超临界流体萃取技术在农药残留分析中的应用研究
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摘要
超临界流体萃取技术是近年来发展起来的一种新型的分离、纯化技术，主要应用于石油、化工、天然产物、食品、化妆品等领域，目前也逐渐应用于环境保护、高分子化学合成、特种材料的制备以及中药现代化的实践中。1986年，Capriel将该技术首次应用到农药残留分析中并获得了成功，国内对SFE技术在农药残留分析中的应用研究仅见零星报道。该技术具有选择性强、萃取速度快、精密度高、有机溶剂用量少、操作简便等优点，而受到农药分析界的高度重视，但限于仪器设备及其精密度而发展缓慢。本论文利用超临界CO_2精确萃取仪优选出六种杀虫剂(定虫隆、虫酰肼、三氟氯氰菊酯、甲氰菊酯、高效氯氰菊酯、氟氯氰菊酯)的超临界流体萃取条件，并以定虫隆为重点，研究了该技术在残留分析中的应用，进行了探索性方法学研究，获得了一些有价值的结论。
(1)本论文中所采取的萃取效果评价方法适宜于农药成分的超临界流体萃取技术研究，以高效液相色谱法或气相色谱法为定量方法，结合萃取前后处理样品的重量损失，得出总物质萃取率、总物质中农药成分含量以及农药成分萃取率三个定量参数，以此三个指标综合评价萃取条件对萃取效果的影响。
(2)本试验选用硅藻土(Celite)作为干燥剂，它与样品的比例约为1：2，即可达到SFE对样品水分含量的要求。
(3)供试农药的SFE萃取宜采用静态与动态相结合的方式，静态时间均为20min，之后进行动态萃取。
(4)对定虫隆、高效氯氰菊酯和氟氯氰菊酯动态萃取的三个因素：压力、温度和CO_2流量设计了三因素五水平正交试验，对虫酰肼、三氟氯氰菊酯和甲氰菊酯设计了五因素四水平正交试验(五因素为：温度、压力、CO_2流量、改性剂添加量和静态萃取时间)，分别得出了影响供试农药成分的较优萃取条件；确定了适宜的改性剂及其添加量。
(5)收集溶剂的选择试验证明，对定虫隆及四种拟除虫菊酯类农药宜用甲醇作为收集溶剂；虫酰肼宜用丙酮作为收集溶剂。
(6)以SFE作为农残分析样品前处理技术，其灵敏度、准确度及精密度均符合农药残留对样品前处理的要求。
(7)SFE与常规萃取方法相比较，SFE萃取在1h左右可完成萃取过程，而传统方法则需2d；且SFE中有机溶剂用量仅约为传统方法用量的十分之一。
Supercritical fluid extraction(SFE) is a new developed technique for extraction .separation and purification. As a pre-treatment of sample, SFE offers better precision, shorter analysis time, and a reduction of solvent usage comparing with traditional extraction methods. SFE were mainly used in the fields of oil, chemical engineering, natural products, food, cosmetics etc. Recently it had been used in environmental protection, macromolecular chemical synthesis, as well as the preparation of special material. In 1986,Capriel successfully put SFE into the practice of pesticide residue analysis. Application of SFE on pesticide residue analysis was seldom studied in China. In this paper the extraction conditions of chlorfluazuron, tebufenozide, cyhalothrin, fenpropathrin, cypermethrin, cyfluthrin and the application of SFE on pesticide residue analysis using chlorfluazuron were studied. In our experiments we did some methodology researches, drew some useful conclusions and accumulated some experience.
1. The evaluate methods of extraction efficiency applied in this paper have been proved to be suitable to the research of SFE on pesticides. The quantitative methods were HPLC or GC. According to three indexes to evaluate extraction efficiency(namely: extraction ratio of gross compounds, content of pesticide in gross compounds, recovery of pesticide).
2. Celite was used as drying agent, the ratio of Celite and matrix was 1: 2.
3. The pattern of SFE was the connection of static and dynamic extraction. Of all the six pesticides, suitable static time was 20min and then followed by dynamic extraction.
4. The orthogonal design were conducted with 3 factors and Slevels for chlorfluazuron, cypermethrin, cyfluthrin (the factors were pressure, temperature and volume of CO2) .As to tebufenozide, cyhalothrin and fenpropathrin, orthogonal design were conducted with 5 factors and 41evels(the factors were pressure, temperature, volume of CO2, doses of modifier and static time). The most important factors were respectively obtained. The optimum extraction conditions of six pesticides were determined. To the three indexes of chlorfluazuron, temperature was the most remarkable factors. Modified with methonal(0.08ml/g(nlatrjx))was suitable to the extraction of chlorfluazuron. The trapping solvent was methonal. In a general, the extraction conditions of chlorfluazuron were: pressure 3000PSI,temperature 75 ,volume of CO2 50ml,doses of modifier0.08ml/g(matrix) and static time 20min. The optimum extraction conditions of tebufenozide were: pressure 7000PSI,temperature 60 ,volume of CO21 Oml,doses of modifier 0.
04ml/g(matrjx) and static time 20min,the trapping solvent was acetone. The optimum extraction conditions of
cyhalothrin and fenpropathrin were: pressure 5000PSI,temperature 45 ,volume of CO2 25ml,doses of modifier 0.04ml/g(matriX) and static time 20min. The optimum extraction conditions of cypermethrin and cyfluthrin were: pressure 4000PSI,temperature 65 ,volume of CO2 10ml,doses of modifier 0.05ml/g(matrix) and static time 20min and pressure 6000PSI,temperature 45,volume of CO2 30ml,doses of modifier 0.075ml/g(matrjx) and static time 20min.
5. The choice of trapping solvent depends on the physical-chemical properties of compounds. The experiments showed the suitable trapping solvent of chlorfluazuron, cyhalothrin, fenpropathrin, cypermethrin and cyfluthrin were methonal, the solvent of tebufenozide was acetone.
The application of SFE on pesticide residue analysis has extensive prospects. Although some conclusions were gained in our work, further research is still needed.
(1)本论文中所采取的萃取效果评价方法适宜于农药成分的超临界流体萃取技术研究，以高效液相色谱法或气相色谱法为定量方法，结合萃取前后处理样品的重量损失，得出总物质萃取率、总物质中农药成分含量以及农药成分萃取率三个定量参数，以此三个指标综合评价萃取条件对萃取效果的影响。
(2)本试验选用硅藻土(Celite)作为干燥剂，它与样品的比例约为1：2，即可达到SFE对样品水分含量的要求。
(3)供试农药的SFE萃取宜采用静态与动态相结合的方式，静态时间均为20min，之后进行动态萃取。
(4)对定虫隆、高效氯氰菊酯和氟氯氰菊酯动态萃取的三个因素：压力、温度和CO_2流量设计了三因素五水平正交试验，对虫酰肼、三氟氯氰菊酯和甲氰菊酯设计了五因素四水平正交试验(五因素为：温度、压力、CO_2流量、改性剂添加量和静态萃取时间)，分别得出了影响供试农药成分的较优萃取条件；确定了适宜的改性剂及其添加量。
(5)收集溶剂的选择试验证明，对定虫隆及四种拟除虫菊酯类农药宜用甲醇作为收集溶剂；虫酰肼宜用丙酮作为收集溶剂。
(6)以SFE作为农残分析样品前处理技术，其灵敏度、准确度及精密度均符合农药残留对样品前处理的要求。
(7)SFE与常规萃取方法相比较，SFE萃取在1h左右可完成萃取过程，而传统方法则需2d；且SFE中有机溶剂用量仅约为传统方法用量的十分之一。
Supercritical fluid extraction(SFE) is a new developed technique for extraction .separation and purification. As a pre-treatment of sample, SFE offers better precision, shorter analysis time, and a reduction of solvent usage comparing with traditional extraction methods. SFE were mainly used in the fields of oil, chemical engineering, natural products, food, cosmetics etc. Recently it had been used in environmental protection, macromolecular chemical synthesis, as well as the preparation of special material. In 1986,Capriel successfully put SFE into the practice of pesticide residue analysis. Application of SFE on pesticide residue analysis was seldom studied in China. In this paper the extraction conditions of chlorfluazuron, tebufenozide, cyhalothrin, fenpropathrin, cypermethrin, cyfluthrin and the application of SFE on pesticide residue analysis using chlorfluazuron were studied. In our experiments we did some methodology researches, drew some useful conclusions and accumulated some experience.
1. The evaluate methods of extraction efficiency applied in this paper have been proved to be suitable to the research of SFE on pesticides. The quantitative methods were HPLC or GC. According to three indexes to evaluate extraction efficiency(namely: extraction ratio of gross compounds, content of pesticide in gross compounds, recovery of pesticide).
2. Celite was used as drying agent, the ratio of Celite and matrix was 1: 2.
3. The pattern of SFE was the connection of static and dynamic extraction. Of all the six pesticides, suitable static time was 20min and then followed by dynamic extraction.
4. The orthogonal design were conducted with 3 factors and Slevels for chlorfluazuron, cypermethrin, cyfluthrin (the factors were pressure, temperature and volume of CO2) .As to tebufenozide, cyhalothrin and fenpropathrin, orthogonal design were conducted with 5 factors and 41evels(the factors were pressure, temperature, volume of CO2, doses of modifier and static time). The most important factors were respectively obtained. The optimum extraction conditions of six pesticides were determined. To the three indexes of chlorfluazuron, temperature was the most remarkable factors. Modified with methonal(0.08ml/g(nlatrjx))was suitable to the extraction of chlorfluazuron. The trapping solvent was methonal. In a general, the extraction conditions of chlorfluazuron were: pressure 3000PSI,temperature 75 ,volume of CO2 50ml,doses of modifier0.08ml/g(matrix) and static time 20min. The optimum extraction conditions of tebufenozide were: pressure 7000PSI,temperature 60 ,volume of CO21 Oml,doses of modifier 0.
04ml/g(matrjx) and static time 20min,the trapping solvent was acetone. The optimum extraction conditions of
cyhalothrin and fenpropathrin were: pressure 5000PSI,temperature 45 ,volume of CO2 25ml,doses of modifier 0.04ml/g(matriX) and static time 20min. The optimum extraction conditions of cypermethrin and cyfluthrin were: pressure 4000PSI,temperature 65 ,volume of CO2 10ml,doses of modifier 0.05ml/g(matrix) and static time 20min and pressure 6000PSI,temperature 45,volume of CO2 30ml,doses of modifier 0.075ml/g(matrjx) and static time 20min.
5. The choice of trapping solvent depends on the physical-chemical properties of compounds. The experiments showed the suitable trapping solvent of chlorfluazuron, cyhalothrin, fenpropathrin, cypermethrin and cyfluthrin were methonal, the solvent of tebufenozide was acetone.
The application of SFE on pesticide residue analysis has extensive prospects. Although some conclusions were gained in our work, further research is still needed.
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132． Sie S. T., Beersum W. van, Rijinders G W. A. Sep .Sci. 1966,1:459
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134． Sie S. T. et al. Sep. Sci. 1967,2:729
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148． Van Welie G S A, Diepen G A M. Rec. Trav. Chem. 1961,80:673
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150． Williams D F. Chem Eng Sci, 1981, (36) :1769
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