Optimization of Pirimicarb and Its Metabolites by Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry
Abstract
Pesticides enhance crop productivity but leave residues that threaten the health and the environment, necessitating sensitive analytical methods to detect widely used compounds like pirimicarb. This study focuses on optimizing the analysis of pirimicarb and its metabolites using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Key instrumental parameters including interface temperature, desolvation line temperature, heat block temperature, column oven temperature, collision-induced dissociation (CID) gas pressure, and interface voltage were systematically optimized to enhance method sensitivity and reliability. Among the tested conditions, interface temperatures of 150 °C and 400 °C provided the highest signal intensity for pirimicarb, while pirimicarb-desmethyl responded best at 250 °C, and pirimicarb-desmethyl-formamido showed maximum signals at 150 °C and 300 °C. For desolvation line temperature, 150 °C yielded the highest intensities for pirimicarb and pirimicarb-desmethyl, whereas 200 °C was optimal for pirimicarb-desmethyl-formamido. Pirimicarb exhibited peak response at a heat block temperature of 300 °C, while pirimicarb-desmethyl showed comparable intensities at 100, 200, and 350 °C, and pirimicarb-desmethyl-formamido responded best at 100 and 200 °C. Column oven temperatures of 40 °C and 50 °C enhanced the response for pirimicarb, with pirimicarb-desmethyl and pirimicarb-desmethyl-formamido showing optimal intensities at 50 °C. Additionally, a CID gas pressure of 270 kPa and interface voltage of 4.0 kV produced the highest ionization efficiency across all analytes. The results demonstrated that specific parameter adjustments significantly improved ionization efficiency and signal intensity, leading to a more robust analytical method. This study underscores the importance of systematic parameter optimization in LC-MS/MS for accurate pesticide residue detection and provides a framework for future research on other pesticide groups.
Keywords
Food safety, LC–MS/MS, method validation, pesticide residue, electrospray ionization
Supporting Institution
Tokat Gaziosmanpaşa University Scientific Research Projects Coordination Unit
Project Number
Grant Project No: 2023/96
References
- O. Tiryaki, R. Canhilal, S. Horuz, The use of pesticides and their risks, Erciyes University Journal of Institue of Science and Technology 26 (2) (2010) 154-169.
- R. J. Hillocks, Farming with fewer pesticides: EU pesticide review and resulting challenges for UK agriculture, Crop Protection 31 (1) (2012) 85-93.
- V. P. Kalyabina, E. N. Esimbekova, K. V. Kopylova, V. A. Kratasyuk, Pesticides: formulants, distribution pathways and effects on human health–a review. Toxicology Reports 8 (2021) 1179-1192.
- A. Sabarwal, K. Kumar, R. P. Singh, Hazardous effects of chemical pesticides on human health–cancer and other associated disorders, Environmental Toxicology and Pharmacology 63 (2018) 103-114.
- T. Balkan, Ö. Yılmaz, Efficacy of some washing solutions for removal of pesticide residues in lettuce, Beni-Suef University Journal of Basic and Applied Sciences 11 (2022) 143.
- Y. A. Mohamed, M. H. Meabed, K. M. Abougaba, F. A. Sayed, N. N. Welson, R. E. Ibrahim, A comparative study: rural versus urban children as regard exposure to organophosphorus pesticides using cholinesterase enzyme activity, Beni-Suef University Journal of Basic and Applied Sciences 11 (2022) 6.
- G. S. Nunes, P. Skládal, H. Yamanaka, D. Barceló, Determination of carbamate residues in crop samples by cholinesterase-based biosensors and chromatographic techniques, Analytica Chimica Acta 362 (1) (1998) 59-68.
- C. Soler, B. Hamilton, A. Furey, K. J. James, J. Mañes, Y. Picó, Optimization of LC–MS/MS using triple quadrupole mass analyzer for the simultaneous analysis of carbosulfan and its main metabolites in oranges, Analytica Chimica Acta 571 (1) (2006) 1-11.
- S. W. Chung, B. T. Chan, Validation and use of a fast sample preparation method and liquid chromatography–tandem mass spectrometry in analysis of ultra-trace levels of 98 organophosphorus pesticide and carbamate residues in a total diet study involving diversified food types, Journal of Chromatography A 1217 (29) (2010) 4815-4824.
- Z. N. Garba, A. K. Abdullahi, A. Haruna, S. A. Gana, Risk assessment and the adsorptive removal of some pesticides from synthetic wastewater: a review, Beni-Suef University Journal of Basic and Applied Sciences 10 (2021) 19.