【作者】 李洋；

【导师】 操海群；

【作者基本信息】 安徽农业大学 ， 农药学， 2015， 硕士

【摘要】 建立了甲氰菊酯、高效氯氟氰菊酯、高效氯氰菊酯和氰戊菊酯等4种拟除虫菊酯杀虫剂在枸杞、甘草、金银花、菊花等4种药茶及其茶汤中的多残留分析方法,研究了在不同浸泡条件下,供试拟除虫菊酯杀虫剂从药茶向茶汤转移的规律;探讨了拟除虫菊酯类杀虫剂在药茶浸泡过程中浸出率差异的原因;并以枸杞为例,开展了拟除虫菊酯类杀虫剂残留在饮茶过程中的安全性评价。主要实验结果如下:1.枸杞、甘草、菊花、金银花及其茶汤中拟除虫菊酯类杀虫剂多残留分析方法的建立枸杞、甘草、菊花和金银花等药茶样品均用乙腈为提取溶剂,机械震荡方式提取,Florisil SPE小柱净化;药茶的茶汤样品由二氯甲烷萃取,GC-ECD检测。添加回收实验结果表明:在0.01~0.5 mg·kg-1(药茶)和0.002~0.2 mg·kg-1(茶汤)的添加浓度范围内,甲氰菊酯、高效氯氟氰菊酯、高效氯氰菊酯和氰戊菊酯4种拟除虫菊酯类杀虫剂在药茶中平均添加回收率分别为84.5%~101.6%、84.5%~110.5%、80.2%~94.7和84.3%~103.5%,变异系数分别为4.33%~10.22%、5.22%~9.21%、5.32%~11.23%和2.31%~10.11%;在茶汤中的品均回收率分别为80.85%~112.44%、89.4%~110.40%、81.4%~115.4%和80.2%~113.5%,变异系数分别为3.03%~8.48%、5.03%~10.50%、4.43%~11.03%和4.23%~9.42%;方法的准确性、灵敏度和精确性均满足农药残留分析的要求。2.枸杞中供试拟除虫菊酯类杀虫剂在浸泡过程中的转移规律研究了浸泡次数、浸泡时间、浸泡温度和茶水比等不同浸泡条件对枸杞中4种拟除虫菊酯类杀虫剂浸出率的影响。结果表明,供试农药浸出率随着浸泡次数的增加而显著降低,前2次浸出率分别占总浸出率的85.75%、79.55%、81.65%和81.19%。供试农药的浸出率随着浸泡时间(2min~30min)的增加而显著增加,分别达到4.28%、2.59%、3.69%和3.42%。但是浸泡时间超过20min时,浸出率趋于平稳或微弱减小。供试农药的浸出率随着浸泡温度的增加而增加,4种供试农药的浸出率在100°C(沸水)时达到最高,分别为4.21%、2.72%、3.84%和3.51%。供试农药的浸出率随着茶水比的减小(1:30~1:100)而增加,茶水比为1:100时,4种供试农药的浸出率分别为4.57%、3.18%、4.41%和3.18%。3.甘草中供试拟除虫菊酯类杀虫剂在浸泡过程中的转移规律研究了浸泡次数、浸泡时间、浸泡温度和茶水比等不同浸泡条件对甘草中4种拟除虫菊酯类杀虫剂浸出率的影响。结果表明,供试农药浸出率随着浸泡次数的增加而显著降低,前2次浸出率分别占总浸出率的85.90%、100%、88.41%和84.32%。供试农药的浸出率随着浸泡时间(2min~30min)的增加而显著增加,分别达到3.32%、1.7%、2.91%和2.48%。但是浸泡时间超过20min时,浸出率趋于平稳或微弱减小。供试农药的浸出率随着浸泡温度的增加而增加,4种供试农药的浸出率在100°c(沸水)时达到最高,分别为3.25%、1.45%、2.65%和2.43%。供试农药的浸出率随着茶水比的减小(1:30~1:100)而增加,茶水比为1:100时,4种供试农药的浸出率分别为3.39%、2.01%、3.08%和3.11%。4.金银花中供试拟除虫菊酯类杀虫剂在浸泡过程中的转移规律研究了浸泡次数、浸泡时间、浸泡温度和茶水比等不同浸泡条件对甘草中4种拟除虫菊酯类杀虫剂浸出率的影响。结果表明,供试农药浸出率随着浸泡次数的增加而显著降低,前2次浸出率分别占总浸出率的100%、83.86%、100%和100%。供试农药的浸出率随着浸泡时间(2min~30min)的增加而显著增加,分别达到5.81%、3.65%、5.34%和5.04%但是浸泡时间超过20min时,浸出率趋于平稳或微弱减小。供试农药的浸出率随着浸泡温度的增加而增加,4种供试农药的浸出率在100°c(沸水)时达到最高,分别为5.81%、3.65%、5.34%和5.04%。供试农药的浸出率随着茶水比的减小(1:30~1:100)而增加,茶水比为1:100时,4种供试农药的浸出率分别为6.70%、4.03%、5.97%和4.91%。5.菊花花中供试拟除虫菊酯类杀虫剂在浸泡过程中的转移规律研究了浸泡次数、浸泡时间、浸泡温度和茶水比等不同浸泡条件对甘草中4种拟除虫菊酯类杀虫剂浸出率的影响。结果表明,供试农药浸出率随着浸泡次数的增加而显著降低,前2次浸出率分别占总浸出率的89.03%、100%、83.94%和100%。供试农药的浸出率随着浸泡时间(2min~30min)的增加而显著增加,分别达到5.78%、4.02%、5.51%和5.08%。但是浸泡时间超过20min时,浸出率趋于平稳或微弱减小。供试农药的浸出率随着浸泡温度的增加而增加,4种供试农药的浸出率在100°c(沸水)时达到最高,分别为5.43%、3.96%、5.23%和4.87%。供试农药的浸出率随着茶水比的减小(1:30~1:100)而增加,茶水比为1:100时,4种供试农药的浸出率分别为6.30%、3.54%、5.17%和4.28%。6.药茶中拟除虫菊酯类杀虫剂浸出率差异的原因分析对比了在茶水比为1:50,浸泡温度为100°c(沸水),浸泡1次,浸泡时间为10min的条件下,不同药茶中4种供试拟除虫菊类酯类杀虫剂的浸出率差异较为显著,其中金银花和菊花中的供试农药浸出率相对较高,而枸杞和甘草中的浸出率较低。这可能与药茶中果胶、淀粉和蛋白质含量差异有关。对于不同供试农药而言,在相同浸泡条件下,4种药茶中的浸出率均表现出甲氰菊酯>高效氯氰菊酯>氰戊菊酯>高效氯氰菊酯。通过比较供试农药的水溶解度(ws)以及辛醇-水分配系数(kow)发现,不同农药浸出率与上述两个参数存在明显相关性。分别以log1/ws的值和logkow值为横坐标,浸出率值为纵坐标,绘制线性曲线图得出4种药茶中Log1/Ws与浸出率的关系式分别为y=-0.2545x+4.4937、y=-0.2581x+3.5664、y=-0.3174x+6.4587和y=-0.2887x+6.2645,相关系数R2均大于0.96。与浸出率的关系分为分别为:y=-1.2504x+11.021、y=-1.2822x+10.274、y=-1.4404x+13.807和y=-1.6078x+14.901,相关系数R2均大于0.97,其中y代表浸出率,x分别代表Log1/Ws和Log Kow。7拟除虫菊酯类杀虫剂残留在饮茶过程中的安全性评价以枸杞为例,参考王运浩等人提出的茶叶中农药定量安全性评价体系,对枸杞中4种拟除虫菊酯杀虫剂残留在饮用过程中进行了安全性评价。根据供试农药的MRL值和实验所得供试农药在枸杞中的最大浸出率,算出每日可通过饮茶进入人体的最大摄入量,与ADI值计算出安全系数。甲氰菊酯、高效氯氟氰菊酯、高效氯氰菊酯和氰戊菊酯的安全性系数分别为179、198、13400和1378,枸杞中拟除虫菊酯类杀虫剂残留通过饮茶方式对人体健康的风险较小,安全性高。更多还原

【Abstract】 The multi-residue analytical method of pyrethroid insecticides on some herbs(Lycium barbarum L,Glycyrrhiza uralensis,Lonicera japonica and Dendranthema morifolium)was set up.In order to investigate dissipation behaviour of Fenpropathrin,Beta-cypermethrin,Lambda-cyhalothrin and Fenvalerate during the infusion process.The resons for difference transfer of pyrethroid insecticides has be Studied;and safety evaluation of pyrethroid insecticides in Lycium barbarum L tea was reported.The main results are as follows.1 The multi-residue analytical method for pyrethroid insecticides in 4 herbal teas and their infusion.The herbal teas samples were extracted with acetonitrile by mechanical shaking and cleaned up by Florisil SPE.The cooled infusion extract was subjected to partitioning with dichloromethane.All the samples were detected by GC-ECD.As the fortified concentration were 0.01~0.5mg·kg-1(herbal teas)and 0.002~0.2 mg·kg-1(infusion),the average recoveries of Fenpropathrin,Beta-cypermethrin,Lambda-cyhalothrin and Fenvalerate in the herbal teas were ranged between 80.2%~110.5%,the coefficient of variation were 2.31%~11.23%;The average recoveries in infusion were ranged between 80.2%~115.4%,the coefficient of variation were 3.03%~ 11.03%.These results showed that the accuracy and sensitivity of themethod meet the requirement of pesticide residue analysis.2 Influence on the transfer of from Lycium barbarum L to infusion in different soaking conditions.The transfer of pyrethroid insecticides from Lycium barbarum L teas to infusion in different soaking conditions(tea/water ratio,infusing times,infusing duraion,and infusing temperature)was studied.The result shows that: the transfer of the 4 pyrethroid insecticides decreased significantly with the increasing of soak times,the transfer of two previous respectively accounted for 85.75%,79.55%,81.65% and 81.19%.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing duration,4.28%,2.59%,3.69% and 3.42%,the transfer rate remain stable or decrease slightly after 20 minutes.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing temperature,the transfer rate were respectively 4.21%,2.72%,3.84% and 3.51% at 100 °C the transfer of the 4 pyrethroid insecticides increased with the decreaseing of the tea/waterratio(1:30-1:100).The maximum transfer rates were respectively 4.57%、3.18%、4.41% and 3.18%.3 Influence on the transfer of pesticides from Glycyrrhiza uralensis teas to infusion in different soaking conditions.The transfer of pyrethroid insecticides from Glycyrrhiza uralensis teas to infusion in different soaking conditions(tea/water ratio,infusing times,infusing duraion,and infusing temperature)was studied.The result shows that: the transfer of the 4 pyrethroid insecticides decreased significantly with the increasing of soak times,the transfer of two previous respectively accounted for 85.90%,100%,88.41% and 84.32%.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing duration,The maximum transfer rates were respectively 3.32%,1.7%,2.91% and2.48%,the transfer rate remain stable or decrease slightly after 20 minutes.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing temperature,the transfer rate were respectively 3.25%,1.45%,2.65% and 2.43% at100°C The transfer of the 4 pyrethroid insecticides increased with the decreaseing of the tea/water ratio(1:30-1:100).The maximum transfer rates were respectively 3.39%,2.01%,3.08% and 3.11%.4 Influence on the transfer of pesticides from lonicera japonica to infusion in different soaking conditions.The transfer of pyrethroid insecticides from lonicera japonica teas to infusion in different soaking conditions(tea/water ratio,infusing times,infusing duraion,and infusing temperature)was studied.The result shows that: the transfer of the 4 pyrethroid insecticides decreased significantly with the increasing of soak times,the transfer of two previous respectively accounted for 100%,83.86%,100% and 100%.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing duration,4.28%,2.59%,3.69% and 3.42%,the transfer rate remain stable or decrease slightly after 20 minutes.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing temperature,the transfer rate were respectively 4.21%,2.72%,3.84% and 3.51% at 100°C the transfer of the 4 pyrethroid insecticides increased with the decreaseing of the tea/waterratio(1:30-1:100).The maximum transfer rates were respectively 6.70%,4.03%,5.97% and 4.91%.5 Influence on the transfer of pesticides from Dendranthema morifolium to infusion in different soaking conditions.The transfer of pyrethroid insecticides from Dendranthema morifolium teas to infusion in different soaking conditions(tea/water ratio,infusing times,infusing duraion,and infusing temperature)was studied.The result shows that: the transfer of the4 pyrethroid insecticides decreased significantly with the increasing of soak times,the transfer of two previous respectively accounted for 89.03%,100%,83.94% and 100%.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing duration,5.78%,4.02%,5.51% and 5.08%,the transfer rate remain stable or decrease slightly after 20 minutes.The transfer of 4 pyrethroid insecticides increases with the increasing of the infusing temperature,the transfer rate were respectively 5.43%,3.96%,5.23% and 4.87% at 100°C the transfer of the 4 pyrethroid insecticides increased with the decreaseing of the tea/waterratio(1:30-1:100).The maximum transfer rates were respectively 6.30%,3.54%,5.17% and 4.28%.6 The difference transfer of pyrethroid insecticides in herbal teasThe transfer of pyrethroid insecticides at same infusing conditions(1 time,100°C,10 min,1:50)in different herbal teas was compared.There were significant differences between the 4 herbal teas,the transfer of pyrethroid insecticides in lonicera japonica and Dendranthema morifolium is higher than transfer in Lycium barbarum L and Glycyrrhiza uralensis.The transfer rates of the 4 pyrethroid insecticides were also compared.The transfer rates of the 4 from largest to smallest were Fenpropathrin,Lambda-cyhalothrin,Fenvalerate and Beta-cypermethrin.The similar trend was found in the water solubility(Ws)and Octanol-water partition coefficient(Kow)of the 4 pyrethroid insecticides.The Log1/Ws and Log were considered as abscissa,and the transfer rates were considered as ordinate.The linear equations between Log1/Ws with the transfer rates is respectively y=-0.2545x+4.4937,y=-0.2581x+3.5664,y =-0.3174x+ 6.4587 and y =-0.2887 x + 6.2645,correlation coefficients were higher than 0.96.The linear equations between Log Kow with the transfer rates is respectively y=-1.2504x+11.021,y=-1.2822x+10.274,y=-1.4404x+13.807 and y=-1.6078x+14.901,correlation coefficients were higher than 0.97.7 Safety evaluations of pyrethroid insecticides residues in herbal teasLycium barbarum L,for instance the afety evaluations of pyrethroid insecticides residues was given according to the safety evaluation system were made by Wang Yunhao,et al.The safety factors of the 4 pyrethroid insecticides are respectively 179,198,13400 and 1378.更多还原