Tucker S P, Reynolds J M, Wickman D C, Hines C J, Perkins J B
National Institute for Occupational Safety and Health, Cincinnati, Ohio, USA.
Appl Occup Environ Hyg. 2001 Jun;16(6):698-707. doi: 10.1080/10473220116794.
Sampling and analytical methods were developed for commonly used chloroacetanilide, chlorotriazine, and 2,4-D herbicides in hand washes, on dermal patches, and in air. Eight herbicides selected for study were alachlor, atrazine, cyanazine, 2,4-dichlorophenoxyacetic acid (2,4-D), metolachlor, simazine, and two esters of 2,4-D, the 2-butoxyethyl ester (2,4-D, BE) and the 2-ethylhexyl ester (2,4-D, EH). The hand-wash method consisted of shaking the worker's hand in 150 mL of isopropanol in a polyethylene bag for 30 seconds. The dermal-patch method entailed attaching a 10-cm x 10-cm x 0.6-cm polyurethane foam (PUF) patch to the worker for exposure; recovery of the herbicides was achieved by extraction with 40 mL of isopropanol. The air method involved sampling with an OVS-2 tube (which contained an 11-mm quartz fiber filter and two beds of XAD-2 resin) and recovery with 2 mL of 10:90 methanol:methyl t-butyl ether. Analysis of each of the three sample types was performed by gas chromatography with an electron-capture detector. Diazomethane in solution was employed to convert 2,4-D as the free acid to the methyl ester in each of the three methods for ease of gas chromatography. Silicic acid was added to sample solutions to quench excess diazomethane. Limits of detection for all eight herbicides were matrix-dependent and, generally, less than 1 microgram per sample for each matrix. Sampling and analytical methods met NIOSH evaluation criteria for all herbicides in hand-wash samples, for seven herbicides in air samples (all herbicides except cyanazine), and for six herbicides in dermal-patch samples (all herbicides except cyanazine and 2,4-D). Speciation of 2,4-D esters and simultaneous determination of 2,4-D acid were possible without losses of the esters or of other herbicides (acetanilides and triazines) being determined.
针对洗手液、皮肤贴片和空气中常用的氯代乙酰苯胺、氯代三嗪和2,4 - D除草剂，开发了采样和分析方法。选择用于研究的8种除草剂为甲草胺、莠去津、氰草津、2,4 - 二氯苯氧乙酸（2,4 - D）、异丙甲草胺、西玛津以及2,4 - D的两种酯类，即2 - 丁氧基乙酯（2,4 - D，BE）和2 - 乙基己酯（2,4 - D，EH）。洗手方法是将工人的手在装有150 mL异丙醇的聚乙烯袋中摇晃30秒。皮肤贴片方法是将一块10 cm×10 cm×0.6 cm的聚氨酯泡沫（PUF）贴片贴在工人身上进行暴露；通过用40 mL异丙醇萃取来回收除草剂。空气采样方法是用OVS - 2管（其中包含一个11 mm的石英纤维过滤器和两床XAD - 2树脂）进行采样，并用2 mL 10:90的甲醇：甲基叔丁基醚进行回收。通过带有电子捕获检测器的气相色谱法对三种样品类型中的每一种进行分析。在三种方法中，均使用溶液中的重氮甲烷将游离酸形式的2,4 - D转化为甲酯，以便于气相色谱分析。向样品溶液中加入硅酸以淬灭过量的重氮甲烷。所有8种除草剂的检测限取决于基质，通常每种基质的每个样品低于1微克。采样和分析方法符合美国国家职业安全与健康研究所（NIOSH）对洗手液样品中所有除草剂、空气样品中7种除草剂（除氰草津外的所有除草剂）以及皮肤贴片样品中6种除草剂（除氰草津和2,4 - D外的所有除草剂）的评估标准。在不损失所测定的酯类或其他除草剂（乙酰苯胺类和三嗪类）的情况下，可以对2,4 - D酯进行形态分析并同时测定2,4 - D酸。
