College of Chemistry and Pharmaceutical Sciences, Qingdao Agricultural University, Qingdao, China.
Innovation Center for Traditional Chinese Veterinary Medicine, College of Veterinary Medicine, China Agricultural University, Beijing, China.
Rapid Commun Mass Spectrom. 2023 Jul 15;37(13):e9518. doi: 10.1002/rcm.9518.
The residues of fipronil and its metabolites in chicken eggs pose a threat to human health, so regular monitoring is necessary. However, the pretreatments of the existing detection methods are complex and time-consuming. A simple and streamlined pretreatment method is needed to improve the detection efficiency.
A rapid, efficient, and facile approach employing the quick, easy, cheap, effective, rugged, and safe (QuEChERS) method with online solid-phase extraction liquid chromatography tandem Q Exactive Orbitrap high-resolution mass spectrometry (online-SPE-LC-HRMS) was established and evaluated for the determination of fipronil, fipronil-desulfinyl, fipronil-sulfone, and fipronil-sulfide in chicken eggs. An improved sample preparation technique combining QuEChERS and online-SPE was developed. Negative targeted ion fragmentation scanning and targeted-selected ion monitoring of HRMS were adopted to identify and quantify the target analytes.
The proposed pretreatment method took a few steps in <13 min to achieve excellent recoveries and negligible interference. High selectivity was acquired with the adoption of Q/Orbitrap HRMS. The limit of quantification (LOQ) of the analytes was 2.5 μg kg , meeting the detection requirements of the maximum residue level enacted by the Codex Alimentarius Commission, Japan, and the United States for the sum of fipronil and its metabolites. Extraction recoveries at three spiked concentration levels were within 84.56% to 93.84%, with relative standard deviation ≤5.87%.
The established method is efficient and easy to operate and displays satisfactory LOQs, recoveries, accuracy, and precision. This approach serves as a reference method for monitoring eggs while providing potential solutions for fipronil determination in more complicated matrices.
氟虫腈及其代谢物在鸡蛋中的残留对人体健康构成威胁，因此需要定期监测。然而，现有的检测方法的预处理过程复杂且耗时。需要一种简单而精简的预处理方法来提高检测效率。
建立并评估了一种快速、高效、简便的方法，采用 QuEChERS 方法与在线固相萃取液相色谱串联 Q Exactive Orbitrap 高分辨率质谱（online-SPE-LC-HRMS）相结合，用于测定鸡蛋中的氟虫腈、氟虫腈去磺酰基、氟虫腈砜和氟虫腈亚砜。开发了一种结合 QuEChERS 和在线 SPE 的改进样品制备技术。采用 HRMS 的负靶向离子碎裂扫描和靶向选择离子监测对目标分析物进行鉴定和定量。
该预处理方法在<13 分钟内只需几个步骤即可实现优异的回收率和可忽略的干扰。采用 Q/Orbitrap HRMS 获得了高选择性。各分析物的定量限（LOQ）为 2.5μg/kg，符合食品法典委员会、日本和美国对氟虫腈及其代谢物总和规定的最大残留限量的检测要求。在三个加标浓度水平下，提取回收率在 84.56%至 93.84%之间，相对标准偏差≤5.87%。
该方法高效、易于操作，具有令人满意的 LOQ、回收率、准确性和精密度。该方法为监测鸡蛋提供了参考方法，并为更复杂基质中氟虫腈的测定提供了潜在解决方案。
