A liquid chromatography-tandem mass spectrometry multiresidue method for quantification of specific metabolites of organophosphorus pesticides, synthetic pyrethroids, selected herbicides, and DEET in human urine
A liquid chromatography-tandem mass spectrometry multiresidue method for quantification of specific metabolites of organophosphorus pesticides, synthetic pyrethroids, selected herbicides, and DEET in human urine
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DOI：
10.1021/ac0355404
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发表时间：
2004-05-01
影响因子：
7.4
通讯作者：
Barr, DB
中科院分区：
文献类型：
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作者：
Olsson, AO;Baker, SE;Barr, DB
流行病学研究中经常需要能够估计人体低剂量接触常用农药的能力。因此，需要快速、稳健的方法来测量同一样品中的多种分析物。我们开发了一种对人体尿液中 19 种常用农药标记物进行高通量分析的方法。分析物包括七种有机磷农药的特定代谢物、五种合成拟除虫菊酯的代谢物、六种除草剂或其代谢物以及一种驱虫剂。人尿 (2 mL) 中加入稳定同位素标记的分析物类似物，进行酶水解，使用固相萃取进行萃取，浓缩，并使用高效液相色谱-串联质谱进行分析。将样品分为两部分，并在两种不同的质谱仪上进行分析，一种使用大气压化学电离 (APCI)，另一种使用涡轮离子喷雾大气压电离 (US)。除拟除虫菊酯代谢物外的所有分析物均使用 APCI 进行分析。所有分析物的检测限范围为 0.1 至 1.5 ng/mL 尿液，其中大多数 (17) 低于 0.5 ng/mL。不同分析物的分析精度（按日内和日间变化估计）分别为 3-14% 和 4-19%。分析物的萃取回收率为 68% 至 114%。包括校准标准品和质量控制样品在内的吞吐量相当于每天 50 个样品。然而，TIS 应用程序的分析时间要短得多，并且如果仅对拟除虫菊酯代谢物数据感兴趣，则吞吐量可以增加至 100-150 个样本/天。
The ability to estimate low-dose human exposure to commonly used pesticides often is requested in epidemiologic studies. Therefore, fast and robust methods are necessary that can measure many analytes in the same sample. We have developed a method for high-throughput analysis of 19 markers of commonly used pesticides in human urine. The analytes were seven specific metabolites of organophosphorus pesticides, five metabolites of synthetic pyrethroids, six herbicides or their metabolites, and one insect repellant. Human urine (2 mL) was spiked with stable isotopically labeled analogues of the analytes, enzymatically hydrolyzed, extracted using solid-phase extraction, concentrated, and analyzed using high-performance liquid chromatography-tandem mass spectrometry. The sample was divided into two portions and analyzed on two different mass spectrometers, one using atmospheric pressure chemical ionization (APCI) and the other using turbo ion spray atmospheric pressure ionization (US). All analytes except the pyrethroid metabolites were analyzed using APCI. The detection limits for all analytes ranged from 0.1 to 1.5 ng/mL of urine, with the majority (17) below 0.5 ng/mL. The analytical precision for the different analytes, estimated as both the within-day and between-day variation, was 3-14 and 4-19%, respectively. The extraction recoveries of the analytes ranged from 68 to 114%. The throughput, including calibration standards and quality control samples, is similar to50 samples a day. However, the analysis time with the TIS application is much shorter, and if only pyrethroid metabolite data are of interest, the throughput can be increased to 100-150 samples/day.