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目的 建立基于冷冻诱导-液液萃取和超高效液相色谱-串联质谱的快速分析方法，用于测定人尿液中高氯酸盐的含量。方法 尿液样品在加入稳定同位素标记内标后，以乙腈-水(60∶40,V/V)混合液离心，于-40℃静置30 min,取上清液经乙腈10倍稀释，采用Poroshell 120 PFP色谱柱(50 mm×2.1 mm, 1.9μm)分离，甲醇和1%乙酸水溶液梯度洗脱，超高效液相色谱-串联质谱法测定高氯酸盐，并以内标法定量。结果 方法线性关系良好，决定系数R2>0.999,检出限和定量限分别为0.3和1.0μg/L,低、中和高添加水平的平均回收率为101.2%～106.7%,日内和日间相对标准偏差均低于5%(n=6),人尿液标准参考物质(SRM 3668)高氯酸盐的测定结果为(2.75±0.11)和(13.67±0.34)μg/L,均在参考值范围内。对国内243份尿液样品进行测定，高氯酸盐检出率为100%,含量范围为1.91～87.41μg/L,中位数为18.74μg/L。结论 本方法前处理简单，具有检测时间短、高灵敏度、高精密度和高准确度的特点，能够满足大规模人尿液高氯酸盐的检测需求。
Abstract：OBJECTIVE To develop a rapid analytical method based on cold-induced liquid-liquid extraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry(CI-LLE-UPLC-MS/MS) for the determination of perchlorate in human urine.METHODS After spiking urine samples with stable isotope-labeled internal standards, the samples were centrifuged with a mixture of acetonitrile and water(60∶40, V/V) and then kept at-40 ℃ for 30 min. The supernatant was diluted tenfold with acetonitrile and separated on a Poroshell 120 PFP column(50 mm×2.1 mm, 1.9 μm) with a gradient elution of methanol and 1% acetic acid aqueous solution. Perchlorate was quantified by UPLC-MS/MS using the internal standard method.RESULTS The method exhibited good linearity(coefficient of determination R2>0.999), with a detection limit of 0.3 μg/L and a quantification limit of 1.0 μg/L. The average recoveries at low, medium, and high spiked levels were 101.2%-106.7%, and the intra-day and inter-day relative standard deviations were both less than 5%(n=6). The determination result of perchlorate in the human urine standard reference material(SRM 3668) were(2.75±0.11) and(13.67±0.34) μg/L, both within the reference ranges. Analysis of 243 real urine samples from China revealed a 100% detection rate for perchlorate, with concentrations ranging from 1.91 to 87.41 μg/L and a median value of 18.74 μg/L.CONCLUSION The method features simple pretreatment, rapid detection, and high sensitivity, precision, and accuracy, making it suitable for large-scale detection of perchlorate in human urine.
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基本信息:
DOI：10.19813/j.cnki.weishengyanjiu.2026.04.021
中图分类号:O657.63;R114
引用信息:
[1]杨思宇,葛鑫宇,张弛,等.冷冻诱导-液液萃取-超高效液相色谱-串联质谱法测定人尿液中高氯酸盐[J].卫生研究,2026,55(04):669-675.DOI:10.19813/j.cnki.weishengyanjiu.2026.04.021.
基金信息:
国家自然科学基金(No.21976046)
2025-10-14
2025
2026-04-08
2026-04-21
2026
1
2026-07-15
2026-07-15