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代森联及乙撑硫脲在柑橘园中的残留降解行为及其毒性作用研究
Study on the Residue Behavior of Metiram and ETU in Orangery and Its Toxicity Effects
【作者】 罗敏;
【导师】 郭正元;
【作者基本信息】 湖南农业大学 , 环境科学, 2010, 硕士
【摘要】 代森联是一种优良的保护性杀菌剂。代森联70%水分散性粒剂,商品名称为“品润”。近年来,品润在我国特别是在南方各省区得到了广泛的使用,以前对其的研究主要集中在其对果菜病害的防治,而对其残留降解行为和毒性作用的研究甚少。本论文通过设计田间试验,研究了代森联及其主要代谢物乙撑硫脲在柑橘园中的残留降解行为。通过实验室模拟,研究了控制条件下,代森联70%水分散性粒剂对三叶浮萍和泥鳅的毒性效应,及乙撑硫脲对水蚤的毒性作用。主要研究结果如下:(1)代森联在柑橘及橘园土壤中的残留分析方法采用顶空气相色谱法。样品中的代森联在加热的密闭顶空瓶中,遇HCl/SnCl2时,消化反应生成二硫化碳气体,用气相色谱法测定二硫化碳的量,代表代森联农药的残留量。经测定,代森联的最小检出量为1.9×10-10g,代森联在柑橘及橘园土壤中的最低检测限:橘皮为0.06mg/kg,橘肉为0.05mg/kg,全果为0.05mg/kg,橘园土壤为0.06mg/kg。当添加水平为0.5-5.0 mg/kg时,代森联在橘皮、橘肉、全果和橘园土壤中的平均回收率分别为86.15%-96.95%,86.28%-101.97%,81.61%-91.89%,88.90%-106.26%,变异系数分别为5.38%-7.62%,4.19%-8.02%,2.36%-6.19%,5.28%-9.64%,该分析方法的准确性、精确性以及灵敏度均达到了农药残留分析的技术要求。(2)建立了乙撑硫脲在柑橘及橘园土壤中的残留分析方法。样品中乙撑硫脲采用甲醇提取,经弗罗里硅土和中性氧化铝的混合物柱净化,选定液相色谱(HPLC)的紫外检测器对其进行测定。乙撑硫脲的最小检测量为1.2×10-l0g。乙撑硫脲在柑橘及橘园土壤中的最低检出限:橘皮、橘肉为0.01 mg/kg,全果为0.009mg/kg,橘园土壤为0.008 mg/kg。当添加水平为0.1-2.0mg/kg时,乙撑硫脲在橘皮、橘肉、全果和橘园土壤中的平均回收率分别为91.35%-98.04%、91.98%-94.66%,83.85%-88.56%、87.55%-93.71%,变异系数分别为3.87%-5.17%、4.17%-5.23%,1.98%-5.38%、4.15%-5.48%,该分析方法的准确性、精确性以及灵敏度均达到了农药残留分析的技术要求。(3)对代森联及其主要代谢物乙撑硫脲在湖南、浙江和贵州三地柑橘园中的残留降解行为进行了两年的研究。结果表明:代森联及其主要代谢物乙撑硫脲随外界环境的变化,其残留降解规律也会发生变化。其中,2007年代森联在湖南和浙江两地橘园土壤中的半衰期分别为27.61d、7.16d;在柑橘全果中的半衰期分别为9.55d、8.39d;2008年代森联在湖南和贵州两地橘园土壤中的半衰期分别为11.53d、14.94d。在柑橘全果中的半衰期分别为11.23d、7.63d。试验结果表明:代森联在橘园中消解较快。代森联在柑橘及橘园土壤中的残留量与施药量和施药次数等因素有关,一般而言,施药量越大、施药次数越多,代森联在柑橘及橘园土壤中的残留量也越高。取样时间,特别是距最后一次施药后的取样时间的长短与代森联在柑橘及橘园土壤中的残留量呈正相关,即取样时间越短,残留量越高。此外,湖南、浙江、贵州两年的橘皮、橘肉、全果和土壤中均未检出乙撑硫脲残留。(4)分别采用静态试验法和半静态试验法研究了代森联70%水分散性粒剂对三叶浮萍和泥鳅的毒性作用。通过实验,得出代森联70%水分散性粒剂对三叶浮萍的24,48,72和96 h的半数抑制浓度(IC50)分别为11.75,4.31,3.29和2.67mg/L,品润对三叶浮萍的生长作用表现为明显的“低(浓度)促高(浓度)抑”或“长(作用时间)抑短(作用时间)促”的毒性效应。24,48,72和96h代森联70%水分散性粒剂对泥鳅的半致死浓度(LC50)分别为100.26,29.29,19.63和15.14 mg/L,安全浓度(SC)为0.2190mg/L,结果表明,代森联70%水分散性粒剂对泥鳅为高毒级。(5)采用48h静态试验法研究了乙撑硫脲(ETU)对水蚤的毒性作用。通过实验,得出ETU对水蚤的24、48 h的半数运动受抑制浓度(EC50)分别为1.14、0.64g/L,ETU对水蚤的24、48 h的半数致死浓度(LC50)分别为344.49、3.49 g/L,安全浓度(SC)为10.62mg/L。结果表明,ETU对水蚤为微毒级。
【Abstract】 Metiram belongs to a great prophylactic synthetic fungicide. The soluble granulated material which includes 70% metiram, its trade name is Pinrun. In recent years, Pinrun was widespread used in our country,specially in the south area. Previous studies focused mainly on its prevention and cure to the diseases of fruit and vegetable plants, little information was available about its residue behavior and the toxicity effects. In order to provide some fundamental data for assessing the environment safety and scientific application, the degradation of metiram and ETU in orangery, the toxicity effects of ETU on Daphnia magna, the toxicity effects of Pinrun on Lemna paucicostata and Misgurnus anguillicadatus were studied, under control conditions by simulating methods in laboratory. The main results were follows:Firstly, The gas chromatograph analysis method was used as the residue analysis method for metiram in orange and soil. Samples containing metiram were placed in hemetic vials and heated. The metiram reacted with HCl/SnCl2 and Produced CS2. The solution of CS2 was then analysed by gas chromatograph. The amount of CS2 was a scale of metiram residues on various media, what was accepted for describing the residue magnitude of metiram worldwide. After detecting, it was showed that the minimum detectable amount of metiram was 1.9×10-10g. Furthermore, the lowest detectable concentrations of metiram in the orange skins, the orange meat, the entire fruit and the orangery soil were 0.06mg/kg,0.05mg/kg,0.05mg/kg and 0.06mg/kg, respectively. When the added amount of metiram is changed from 0.5 to 5.0 mg/kg in sample, the average recoveries of the metriam on the orange skins, the orange meat, the entire fruit and the orangery soil were changed from 86.15% to 96.95%,86.28% to 101.97%,81.61% to 91.89% and 88.90% to 106.26%, respectively. The coefficient of variations were changed from 5.38% to 7.62%,4.19% to 8.02%, 2.36% to 6.19% and 5.28% to 9.64%, respectively. The method validation data well fitted the analytical criterion for pesticide residue.Secondly, the residue analysis methods for ethylenethiourea (ETU) in orange and soil were established. The ETU residues in samples were extracted by methanol. Then the extract was purified by a chromography column which was filed with the mix-material of aluminum oxide and florisil. For determination of ETU in samples, a HPLC with UV detector was use. After detecting, it was showed that the minimum detectable amount of ETU was 1.2×10-10g. Furthermore, the lowest detectable concentrations of ETU in the orange skins, the orange meat, the entire fruit and the orangery soil were O.Olmg/kg, O.Olmg/kg, 0.009mg/kg and 0.008mg/kg, respectively. When the added amount of ETU is changed from 0.1 to 2.0 mg/kg in samples, the average recoveries of the ETU on the orange skins, the orange meat, the entire fruit and the orangery soil were changed from 91.35% to 98.04%,91.98% to 94.66%,83.85% to 88.56% and 87.55% to 93.71%, respectively. The coefficient of variations were changed from 3.87% to 5.17%,4.17% to 5.23%,1.98% to 5.38% and 4.15% to 5.48%, respectively. The method validation data well fitted the analytical criterion for pesticide residue.Tirdly, the reside decline behaviors of Metiram and ETU were studied in orangery in Hunan, Zhejiang and Guizhou province for two years. And the results revealed that the decline rules of Metiram and ETU changed as well as the exterior surroundings changed. In year 2007, the decline half-lives of Metiram in soil planted orange in Hunan and Zhejiang were 27.61 days and 7.16 days, respectively. The decline half-lives of Metiram in orange in Hunan and Zhejiang were 9.55 days and 8.39 days, respectively. In year 2008, the decline half-lives of Metiram in soil planted orange in Hunan and Guizhou were 11.53 days and 14.94 days, respectively. The decline half-lives of Metiram in orange in Hunan and Guizhou were 11.23 days and 7.63 days, respectively. It was showed that the decline of Mentiram in orangery was pretty quick. Also, the residue amount of Metiram depends on many factors such as the sprinkling quantity and times. Normally, the residue amounts of Metiram in both soil and orange were higher at a great and frequent sprinkling quantity. Then for the sampling time, the residue amount obviously represents a direct correlation with the time interval between sampling and sprinkling. That is to say:the shorter the interval, the higher the residue amount. In addition, it was detected that the ETU residue amount could hardly be found in whole samples.Fourthly, static and half static experiments were performed to study the toxicity effects of Pinrun on Lemna paucicostata and Misgurnus anguillicadatus. The results showed that IC50 value influenced by Pinrun unden different tested time (24,48,72 and 96h) were 11.75,4.31,3.29 and 2.67mg/L. The low concentration or the short duration of action promoted the growth of Lemna paucicostata, and the high concentration or long duration of action inhibited its growth. The results also showed that LC50 value influenced by Pinrun unden different tested time (24,48,72 and 96h)were 100.26,29.29,19.63 and 15.14 mg/L, the safe concentration(SC) was 0.2190mg/L. The toxicity rank of Pinrun on Misgurnus anguillicadatus was high.Fifthly, static experiment was performed to study the toxicity effects of ETU on Daphnia magna. The results-showed that EC50 value influenced by ETU unden different tested time (24 and 48h) were 1.14,0.64g/L. LC50 value influenced by ETU unden different tested time (24 and 48h) were 344.49,3.49g/L,the safe concentration(SC) was 10.62mg/L.The toxicity rank of ETU on Daphnia magna was weak.
【Key words】 Metiram; Ethylenethiourea; Orangery; Residue Behavior; Aquatic organism; Toxicity;
- 【网络出版投稿人】 湖南农业大学 【网络出版年期】2011年 04期
- 【分类号】X592
- 【被引频次】6
- 【下载频次】391