【作者】 范伟；

【导师】 徐溢；

【作者基本信息】 重庆大学 ， 分析化学， 2006， 硕士

【摘要】 本论文针对目前我国农药残留一些常规分析方法中存在的操作过程冗长,使用大量有毒溶剂,不能进行即时检测,对环境和操作人员身体健康构成一定程度威胁等缺陷,在综述国内外农药残留分析检测技术进展情况的基础上,结合农残分析检测的要求,将固相萃取（SPE）前处理技术与高效液相色谱（HPLC）检测技术相结合,以Florisil为填料自制了SPE小柱,建立检测阿维菌素残留的SPE-HPLC方法。结果表明,该方法满足农残分析检测的要求,克服了液液萃取技术及一般柱层析的缺点,试验过程简单、溶剂省、重现性好、回收率高、耗费时间少,并减少了杂质的引入,且易于操作,经济适用。同时,利用建立的SPE-HPLC方法对田间阿维菌素的残留动态进行了分析研究,具有较强的实际意义和应用价值。本研究以Florisil为填料自制了SPE小柱,对土壤和甘蓝样品中的阿维菌素进行了提取、净化等前处理,并选取添加浓度为0.05mg/kg的土壤为对象,与SPE商品柱的柱效作了对比,自制SPE小柱的平均回收率89.94%,略高于SPE商品柱的平均回收率89.24%;使用SPE小柱相对标准偏差1.82%,略低于SPE商品柱的2.73%,结果表明自制SPE柱的柱效与SPE商品柱的柱效相当,且自制SPE柱更为经济实用。以N-甲基咪唑和三氟醋酸酐为衍生剂生成阿维菌素衍生物,对衍生化反应条件进行了比较选择,并针对阿维菌素衍生物可以发射荧光的性质,用荧光检测器代替了常用的紫外检测器,排除了土壤、甘蓝样品中复杂物质的干扰,提高了检测的灵敏度和选择性,最低检出浓度为0.001mg/kg,在10-200μL/mL线性范围内标准曲线的相关系数为0.999。通过3个浓度的添加实验,对SPE-HPLC方法的可行性进行了验证,回收率和相对标准偏差均满足农残分析检测的要求,方法可行。在此基础上,以建立的SPE-HPLC方法对田间土壤和甘蓝中阿维菌素的残留动态作了研究分析,结果表明,阿维菌素在甘蓝上随着时间的变化逐渐减少,24h后几乎不能检出,高施药区甘蓝上阿维菌素的降解速度初期较低施药区快,后期则两者相当。高施药区的降解动态方程为Ct=1006.30e^-0.24X,半衰期为2.8h,低施药区的降解动态方程为Ct=461.64e^-0.24X,半衰期为2.9h;阿维菌素在土壤中随着时间的变化逐渐减少,12h后几乎不能检出。更多还原

【Abstract】 In this research, a novel chromatographic analysis method is established to analyze pesticide residua by combining solid-phase extraction technology（SPE）with high performance liquid chromatography（HPLC）,aiming to overcome the defect in general method in pesticide residue analysis such as: solvent toxicity, bio-hazard, which is proved to meet the basic demand of pesticide residua analysis and possesses high recovery rate, less-time cost, good repeatability and feasibility. Meanwhile ,study on dynamically controlling rudimental of avermyctins in field soil and broccoli is performed by using SPE-HPLC method, the results obtained indicates that this method is practical and effective for instructing the field application of avermyctins .In this thesis, positive SPE column, filling with Florisil, is firstly prepared, The chromatographic performance of the pre-treated soil sample and broccoli is studied in detail by SPE-HPLC method and compared with that of the commercial SPE sample. The average recovery rate and the variation coefficient is 89.24%、89.94% and 2.73% 1.82% respectively, It is indicated that column-efficiency is approximately equal, however, the homemade SPE-column is more superior on economy. Avermyctins derivative is synthesized from trifluoroacetic anhydride and N-methylimida zole. Spectroscopic analysis is applied to determine avermyctins derivative to expel the interfere of the impurity in the soil sample and the broccoli, the detectable limit reaches 0.001mg/kg, the linearity range of avermyctins stand curve is from 10ng/mL to 200 ng/mL and the correlate coefficient is 0.999. The feasibility of the SPE-HPLC method is validated by standard appending 0.005mg/kg, 0.05mg/kg and 0.1 mg/kg respectively, in this way, when the concentration is 0.005mg/kg, the recovery rate is between 81.12% and 103.28%, correlation coefficient is between 6.33% and 7.61%; when the concentration is 0.05mg/kg, the recovery is between 84.56% and 100.37%, correlation coefficient is 2.46% to 4.65%; and when the concentration is 0.1mg/kg, the recovery is 87.98% to 104.14%, correlation coefficient is 2.90% to 4.33%, all the test data are meet the rudimental pesticide analytical demand. Based on those experiment results, the SPE-HPLC method is set up to dynamically analyze rudimental avermyctins in soil and broccoli. The result showed that the digest dynamic equation and half-life of avermyctins in broccoli are Ct=1006.30e^-0.24X、2.8h , Ct=461.64e^-0.24X、2.9h , respectively under the condition of avermyctins is 13.5g/hm2 and 27g/hm² in broccoli.更多还原