葡萄酒中甲霜灵检测方法的研究
摘要
甲霜灵是具保护和治疗作用的低毒杀菌剂,可被植物的根、茎、叶吸收,并随植物体内水份运转而转移到植物的各器官,可以作茎叶处理,种子处理和土壤处理,可以用来防止葡萄的一些病害。在作物上的研究多集中在农药的多残留分析上,我国对甲霜灵在葡萄酒中的残留检测标准方法尚未建立。
本文的研究目的是建立葡萄酒中甲霜灵残留的提取检测方法,研究采用样品经预处理后结合GC/MS的方法对葡萄酒中甲霜灵残留进行检测。主要对液/液萃取(Liquid/liquid extraction, LLE)、加速溶剂萃取(Accelerate solvent extraction, ASE)、固相微萃取(Solid phase microextration, SPME)及固相萃取柱萃取(Solid phase extration, SPE)四种前处理方法的最佳萃取参数、准确度和精确度进行了研究,并建立葡萄汁中的甲霜灵含量的检测方法。通过以上研究,得到了如下结论:
加速溶剂萃取萃取葡萄酒中甲霜灵的最佳参数为:采用正己烷:丙酮=1:1(v:v),提取压力为1200psi,提取温度为50℃,提取时间为10min,循环萃取两次。在确定的条件下,甲霜灵在葡萄酒中回收率为90.50～101.2%,相对标准偏差为1.46～3.28%,最低检出浓度为0.01μg/mL。
溶剂萃取法的最佳参数为:用丙酮和乙酸乙酯混合溶剂提取,方法的检出限高于0.05μg/mL,利用溶剂萃取法检出的甲霜灵回收率为74.0～112.8%,变异系数为1.54～3.58%。
固相萃取法的最佳参数:样品用的二氯甲烷提取,提取液过C18小柱,用25%的丙酮+正己烷过柱,固相萃取法的回收率为79.12～87.2%,变异系数为2.17～4.54%,最低检出浓度>0.05μg/mL。
固相微萃取法不适合葡萄酒中甲霜灵残留的检测。
稳定性试验表明,浓度为4.85μg/mL的甲霜灵的标准溶液(二氯甲烷溶解)在4℃条件下最少可贮存2个月;葡萄酒提取液中甲霜灵浓度在1.0μg/mL时,在-20℃和4℃条件下至少可贮存两周。
本研究建立的葡萄酒中甲霜灵残留检测的标准方法精密度和准确度较高,并且简便、快捷、环保,适合用于我国葡萄酒中甲霜灵残留的检测。
Metaxyl is a low poisonous bactericide which can be absorbed by root, culm and foliage, it can transfer to each apparatus with water in plant and can be used to dispose culm and foliage, seed and soil to prevent some diseases of grape. The residual analytical method of this bactericide is singularly reported, its national standard method has not been established yet.
The purpose of the paper was to set up the standard method for measuring metaxyl in table wine. The paper mainly describes the sample-pretreated methods for analyzing metaxyl in table wines in combination with a gas chromatographic/mass spectrometric (GC/MS) system. Parameters were optimized of the sample-pretreated methods including liquid/liquid extraction, accelerate solvent extraction, solid phase micro extraction and solid/liquid extraction. Furthermore, the method for determining metaxyl in grape juice was established. Following the upward study, the results were as follows:
The optimized parameters of the accelerate solvent extraction of table wine were: hexane:acetone=1:1,pressure was 1200psi,temprature was 50℃,time was 10min,circle was 2 times. Using the established method, the recoveries and the precision of metaxyl were between 90.50～101.2% and 1.46～3.28%,The limits of detection were 0.01μg/mL.
The optimized parameters of the liquid/liquid extraction of table wine were: the wine samples were extracted by acetone and ethyl acetate, the recoveries and the precision of metaxyl were between 74.0～112.8% and 1.54～3.58%,The limits of detection were higher than 0.05μg/mL.
The optimized parameters of the solid phase microextraction of table wine were: the wine samples were extracted by dichloromethane, the extracted liquid passed the C18 columella,the recoveries and the precision of solid phase microextraction were between 79.12～87.2% and 1.54～3.58%,The limits of detection were higher than 0.05μg/mL.
SPME was not fit for extracting metaxyl from wine.
Stability test indicated: The standard solution of metaxyl (diluted with dichloromethane ) at 4.85μg/mL can be stored two months at 4℃;Metaxyl in extract solution of wine can be stored two weeks at 4℃or at -20℃.
The developed standard method of determination of metaxyyl in table wines was simple, fast, reproducible and accurate, and the method could be applicable for routine determination of metaxyl in table wines.
本文的研究目的是建立葡萄酒中甲霜灵残留的提取检测方法,研究采用样品经预处理后结合GC/MS的方法对葡萄酒中甲霜灵残留进行检测。主要对液/液萃取(Liquid/liquid extraction, LLE)、加速溶剂萃取(Accelerate solvent extraction, ASE)、固相微萃取(Solid phase microextration, SPME)及固相萃取柱萃取(Solid phase extration, SPE)四种前处理方法的最佳萃取参数、准确度和精确度进行了研究,并建立葡萄汁中的甲霜灵含量的检测方法。通过以上研究,得到了如下结论:
加速溶剂萃取萃取葡萄酒中甲霜灵的最佳参数为:采用正己烷:丙酮=1:1(v:v),提取压力为1200psi,提取温度为50℃,提取时间为10min,循环萃取两次。在确定的条件下,甲霜灵在葡萄酒中回收率为90.50～101.2%,相对标准偏差为1.46～3.28%,最低检出浓度为0.01μg/mL。
溶剂萃取法的最佳参数为:用丙酮和乙酸乙酯混合溶剂提取,方法的检出限高于0.05μg/mL,利用溶剂萃取法检出的甲霜灵回收率为74.0～112.8%,变异系数为1.54～3.58%。
固相萃取法的最佳参数:样品用的二氯甲烷提取,提取液过C18小柱,用25%的丙酮+正己烷过柱,固相萃取法的回收率为79.12～87.2%,变异系数为2.17～4.54%,最低检出浓度>0.05μg/mL。
固相微萃取法不适合葡萄酒中甲霜灵残留的检测。
稳定性试验表明,浓度为4.85μg/mL的甲霜灵的标准溶液(二氯甲烷溶解)在4℃条件下最少可贮存2个月;葡萄酒提取液中甲霜灵浓度在1.0μg/mL时,在-20℃和4℃条件下至少可贮存两周。
本研究建立的葡萄酒中甲霜灵残留检测的标准方法精密度和准确度较高,并且简便、快捷、环保,适合用于我国葡萄酒中甲霜灵残留的检测。
Metaxyl is a low poisonous bactericide which can be absorbed by root, culm and foliage, it can transfer to each apparatus with water in plant and can be used to dispose culm and foliage, seed and soil to prevent some diseases of grape. The residual analytical method of this bactericide is singularly reported, its national standard method has not been established yet.
The purpose of the paper was to set up the standard method for measuring metaxyl in table wine. The paper mainly describes the sample-pretreated methods for analyzing metaxyl in table wines in combination with a gas chromatographic/mass spectrometric (GC/MS) system. Parameters were optimized of the sample-pretreated methods including liquid/liquid extraction, accelerate solvent extraction, solid phase micro extraction and solid/liquid extraction. Furthermore, the method for determining metaxyl in grape juice was established. Following the upward study, the results were as follows:
The optimized parameters of the accelerate solvent extraction of table wine were: hexane:acetone=1:1,pressure was 1200psi,temprature was 50℃,time was 10min,circle was 2 times. Using the established method, the recoveries and the precision of metaxyl were between 90.50～101.2% and 1.46～3.28%,The limits of detection were 0.01μg/mL.
The optimized parameters of the liquid/liquid extraction of table wine were: the wine samples were extracted by acetone and ethyl acetate, the recoveries and the precision of metaxyl were between 74.0～112.8% and 1.54～3.58%,The limits of detection were higher than 0.05μg/mL.
The optimized parameters of the solid phase microextraction of table wine were: the wine samples were extracted by dichloromethane, the extracted liquid passed the C18 columella,the recoveries and the precision of solid phase microextraction were between 79.12～87.2% and 1.54～3.58%,The limits of detection were higher than 0.05μg/mL.
SPME was not fit for extracting metaxyl from wine.
Stability test indicated: The standard solution of metaxyl (diluted with dichloromethane ) at 4.85μg/mL can be stored two months at 4℃;Metaxyl in extract solution of wine can be stored two weeks at 4℃or at -20℃.
The developed standard method of determination of metaxyyl in table wines was simple, fast, reproducible and accurate, and the method could be applicable for routine determination of metaxyl in table wines.
引文
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