Pesticide Chemistry and Toxicology Laboratory, Department of Agricultural Biotechnology and Research Institute of Agriculture and Life Sciences, Seoul National University, Seoul, 08826, Republic of Korea.
Pesticide Chemistry and Toxicology Laboratory, Department of Agricultural Biotechnology and Research Institute of Agriculture and Life Sciences, Seoul National University, Seoul, 08826, Republic of Korea.
Chemosphere. 2022 Dec;309(Pt 1):136725. doi: 10.1016/j.chemosphere.2022.136725. Epub 2022 Oct 5.
Simultaneous multiresidual pesticide analysis of saliva samples was performed using scaled-down QuEChERS extraction with LC-MS/MS and GC-MS/MS. The optimum extraction procedure using acidified acetonitrile was applicable to 336 pesticides (287 for LC-MS/MS and 49 for GC-MS/MS). To determine pesticide multiresidues in saliva, 100 μL of the sample was extracted with 200 μL of 0.1% formic acid in acetonitrile, and the initial extract was partitioned with 40 mg of MgSO and 10 mg of NaCl. The organic supernatants (120 μL) were then mixed with acetonitrile (30 μL) for matrix-matching (4:1, v/v), and the final extract solution was injected into the LC-MS/MS (4 μL) and GC-MS/MS (2 μL) systems. The established analytical method showed a good LOQs between 5 and 25 ng/mL with reliable accuracy/precision values and recovery results (50-140%) for the target pesticides. Under the two different storage conditions, most of the analytes did not undergo chemical changes in the saliva samples, whereas some pesticides were more stable in freeze-thaw processes than those left at room temperature. Biomonitoring of farmers (ten mixers and ten sprayers) was successfully applied using the validated method, and two carbamates (fenobucarb and propamocarb) were determined at trace concentrations (12.5-675.0 ng/mL from 11 positively detected samples).
采用经过缩微处理的 QuEChERS 萃取法，结合 LC-MS/MS 和 GC-MS/MS 技术，对唾液样本中的多种残留农药进行了同步分析。采用酸化乙腈的最佳萃取程序适用于 336 种农药（287 种用于 LC-MS/MS，49 种用于 GC-MS/MS）。为了测定唾液中的农药多残留，用 100 μL 样品与 200 μL 0.1%甲酸乙腈混合，并用 40 mg 硫酸镁和 10 mg 氯化钠进行初始萃取。然后将有机上清液（120 μL）与乙腈（30 μL）混合进行基质匹配（4:1，v/v），最终提取液用 LC-MS/MS（4 μL）和 GC-MS/MS（2 μL）系统进样。所建立的分析方法具有良好的 LOQs（5-25 ng/mL），目标农药的准确度/精密度值和回收率结果（50-140%）可靠。在两种不同的储存条件下，大多数分析物在唾液样本中未发生化学变化，而一些农药在冻融过程中比在室温下更稳定。采用经验证的方法成功地对农民（10 名搅拌机和 10 名喷雾器）进行了生物监测，从 11 个阳性检测样本中检测到两种氨基甲酸酯（丁硫克百威和丙硫克百威），浓度为痕量（12.5-675.0 ng/mL）。
