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Simultaneous determination of diquat, paraquat, glufosinate, and glyphosate in plasma by liquid chromatography/tandem mass spectrometry: from method development to clinical application

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Abstract

Diquat (DQ), paraquat (PQ), glufosinate (GLU), and glyphosate (GLYP) are commonly used herbicides that have been confirmed to be toxic to humans. Rapid and accurate measurements of these toxicants in clinical practice are beneficial for the correct diagnosis and timely treatment of herbicide-poisoned patients. The present study aimed to establish an efficient, convenient, and reliable method to achieve the simultaneous quantification of DQ, PQ, GLU, and GLYP in human plasma using liquid chromatography-tandem mass spectrometry (LC-MS/MS) without using derivatization or ion-pairing reagents. DQ, PQ, GLU, and GLYP were extracted by the rapid protein precipitation and liquid-liquid extraction method and then separated and detected by LC-MS/MS. Subsequently, linearity, limit of detection (LOD), limit of quantification (LOQ), precision, accuracy, extraction recovery, matrix effect, dilution integrity, and stability were evaluated to validate the method based on the FDA criteria. Finally, the validated method was applied to real plasma samples collected from 166 Chinese patients with herbicide poisoning. The results showed satisfactory linearity with low LOD (1 ng/mL for DQ and PQ, 5 ng/mL for GLU, and 10 ng/mL for GLYP, respectively) and low LOQ (5 ng/mL for DQ and PQ, 25 ng/mL for GLU and GLYP, respectively). In addition, the precision, accuracy, extraction recovery, and stability of the method were acceptable. The matrix effect was not observed in the analyzed samples. Moreover, the developed method was successfully applied to determine the target compounds in real plasma samples. These data provided reliable evidence for the application of this LC-MS/MS method for clinical poisoning detection.

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Acknowledgements

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Funding

This study was financially supported by the Key Research and Development Project of the Department of Science and Technology of Sichuan Province (No. 2021YFS0274).

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Authors and Affiliations

  1. Department of Laboratory Medicine, West China Hospital, Sichuan University, Chengdu, 610041, Sichuan, China

    Maozhu Liu, Yangjuan Bai, Yamei Li, Yuangao Zou, Yunfei An & Xinhua Dai

  2. Department of Pharmacy, West China Hospital, Sichuan University, Chengdu, 610041, Sichuan, China

    Maozhu Liu

  3. West China School of Basic Medical Science & Forensic Medicine, Sichuan University, Chengdu, 610041, Sichuan, China

    Fei Fan

  4. West China School of Public Health and West China Fourth Hospital, Sichuan University, Chengdu, 610041, Sichuan, China

    Jing Zhang

  5. School of Forensic Medicine, Wannan Medical College, Wuhu, 241002, Anhui, China

    Shiyong Fang

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  1. Maozhu Liu
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Contributions

Xinhua Dai: Conceptualization; methodology; investigation; writing, original draft; writing, review and editing; funding acquisition. Maozhu Liu: Investigation, formal analysis, data curation, writing—original draft. Fei Fan: Investigation, data curation. Jing Zhang: Investigation. Shiyong Fang: Investigation. Yangjuan Bai: Methodology, validation. Yamei Li: Methodology, validation. Yuangao Zou: Methodology, validation. Yunfei An: Methodology, validation. All authors reviewed and approved the final manuscript.

Corresponding author

Correspondence to Xinhua Dai.

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Ethical approval and consent to participate

This study protocol was approved by the Medical Ethics Committee of West China Hospital of Sichuan University (register number: 2022-1832) and West China Fourth Hospital of Sichuan University (register number: HXSY-EC-2022103). All subjects who provided plasma samples signed informed consent.

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The authors declare no competing interests.

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Liu, M., Fan, F., Zhang, J. et al. Simultaneous determination of diquat, paraquat, glufosinate, and glyphosate in plasma by liquid chromatography/tandem mass spectrometry: from method development to clinical application. Anal Bioanal Chem 416, 3073–3083 (2024). https://doi.org/10.1007/s00216-024-05257-1

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