【作者】 林建；

【导师】 吴加伦；

【作者基本信息】 浙江大学 ， 农药学， 2010， 硕士

【摘要】 杭白芍和白术是我国传统的治疗保健用药,其中杭白芍具有平肝止痛、养血调经、敛阴止汗等功效,白术具有健脾益气、燥湿利水、安胎等功效。随着市场需求量的增加,两味中药材种植面积逐年扩大。锈病、灰霉病、根腐病等在杭白芍和白术上危害严重,需要使用化学农药进行防治。本文对防治以上病害的常用农药多菌灵和三唑酮在杭白芍、白术上的消解动态和残留行为进行了研究,为建立农药的安全使用标准提供科学依据。本文建立了用高效液相色谱仪(HPLC)分析杭白芍、白术及土壤中农药多菌灵残留的方法,以及用气相色谱仪分析杭白芍、白术及土壤中农药三唑酮的方法。多菌灵以甲醇和0.2 mol/L盐酸(v:v=90:10)混合液提取,浓缩后调pH值至7.0-7.5,加入二氯甲烷液液分配萃取,浓缩、定容,最后采用紫外-可见光检测器测定。该方法条件下对多菌灵的最小检出量为0.05 ng,新鲜植物组织和土壤中最低检出浓度均为0.0125 mg/kg,平均回收率为77.6%～97.6%,变异系数为1.14～3.24%;三唑酮检测以丙酮提取,二氯甲烷液液分配,弗罗里硅土柱层析净化,石油醚和乙酸乙酯(v:v=90:10)淋洗,浓缩、定容,最后用气相色谱ECD检测器测定。该方法条件下对三唑酮的最小检出量为0.01 ng,新鲜植物组织和土壤中最低检出浓度为0.0025 mg/kg,平均回收率为78.9%～97.1%,变异系数为1.17～2.90%。多菌灵、三唑酮在室内三档恒定温度下的残留动态试验结果表明,温度越高,农药在土壤中的降解越快。在30℃、20℃、10℃条件下,多菌灵在新渥土壤中的半衰期分别为7.22 d、15.93 d、22.35 d,三唑酮在新渥土壤中的降解半衰期为8.84 d、11.00 d、18.63 d。多菌灵、三唑酮农药在田间的两年两地残留试验结果表明,多菌灵在杭白芍土壤中的半衰期为6.51～7.98 d,在杭白芍中的消解半衰期为4.51～6.50 d;三唑酮在杭白芍土壤中的半衰期为5.26～8.56 d,在杭白芍中的消解半衰期为5.16～7.87 d。多菌灵在白术土壤中的半衰期为7.45～9.04 d,在白术中的消解半衰期为5.02～7.01 d;三唑酮在白术土壤中的半衰期为6.55～11.43 d,在白术中的消解半衰期为6.00～7.53 d。多菌灵以两种剂量施药(675 g a.i./hm~2和1000 g a.i./hm~2)30 d后,其在杭白芍中的残留量均低于0.1 mg/kg,在白术上的残留量低于0.2mg/kg;三唑酮以推荐剂量施药30 d后,杭白芍和白术上的残留量均低于0.1mg/kg,以1.5倍推荐剂量施药30 d,白竹乡白术中残留量为0.1319 mg/kg(超过0.1 mg/kg),其余均低于0.1 mg/kg。初加工后多菌灵在杭白芍和白术干样中的残留量为0.0468～0.2518 mg/kg,三唑酮在杭白芍和白术干样中的残留量为0.0552～0.1883 mg/kg。若暂定多菌灵在杭白芍、白术上的MRL值为0.3 mg/kg,三唑酮在杭白芍白术上的MRL值分别为0.2 mg/kg,多菌灵以推荐用药量675 ga.i./hm~2施药,建议在两种药材中最后一次施药与收获的安全间隔期暂定为21 d,三唑酮以推荐用药量60 g a.i./hm~2,建议最后一次施药与收获的安全间隔期为30d。本研究研究了多菌灵、三唑酮这两种农药在浙江省杭白芍主生产区(磐安县新渥镇和大盘镇)及白术主生产区(磐安县新渥镇和缙云县白竹乡)实际使用过程中,在环境土壤和取食部位的农药残留情况,结合室内土壤残留试验降解数据,对多菌灵、三唑酮在杭白芍和白术上的MRL和安全使用间隔期提出了建议。同时也为中药材安全使用标准的制定提供了参考依据。更多还原

【Abstract】 A simple, rapid residue analytical method of carbendazim and triadimefon in White paeony , Large-head Atractylodes and their cultivated soil was developed. The residues of carbendazim were extracted from samples with a methanol and 0.2 M hydrochloric mixture (V:V=90:10), concentrated extracts, regulated the pH to 7.0-7.5 with 2.0 M NaOH, extracted three times with 40ml methylene dichloride and determined by HPLC with a ultraviolet absorption detector. The detectable limit of HPLC estimated for carbendazim is 0.05 ng, and the minimum detectable concentration is 0.0125 mg/kg. The fortified recoveries of carbendazim in analytical samples were in range of 77.6%～97.6%, with relative standard deviations of 1.14～3.24%.The residues of triadimefon were extracted from samples with acetone ,the extracts were cleaned up by liquid-liquid extraction with dichloromethane and florisil column, determined by GC using capillary column equipped with a electron capture detector. The detectable limit of GC-ECD estimated for triadimefon is 0.01 ng, and the minimum detectable concentration is 0.0025 mg/kg. The fortified recoveries of triadimefon in analytical samples were in range of 78.9%～97.1%, with relative standard deviations of 1.17～2.90%.According to the result of residue test under the control condition of 30, 20,10℃, degrading speed of carbendazim and triadimefon in soil were related to the temperature. The higher the temperature was, the higher degrading speed was. The half lives of carbendazim in Xinwo soil were 7.22(30℃), 15.93(20℃), 22.35(10℃) days respectively. The half lives of triadimefon in Xinwo soil were 8.84(30℃), 11.00(20℃), 18.63(10℃) days respectively.Results of field test showed that the half lives of carbendazim were 4.51～6.50 days and 6.51～7.98 days in White paeony and cultivated soil, and were 5.02～7.01 days and 7.45～9.04 days in Large-head Atractylodes and cultivated soil respectively. The half lives of triadimefon were 5.16～7.87 days and 5.26～8.56 days in White paeony and cultivated soil, and were 6.00～7.53 days and 6.55～11.43 days in Large-head Atractylodes and cultivated soil respectively. It is 30 days that the carbendazim residue in White paeony was degraded below 0.1 mg/kg in two dosage (675 g a.i./hm~2 and 1000 g a.i./hm~2) treated trials, and below 0.2 mg/kg in Large-head Atractylodes. It is 30 days that the triadimefon residue was degraded below 0.1 mg/kg in 60 g a.i./hm~2 treated trials. But the residues of triadimefon in Large-head Atractylodes (Baizhu town) were 0.1319 mg/kg in 60 g a.i./hm~2 treated trials. If 0.3mg/kg is recommended as the MRL of carbendazim in White paeony and Large-head Atractylodes, and 0.2 mg/kg as the MRL of carbendazim in White paeony and Large-head Atractylodes, the pre-harvest interval (PHI) of carbendazim in White paeony and Large-head Atractylodes is 21 days for the 675 g a.i./hm~2 treatment, and PHI of triadimefon is 30 days for the 60 g a.i./hm~2 treatment, respectively.更多还原