniel, Reininger Vanessa, Meuli Reto G, Bucheli Thomas D
Environmental Analytics, Agroscope, 8046, Zurich, Switzerland.
Soil Quality and Soil Use, Agroscope, 8046, Zurich, Switzerland.
Anal Bioanal Chem. 2023 Oct;415(24):6009-6025. doi: 10.1007/s00216-023-04872-8. Epub 2023 Aug 8.
A multi-residue trace analytical method is presented to accurately quantify 146 currently used pesticides in (agricultural) soils with varying soil properties. Pesticides were extracted using an optimized quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach and chemical analysis was carried out by liquid chromatography coupled to tandem mass spectrometry (triple quadrupole). Quantification was based on matrix-matched internal standards calibration, using 95 isotopically labeled analyte analogues. In contrast to the common approach of method validation using soils freshly spiked with analytes shortly before the extraction, our method is additionally validated via an in-house prepared partly aged soil, which contains all target pesticides and via agricultural field soils with native pesticide residues. The developed method is highly sensitive (median method limit of quantification: 0.2 ng/g), precise (e.g., median intra-day and inter-day method precision both ~ 4% based on field soils), and true ((i) quantified pesticide concentrations of the partly aged soil remained stable during 6 months, were close to the initially spiked nominal concentration of 10 ng/g, and thus can be used to review trueness in the future; (ii) median freshly spiked relative recovery: 103%; and (iii) participation in a ring trial: median z-scores close to one (good to satisfactory result)). Its application to selected Swiss (agricultural) soils revealed the presence of in total 77 different pesticides with sum concentrations up to 500 ng/g. The method is now in use for routine soil monitoring as part of the Swiss Action Plan for Risk Reduction and Sustainable Use of Plant Protection Products.
本文提出了一种多残留痕量分析方法，用于准确量化不同土壤性质的（农业）土壤中目前使用的146种农药。采用优化的快速、简便、廉价、高效、耐用且安全（QuEChERS）方法提取农药，并通过液相色谱-串联质谱（三重四极杆）进行化学分析。定量基于基质匹配内标校准，使用95种同位素标记的分析物类似物。与提取前不久用分析物新鲜加标的土壤进行方法验证的常见方法不同，我们的方法还通过内部制备的部分老化土壤（包含所有目标农药）和含有天然农药残留的农业田间土壤进行了验证。所开发的方法具有高灵敏度（中位法定量限：0.2 ng/g）、高精度（例如，基于田间土壤的中位日内和日间方法精密度均约为4%）和准确性（(i) 部分老化土壤的定量农药浓度在6个月内保持稳定，接近最初加标的标称浓度10 ng/g，因此可用于未来的准确性评估；(ii) 新鲜加标的中位相对回收率：103%；(iii) 参与能力验证试验：中位z分数接近1（结果良好至令人满意））。将其应用于瑞士选定的（农业）土壤，结果显示总共存在77种不同农药，总浓度高达500 ng/g。该方法现已作为瑞士植物保护产品风险降低和可持续使用行动计划的一部分用于常规土壤监测。
