Simultaneous determination of urinary dialkylphosphate metabolites of organophosphorus pesticides using gas chromatography-mass spectrometry
Simultaneous determination of urinary dialkylphosphate metabolites of organophosphorus pesticides using gas chromatography-mass spectrometry
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DOI：
10.1016/j.jchromb.2005.12.030
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发表时间：
2006-02-17
影响因子：
3
通讯作者：
Takagi, K
中科院分区：
文献类型：
--
作者：
Ueyama, J;Saito, I;Takagi, K
本研究采用五氟苯溴化（PFBBr）衍生化和气相色谱-质谱联用（GC-MS）技术，建立了一种安全、灵敏的同时测定尿中二烷基磷酸盐（DAPs）、有机磷杀虫剂（OPs）代谢物，包括二甲基磷酸盐（DMP）、二乙基磷酸盐（DEP）、二甲基硫代磷酸盐（DMTP）和二乙基硫代磷酸盐（DETP）的方法。考察了几个参数：蒸发时的pH值、衍生化反应的温度和时间、抗氧化剂的使用以及清理步骤。pH为6，用K2CO3调节，反应温度为80℃，衍生化时间为30 min。选择二亚硫酸钠作为抗氧化剂。清理步骤使用Florisil/PSE迷你柱进行，以去除未反应的PFBBr和样品基质。这一建立的程序显著缩短了样品制备时间，仅约3小时，并完全抑制了二烷基硫代磷酸盐的不必要的氧化。在5 mL人尿中，DMP的检出限（LOD）约为0.3 μ g/L， DEP、DMTP和DETP的检出限约为0.1 μ g/L。在1-300 μ g/L的校准范围内，本方法的系列内和日间不精密度小于20.6%，DMP的平均回收率为56.7-60.5%，DEP为78.5-82.7%，DMTP为88.3-103.9%，DETP为84.2-92.4%。该方法检测了有和没有职业暴露于OPs的日本人尿液DAPs的几何平均值，DMP为16.6或27.4，DEP为1.0或0.7，DMTP为1.3或2.3,1.0或1。DETP分别是1mu g/l。本方法除GC-MS外不需要特殊设备，具有快速、安全、灵敏等特点，可用于OPs非职业及职业暴露的常规生物监测。(c) 2006 Elsevier B.V.版权所有
In this study, we developed a safe and sensitive method for the simultaneous determination of urinary dialkylphosphates (DAPs), metabolites of organophosphorus insecticides (OPs), including dimethylphosphate (DMP), diethylphosphate (DEP), dimethylthiophosphate (DMTP), and diethylthiophosphate (DETP), using a pentafluorobenzylbromide (PFBBr) derivatization and gas chromatography-mass spectrometry (GC-MS). Several parameters were investigated: pH on evaporation, reaction temperature and time for the derivatization, the use of an antioxidant for preventing oxidation, and a clean-up step. The pH was set at 6, adjusted with K2CO3, and the reaction temperature and time of derivatization were 80 degrees C and 30 min, respectively. Sodium disulfite was chosen as an antioxidant. The clean-up step was performed with a Florisil/PSE mini-column to remove the unreacted PFBBr and sample matrix. This established procedure markedly shortened the sample preparation time to only about 3 h, and completely inhibited the unwanted oxidization of dialkylthiophosphates. The limits of determination (LOD) were approximately 0.3 mu g/L for DMP, and 0.1 mu g/L for DEP, DMTP, and DETP in 5 mL of human urine. Within-series and between-day imprecision for the present method using pooled urine spiked with DAPs was less than 20.6% in the calibration range of 1-300 mu g/L, and the mean recovery was 56.7-60.5% for DMP, 78.5-82.7% for DEP, 88.3-103.9% for DMTP, and 84.2-92.4% for DETP. This method detected geometric mean values of the urinary DAPs in Japanese with and without occupational exposure to OPs, 16.6 or 27.4 for DMP, 1.0 or 0.7 for DEP, 1.3 or 2.3 for DMTP, and 1.0 or 1. 1 mu g/l for DETP, respectively. The present method, which does not require special equipment except for GC-MS, is quick, safe, and sensitive enough to be adopted in routine biological monitoring of non-occupational as well as occupational exposure to OPs. (c) 2006 Elsevier B.V. All rights reserved.