Nishihara Nanami, Isobe Tomohiko, Takagi Mai, Tajima Toshiki, Kitahara Yugo, Hayashi Mai, Saito Isao, Watanabe Satoru, Iwai-Shimada Miyuki, Ueyama Jun
Department of Biomolecular Sciences, Field of Omics Health Sciences, Nagoya University Graduate School of Medicine.
Health and Environmental Risk Division, National Institute for Environmental Studies.
Environ Health Prev Med. 2025;30:18. doi: 10.1265/ehpm.24-00220.
Icaridin and DEET are common insect repellents widely used on human skin and clothing (skin-insect repellents [skin-IR]) to repel common pests, such as mosquitoes and biting flies. Novel analytical methods for urinary skin-IR exposure biomarkers that can be effectively applied in epidemiological studies and provide strong evidence related to risk assessment associated with daily exposure are required. In this study, we aimed to develop a method for analyzing the concentrations of icaridin, DEET, and two DEET metabolites N,N-diethyl-3-(hydroxymethyl) benzamide and 3-(diethylcarbamoyl) benzoic acid in human urine.
In this analysis, after formic acid-induced acidification of the urine sample, exposure biomarkers were extracted using solid-phase extraction composed of a modified polystyrenedivinylbenzene polymer for reversed phase (hydrophobic) retention. Subsequently, high-performance liquid chromatography-tandem mass spectrometry was performed within 10 min for a separation analysis. The present method was applied to five Japanese adults (aged 20-43 years) who used icaridin or DEET-containing products within a week.
Limits of detection were 0.06-0.11 µg/L. Extraction recoveries were 74%-88%. The intraday and interday variations were 1.5-17.5 and 0.9-15.8% relative standard deviation, respectively. All exposure biomarkers were successfully detected in all five adults. Urinary concentrations of exposure biomarkers reached their maximum values within 15 h after starting to use skin-IR.
This method was successful in measuring urinary exposure biomarkers of skin-IR, including icaridin and DEET. Moreover, this study presents the first application of biomonitoring of urinary icaridin concentrations after using a commercial product.
驱蚊酯和避蚊胺是常用的驱虫剂，广泛应用于人体皮肤和衣物（皮肤用驱虫剂[皮肤-IR]），以驱赶常见害虫，如蚊子和叮咬蝇类。需要能够有效应用于流行病学研究并为与日常暴露相关的风险评估提供有力证据的新型尿皮肤-IR暴露生物标志物分析方法。在本研究中，我们旨在开发一种分析人尿中驱蚊酯、避蚊胺以及两种避蚊胺代谢物N,N-二乙基-3-(羟甲基)苯甲酰胺和3-(二乙氨基甲酰基)苯甲酸浓度的方法。
在本分析中，尿液样品经甲酸诱导酸化后，使用由用于反相（疏水）保留的改性聚苯乙烯-二乙烯基苯聚合物组成的固相萃取法提取暴露生物标志物。随后，在10分钟内进行高效液相色谱-串联质谱分析以进行分离分析。本方法应用于五名在一周内使用过含驱蚊酯或避蚊胺产品的日本成年人（年龄20 - 43岁）。
检测限为0.06 - 0.11μg/L。提取回收率为74% - 88%。日内和日间变化的相对标准偏差分别为1.5% - 17.5%和0.9% - 15.8%。在所有五名成年人中均成功检测到所有暴露生物标志物。使用皮肤-IR后15小时内，暴露生物标志物的尿浓度达到最大值。
本方法成功测量了包括驱蚊酯和避蚊胺在内的皮肤-IR的尿暴露生物标志物。此外，本研究首次报道了使用商业产品后尿中驱蚊酯浓度的生物监测应用。
