Study on Impact Factors of Affecting Liquid-liquid Extraction Efficiency of 12 Nonylphenol Isomers
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摘要: 壬基酚是一种新型持久性有机污染物，具有强烈的雌激素效应。近年来壬基酚对水体的污染备受国内外关注，因此实现水体中壬基酚的提取显得尤为重要。目前国内外对于壬基酚萃取效率的研究都是针对总量，对单独异构体萃取效率的研究极少。本文选用传统的液液萃取方法对壬基酚同分异构体进行提取，并进行GC-MS测试，对影响12种壬基酚同分异构体萃取效率的因素进行研究。通过实验比较不同萃取溶剂、萃取溶剂不同用量、不同盐度、不同pH条件下12种壬基酚同分异构体的回收率，研究优化了液液萃取壬基酚的条件。结果表明，选择二氯甲烷作为萃取溶剂，且用量为60 mL，调节水样 pH<1，氯化钠用量为60 g时，12种壬基酚同分异构体的萃取效率达到88.7%~101.2%，精密度（RSD，n=3）为10.3%~13.6%，检出限9.0~41.4 ng/L。该萃取效率能够达到USEPA规定的回收率在70%~130%范围内，已用于水样中壬基酚的提取。Abstract: Nonylphenol(NP) which has a strong estrogenic effect, is an emerging persistent organic pollutant (POPs). In recent years, NP has caused widespread attention for its pollution in water at home and abroad. Hence, the extraction of NP in water samples is particularly important. However, the study about extraction efficiency of NP was aimed at the total amount, and single isomers were seldom studied. Liquid-liquid extraction, as the most traditional and easiest method for NP's extraction, was chosen in this study for its simple and cheap equipment. Factors which affect the extraction efficiency of 12 NP isomers were studied by Gas Chromatography-Mass Spectrometry (GC-MS). To improve the extraction efficiency of NP, factors such as the type and dosage of extraction solvent, dosage of NaCl and sample's pH were optimized. Results show that the extraction efficiency of 12 isomers was highest when 60 mL methylene chloride was selected as the extraction agent, and pH<1 and 60 g NaCl was added in the water samples. The extraction rates for 12 NP isomers were in the range 88.7%-101.2% with RSDs (n=3) of 10.3%-13.6% and detection limits of 9.0-41.4 ng/L. The optimized method for 12 NP isomers can achieve an expected extraction effect within 70%-130% by USEPA, and has been used successfully for the extraction of NP in water samples.
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Key words:
- nonylphenol isomers /
- liquid-liquid extraction /
- extraction efficiency /
- influence factor
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表 1 12种壬基酚同分异构体的线性回归方程和相关系数
Table 1. Linear regression equations and correlation coefficients of the 12 isomers
壬基酚异构体 回归方程 相关系数R2 NP1 y=3.19×10-2x-2.97×10-2 0.996 NP2 y=1.10×10-1x-1.22×10-1 0.995 NP3 y=4.94×10-2x-5.29×10-2 0.996 NP4 y=3.42×10-2x-2.91×10-2 0.997 NP5 y=8.21×10-2x-7.86×10-2 0.999 NP6 y=3.63×10-2x-2.78×10-2 0.998 NP7 y=4.90×10-2x-4.53×10-2 0.996 NP8 y=1.93×10-2x-1.57×10-2 0.996 NP9 y=4.98×10-2x-4.02×10-2 0.997 NP10 y=2.11×10-2x-1.33×10-2 0.999 NP11 y=1.45×10-2x-1.19×10-2 0.997 NP12 y=6.55×10-2x-4.62×10-2 0.996 注：y表示壬基酚丰度/内标丰度；x表示壬基酚浓度/内标浓度(500 μg/L)。 
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表 2 方法精密度及回收率
Table 2. Precision and recovery tests of the method
壬基酚浓度(μg/L) 各同分异构体空白加标回收率(%) 各同分异构体相对标准偏差(%) 0.3 69.4～125.5 3.8～14 0.5 83.6～129.0 0.72～13 2 70.7～80.4 0.82～5.2 6 82.7～87.3 0.61～2.2
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表 3 方法检出限
Table 3. Detection limits of the method
壬基酚异构体 平均回收率(%) 标准偏差(ng/L) 方法检出限(ng/L) NP1 88.9 2.2 10.2 NP2 104.0 5.6 25.7 NP3 111.2 9.0 41.4 NP4 77.8 2.3 10.7 NP5 83.9 2.6 12.0 NP6 65.7 5.7 26.4 NP7 86.8 2.6 11.9 NP8 86.3 2.0 9.0 NP9 82.8 2.8 12.7 NP10 67.6 3.0 13.7 NP11 81.1 4.8 22.2 NP12 78.5 3.3 15.2
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表 4 大兴再生水灌区壬基酚含量
Table 4. Concentrations of 12 NP isomers in reclaimed water irrigation area in Daxing, Beijing
壬基酚异构体 含量(ng/L) 回收率(%) 北野场RSD(%) 小红门污水厂 黄村污水厂 新凤河 北野场 北野场平行 实验室空白 NP1 58.2 40.7 79.2 49.7 38.7 ND 73.2 17.6 NP2 34.6 18.4 212.3 68.0 63.7 ND 85.7 4.6 NP3 92.1 74.0 340.6 130.0 93.9 ND 83.7 22.6 NP4 75.7 41.0 142.5 59.5 50.4 ND 93.9 11.6 NP5 14.4 ND 106.4 33.7 32.7 ND 90.8 2.1 NP6 65.4 36.5 114.4 67.9 58.1 ND 98.2 11.0 NP7 66.5 42.1 221.6 62.7 56.0 ND 85.1 7.9 NP8 73.4 31.9 80.8 64.0 51.4 ND 80.9 15.4 NP9 119.0 53.4 177.0 83.5 70.5 ND 90.3 11.9 NP10 107.0 53.0 109.1 73.2 52.8 ND 82.8 23.0 NP11 60.5 26.8 288.4 93.9 88.7 ND 85.4 4.1 NP12 78.3 35.0 195.3 63.2 58.8 ND 93.4 5.1 注：ND表示未检出。
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