Montesano M Angela, Olsson Anders O, Kuklenyik Peter, Needham Larry L, Bradman A S A, Barr Dana B
Centers for Disease Control and Prevention, 4770 Buford Hwy NE, Mailstop F-17, Atlanta, Georgia 30341, USA.
J Expo Sci Environ Epidemiol. 2007 Jul;17(4):321-30. doi: 10.1038/sj.jes.7500550. Epub 2007 Apr 18.
Because of increasing concern about widespread use of insecticides and fungicides, we have developed a highly sensitive analytical method to quantify urine-specific urinary biomarkers of the organophosphorus pesticides acephate, methamidophos, omethoate, dimethoate, and two metabolites from the fungicides alkylenebis-(dithiocarbamate) family: ethylenethiourea and propylenethiourea. The general sample preparation included lyophilization of the urine samples followed by extraction with dichloromethane. The analytical separation was performed by high-performance liquid chromatography (HPLC), and detection by a triple quadrupole mass spectrometer with and atmospheric pressure chemical ionization source in positive ion mode using multiple reaction monitoring and tandem mass spectrometry (MS/MS) analysis. Two different Thermo-Finnigan (San Jose, CA, USA) triple quadrupole mass spectrometers, a TSQ 7,000 and a TSQ Quantum Ultra, were used in these analyses; results are presented comparing the method specifications of these two instruments. Isotopically labeled internal standards were used for three of the analytes. The use of labeled internal standards in combination with HPLC-MS/MS provided a high degree of selectivity and precision. Repeated analysis of urine samples spiked with high, medium and low concentration of the analytes gave relative standard deviations of less than 18%. For all compounds the extraction efficiency ranged between 52% and 63%, relative recoveries were about 100%, and the limits of detection were in the range of 0.001-0.282 ng/ml.
由于人们越来越关注杀虫剂和杀菌剂的广泛使用，我们开发了一种高度灵敏的分析方法，用于定量检测尿液中有机磷农药乙酰甲胺磷、甲胺磷、氧乐果、乐果以及杀菌剂亚烷基双（二硫代氨基甲酸盐）家族的两种代谢物：乙撑硫脲和丙撑硫脲的特定生物标志物。一般的样品制备包括将尿液样品冻干，然后用二氯甲烷萃取。分析分离通过高效液相色谱（HPLC）进行，检测则使用配备大气压化学电离源的三重四极杆质谱仪，在正离子模式下采用多反应监测和串联质谱（MS/MS）分析。在这些分析中使用了两台不同的赛默飞世尔科技（美国加利福尼亚州圣何塞）三重四极杆质谱仪，一台TSQ 7000和一台TSQ Quantum Ultra；文中给出了比较这两台仪器方法规格的结果。三种分析物使用了同位素标记的内标。标记内标与HPLC-MS/MS结合使用提供了高度的选择性和精密度。对添加了高、中、低浓度分析物的尿液样品进行重复分析，相对标准偏差小于18%。对于所有化合物，萃取效率在52%至63%之间，相对回收率约为100%，检测限在0.001 - 0.282 ng/ml范围内。
