Measurement of dialkyl phosphate metabolites of organophosphorus pesticides in human urine using lyophilization with gas chromatography-tandem mass spectrometry and isotope dilution quantification
Measurement of dialkyl phosphate metabolites of organophosphorus pesticides in human urine using lyophilization with gas chromatography-tandem mass spectrometry and isotope dilution quantification
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DOI：
10.1038/sj.jea.7500322
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发表时间：
2004-05-01
期刊：
影响因子：
--
通讯作者：
Barr, DB
中科院分区：
文献类型：
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作者：
Bravo, R;Caltabiano, LM;Barr, DB
尿中磷酸二烷基酯（DAP）代谢产物已被用于估计人体接触有机磷农药。我们开发了一种定量的方法，至少28种有机磷农药的6 DAP尿代谢产物，使用冻干和化学衍生化，然后使用同位素稀释气相色谱-串联质谱（GC-MS/MS）分析。用DAP的稳定同位素类似物掺入尿样，并使用冻干机从样品中除去水。将干燥的残余物溶解在乙腈和乙醚中，并将DAP化学衍生化为它们各自的氯丙基磷酸酯。将氯丙基磷酸酯浓缩，并使用GC-MS/MS进行分析。该方法的检测限在低μ g/l（十亿分之一）至中等pg/ml范围（万亿分之一）内，变异系数为7- 14%。使用稳定的同位素类似物作为这些代谢物中的每一种的内标物允许针对回收率进行样品特异性调整，从而允许高度的准确度和精密度。使用该方法从孕妇和儿童中采集了约1100份尿样，表明该方法的检测限较低，可用于一般人群研究。
Urinary dialkylphosphate (DAP) metabolites have been used to estimate human exposure to organophosphorus pesticides. We developed a method for quantifying the six DAP urinary metabolites of at least 28 organophosphorus pesticides using lyophilization and chemical derivatization followed by analysis using isotope-dilution gas chromatography-tandem mass spectrometry (GC-MS/MS). Urine samples were spiked with stable isotope analogues of the DAPs and the water was removed from the samples using a lyophilizer. The dried residue was dissolved in acetonitrile and diethyl ether, and the DAPs were chemically derivatized to their respective chloropropyl phosphate esters. The chloropropyl phosphate esters were concentrated, and analyzed using GC-MS/MS. The limits of detection of the method were in the low mug/l (parts per billion) to mid pg/ml range (parts per trillion) with coefficients of variation of 7-14%. The use of stable isotope analogues as internal standards for each of these metabolites allows for sample-specific adjustment for recovery and thus permits a high degree of accuracy and precision. Use of this method with approximately 1100 urine samples collected from pregnant women and children indicate that the low limits of detection allow this method to be used in general population studies.