Simultaneous determination of paraquat and diquat in human plasma by HPLC-DAD: Its application in acute poisoning patients induced by these two herbicides

Guiyan Yuan, Rong Li, Qi Zhao, Xianglin Kong, Yanyan Wang, Xiaojing Wang, Ruichen Guo, Guiyan Yuan, Rong Li, Qi Zhao, Xianglin Kong, Yanyan Wang, Xiaojing Wang, Ruichen Guo

Abstract

Background: Paraquat and diquat are widely used in agricultural production in many countries, which are very toxic to human beings. Paraquat can be detected in some diquat solution sold in the market. The blood concentration of paraquat or diquat is an important indicator for clinical diagnosis of paraquat or diquat poisoning. So, it is very meaningful to develop a method for simultaneous determination of paraquat and diquat in human plasma.

Objective: To develop and validate a HPLC-DAD method for simultaneous determination of paraquat and diquat in human plasma and to apply it in the acute poisoning patients by these two herbicides.

Methods: Paraquat and diquat were simultaneously determined by HPLC-DAD. The plasma was treated using Waters OASIS® Column and then separated on a Thermo Hypersil GOLD (250 × 4.6 mm, 5 μm) Column with the mobile phase consisted of 75 mmol/L sodium heptane sulfonate (containing 0.1 mol/L phosphoric acid, pH 3.0) and acetonitrile (87:13, v:v) at a flow rate of 1.0 mL/min. The full-wavelength scanning was 200-400 nm, and the detection wavelength of paraquat and diquat was 257nm and 310nm, respectively. 120 and 30 plasma samples from patients with paraquat and diquat poisoning were collected and analyzed by the established method.

Results: The standard curve for paraquat and diquat ranged from 0.05 to 20 μg/mL, and the precision of LLOQ for paraquat was 16.49%, which was required to be less than 20%. The precision of other concentrations was less than 14.14%. The recovery of paraquat and diquat was 95.38%-103.97% and 94.79%-98.40%, respectively. The results showed that paraquat and diquat were stable under various storage conditions. 120 plasma samples of paraquat poisoning patients and 30 plasma samples of diquat poisoning patients were determined by the established method. The blood concentration of paraquat ranged from 0.10 to 20.62 μg/mL, with an average of 3.61 μg/mL, while for diquat, the concentration ranged from 0 to 26.59 μg/mL, with an average of 2.00 μg/mL. Among the diquat suspected poisoning samples, 5 samples were detected not only diquat but also paraquat, and 2 samples were detected only paraquat, no diquat.

Conclusion: The HPLC-DAD method established in this study was high throughput, high sensitivity, simple operation, and wide linear ranges. It can be used for the screening analysis and quantitative detection of paraquat and diquat in acute poisoning patients, which can provide basis for the treatment and prognosis of these two herbicides poisoning patients.

Keywords: Diquat; Paraquat; acute poisoning patients; high-performance liquid chromatography; simultaneous determination.

© 2020 The Authors. Journal of Clinical Laboratory Analysis Published by Wiley Periodicals, LLC.

Figures

Figure 1
Figure 1
The typical chromatograms of blank plasma (A‐1, A‐2), standard solution of paraquat and diquat (B‐1, B‐2), and blank plasma spiked with paraquat and diquat (C‐1, C‐2). Note: (A‐1), (A‐2), and (A‐3) were specific chromatograms of paraquat at 257 nm, while (B‐1), (B‐2), and (B‐3) were specific chromatograms of diquat at 310 nm
Figure 2
Figure 2
The chromatograms of paraquat and diquat in paraquat (A) or diquat (B) poisoning samples, and both paraquat and diquat in the same suspected diquat poisoning sample (C)

References

    1. Saeed SA, Wilks MF, Coupe M. Acute diquat poisoning with intracerebral bleeding. Postgrad Med J. 2001;77:329‐332.
    1. Ballard KD, Vickery WE, Nguyen LT, et al. An analytical strategy for quaternary ammonium neuromuscular blocking agents in a forensic setting using LC‐MS/MS on a tandem quadrupole/time‐of‐flight instrument. J Am Soc Mass Spectrom. 2006;17:1457‐1468.
    1. Pateiro‐Moure M, Arias‐Estévez M, Simal‐Gándara J. Critical review on the environmental fate of quaternary ammonium herbicides in soils devoted to vineyards. Environ Sci Technol. 2013;47:4984‐4998.
    1. Baselt RC. Disposition of Toxic Drugs and Chemicals in Man, 5th edn. California: Chemical Toxicology Institute; 2000.
    1. Dinis‐Oliveira RJ, Sarmento A, Reis P, et al. Acute paraquat poisoning: report of a survival case following intake of a potential lethal dose. Pediatr Emerg Care. 2006;22:537‐540.
    1. Tan JT, Letchuman Ramanathan G, Choy MP, et al. Paraquat poisoning: experience in hospital taiping (year 2008‐october 2011). Med J Malaysia. 2013;68:384‐388.
    1. Sun L, Li GQ, Yan PB, et al. Prediction of outcome following paraquat poisoning by arterial lactate concentration‐time data. Exp Ther Med. 2014;8:652‐656.
    1. Seok SJ, Kim YH, Gil HW, et al. The time between paraquat ingestion and a negative dithionite urine test in an independent risk factor for death and organ failure in acute paraquat intoxication. J Korean Med Sci. 2012;27:993‐998.
    1. Wang KC, Chen SM, Hsu JF, et al. Simultaneous detection and quantitation of highly water‐soluble herbicides in serum using ion‐pair liquid chromatography‐tandem mass spectrometry. J Chromatogr B Analyt Technol Biomed Life Sci. 2008;876:211‐218.
    1. Ariffin MM, Anderson RA. LC/MS/MS analysis of quaternary ammonium drugs and herbicides in whole blood. J Chromatogr B Analyt Technol Biomed Life Sci. 2006;842:91‐97.
    1. Ruan XL, Qiu JJ, Wu C, et al. Magnetic single‐walled carbon nanotubes‐dispersive solid‐phase extraction method combined with liquid chromatography‐tandem mass spectrometry for the determination of paraquat in urine. J Chromatogr B Analyt Technol Biomed Life Sci. 2014;965:85‐90.
    1. Yue XJ, Li W, Li PF. Determination of paraquat in plasma by HPLC‐MS/MS. Lab Med. 2018;33:132‐138. (Article in Chinese).

Source: PubMed

Sponsors and Collaborators

Medical Conditions

Drug Interventions

3
Subscribe