Determination of Carbofuran and 3-Hydroxycarbofuran in Groundwater by Small Volume Liquid-Liquid Extraction Combined with GC-MS
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摘要:
克百威和3-羟基克百威是一对典型的农药母体及其代谢产物，由于其水溶性高、毒性大，可通过地表水或地下水进行长距离迁移，对人类健康和环境安全造成危害。以往通常采用液相萃取或固相萃取的方式提取样品中的克百威和3-羟基克百威，但这些方法操作繁琐、耗时较长，不利于室内模拟实验中多组样品的检测。为实现克百威与3-羟基克百威在地下水中的快速定量，本文建立了一种小体积液液萃取的前处理方法进行提取，并采用气相色谱-质谱（GC-MS）进行检测，对影响克百威和3-羟基克百威萃取效率的因素进行了研究。通过实验对比不同萃取剂、不同pH、不同离子强度条件下克百威与3-羟基克百威的回收率，优化了前处理条件。结果表明，选择二氯甲烷作为萃取剂且用量为1mL，调节水样pH=5，氯化钠用量为40g/L时克百威和3-羟基克百威的回收率最高，分别为75.1%~98.6%、55.0%~66.3%。性能评价结果显示，方法精密度和方法准确度满足测试要求（相对标准偏差 < 10%，n=5），克百威和3-羟基克百威的方法检出限分别为15.3μg/L、10.2μg/L。该方法操作简便、快速、消耗溶剂少，与传统的液液萃取法相比，本方法耗时约为前者的1/8，消耗溶剂量约比前者小2个数量级，能够满足室内模拟实验需求。
Abstract:BACKGROUND Carbofuran and 3-hydroxycarbofuran are typical pesticides with the relationship of parent and metabolite. Due to high water solubility and toxicity, carbofuran and 3-hydroxycarbofuran can be transported through surface water or groundwater for long distances, causing harm to human health and environmental safety. In the past, carbofuran and 3-hydroxycarbofuran in samples were usually extracted by liquid or solid phase extraction. However, these methods are cumbersome to operate and time-consuming, which is not conducive to the detection of multiple sets of samples in indoor simulation experiments.
OBJECTIVES In order to realize the rapid quantification of carbofuran and 3-hydroxycarbofuran in groundwater.
METHODS A small volume liquid-liquid extraction pretreatment method was established for extraction, combined with gas chromatography-mass spectrometry to detect factors affecting the extraction efficiency of carbofuran and 3-hydroxycarbofuran. To improve the extraction efficiency of carbofuran and 3-hydroxycarbofuran, [JP] factors such as the type of extraction solvent, pH and dosage of NaCl were optimized.
RESULTS Results showed that the extraction efficiency of carbofuran and 3-hydroxycarbofuran was highest when 1mL methylene chloride was selected as the extraction agent under pH=5, and 40g/L NaCl was added in the water samples. The extraction recoveries for carbofuran and 3-hydroxycarbofuran were 75.1%-98.6% and 55.0%-66.3%, respectively. The performance evaluation results showed that the instrument precision and method precision meet test requirements (n=5, relative standard deviation < 10%). The detection limits of carbofuran and 3-hydroxycarbofuran in water were 15.3μg/L and 10.2μg/L, respectively.
CONCLUSIONS This method is simple and fast with less solvent. Compared with the traditional liquid-liquid extraction method, this method takes about 1/8 time of the former, and consumes about two orders of magnitude less solvent than the former, which can meet the needs of indoor simulation experiments.
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表 1 分析物目标离子质量数
Table 1. Characteristic ions for target compounds
化合物 CAS登录号 定量离子 参考离子 克百威 1563-66-2 164 149，122 3-羟基克百威 16655-82-6 137 180，147 苊-d10(IS) 15067-26-2 164 162 2-氟联苯(SS) 321-60-8 172 171 
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表 2 仪器精密度
Table 2. Precision tests of the instrument
目标物质 配制浓度
(μg/L)实测浓度
(μg/L)相对标准偏差
(%)100 79.2±7.3 9.2 克百威 400 394.2±17.1 4.3 800 690.3±15.4 2.2 100 100.0±6.6 6.6 3-羟基克百威 400 419.2±16.9 4.0 800 896.4±20.7 2.3
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表 3 方法准确度
Table 3. Accuracy tests of the method
目标物质 配制浓度
(μg/L)实测浓度
(μg/L)相对标准
偏差(%)回收率
(%)克百威 100 75.4±3.9 5.2 71.1~79.5 800 680.5±20.6 3.0 82.5~88.6 3-羟基克百威 100 43.4±1.4 3.3 41.3~45.9 800 425.3±4.9 1.1 52.7~54.4
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表 4 方法检出限
Table 4. Detection limits of the method
目标物质 配制浓度
(μg/L)实测浓度
(μg/L)相对标准
偏差(%)检出限
(μg/L)克百威 100 81.9±4.9 5.9 15.3 3-羟基克百威 100 42.1±3.3 7.7 10.2
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