噁唑酰草胺在水稻及环境中的残留动态及丙溴磷在土壤中的吸附与迁移研究
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摘要
本文建立了高效液相色谱(HPLC)法同时测定水稻田水、土壤、水稻植株、稻米和稻壳中的噁唑酰草胺及其3种代谢物残留量的分析方法,通过两年的田间试验明确了10%噁唑酰草胺乳油在水稻生长初期使用后噁唑酰草胺及其代谢物在水稻植株、稻田土壤和田水中的残留动态、降解规律以及最终残留量,并研究了丙溴磷在不同地区三种土壤中的吸附和迁移规律,主要结论如下：
1.建立了高效液相色谱(HPLC)法同时测定水稻及环境中噁唑酰草胺及其3种代谢物残留量的分析方法。以乙腈和水的混合液作为提取溶剂,硅胶层析柱净化,采用高效液相色谱法以乙腈-水作为流动相,梯度洗脱,紫外检测器224nm检测。结果表明噁唑酰草胺及其3种代谢物HFMPA、HPFMPA、6-CBO在0.5-20mg/L范围内,色谱峰面积与农药浓度呈良好的线性关系,相关系数达0.9993-0.9999,最小检出量分别为0.432ng、0.502ng、0.268ng、0.317ng。4种化合物在土壤、水稻植株、稻米和稻壳中的最低检测浓度均为0.1 mg/kg,在田水中的最低检测浓度为0.02 mg/kg,平均回收率在78.2-106.9%之间,变异系数为2.0-11.7%。该方法能同时提取、净化和检测噁唑酰草胺及其3种代谢物,且重现性好,方法的灵敏度、准确度均能达到农药残留分析的要求,适用于对实际样品中噁唑酰草胺及其代谢物残留量的分析与检测。
2.研究了10%噁唑酰草胺乳油中噁唑酰草胺及其代谢物在水稻植株、稻田土壤和田水中两年的消解动态。结果表明,噁唑酰草胺在稻田水、土壤、水稻植株中的降解过程符合一级动力学方程Ct=Coe"kt。(?)噁唑酰草胺在稻田水、土壤和水稻植株中的消解半衰期分别为3.3-7.4天,9.1-14.3天和1.5-2.2天。而噁唑酰草胺的三种代谢物HFMPA、HPFMPA和6-CBO的残留量很低,并且消长的规律性不明显。
3.根据噁唑酰草胺及其代谢物在水稻上的最终残留试验研究,在水稻生长初期以10%噁唑酰草胺乳油120-240克(有效成分)/公顷施药1次,最后一次施药距采收间隔天数为83-90天,土壤、水稻植株、稻米和稻壳样品中的噁唑酰草胺及其代谢物的残留量均小于最低检测浓度。说明10%噁唑酰草胺乳油按照推荐剂量在水稻生长初期使用,对水稻和环境是安全的。
4.采用气相色谱法建立了丙溴磷在水和土壤中的残留分析方法。以乙腈进行振荡提取,用气相色谱FPD检测器测定。结果表明在0.2-20mg/L范围内,丙溴磷浓度与色谱峰面积呈良好的线性关系,相关系数为0.9999；丙溴磷在水和土壤中的平均回收率在87.2%-103.6%之间,变异系数为4.8%-9.9%；丙溴磷在水中的最低检测浓度为0.005mg/kg,在土壤中的最低检测浓度为0.05mg/kg,符合农药残留分析要求。
5.采用平衡吸附法和薄层层析法研究了丙溴磷在砂土、壤土和粘土中的吸附和迁移特性。结果表明：丙溴磷在砂土、壤土和粘土中的吸附常数Kd分别为12.70、33.65和74.92,土壤对丙溴磷的吸附能力与土壤有机质含量呈正相关,而丙溴磷在3种土壤中的Rf值由大到小的顺序为砂土>壤土>粘土,与Kd值成负相关关系。丙溴磷的移动性分别表现为在砂土、壤土中不易移动,在粘土中不移动。说明了丙溴磷在3种类型土壤中的吸附性和移动性的试验结果相一致。
In this paper, it was studied that the residue analysis of Metamifop and its three major metabolites and the residue dynamics and final residues in rice plant, paddy water, and soil. Under laboratory conditions, the adsorption and mobility of profenofos in three kinds of soils were also studied using batch equilibrium technique and soil thin layer chromatography. The results could be summarized as followings:
1. The high performance liquid chromatographic method was developed for the simultaneous determination of Metamifop and its three major metabolites in rice and environment. Residues were extracted with a mixture of acetonitrile and water, followed by cleanup with a silica gel column, and determinationed by HPLC with a linear gradient elution program of acetonitrile and water as the mobile phase and ultraviolet detection at 224 nm.The results showed that the linear range of Metamifop and its metabolites were from 0.5 to 20mg/L, the correlation coefficients were 0.9993 to 0.9999, the limit of detection were 0.432ng,0.502ng,0.268ng,0.317ng, respectively. The minimum detectable concentration of the 4 analytes in soil, rice straw,rice hulls and unpolished grain samples were all O.lmg/kg, and 0.02mg/kg in paddy water samples.Average recoveries were 78.2 to 106.9%,and the coefficient of variation ranged from 2.0 to 11.7%. Under the same operation condition, good chromatographic separation of the 4 analytes was achieved. The Sensitivity, accuracy and repeatability of the method were fitted for the requirement of pesticide residue analysis and detection, and it was easy to perform in practice.
2. Degradation dynamic of 10% Metamifop EC and its metabolites in rice and environment was studied by a two-year field experiment. The results showed that the degradation procedure of Metamifop in paddy water, soil and rice straw all accorded with the one-level dynamic equation Ct=Coe-kt; the half-life of Metamifop in paddy water, soil and rice straw were 3.3-7.4d,9.1-14.3d and 1.5-2.2d, respectively. The degradation of its three major metabolites (HFMPA, HPFMPA and 6-CBO) was irregular.
3. Terminal residue of Metamifop and its metabolites in rice plant and soil was studied by a two-year field experiment. The results showed that when 10% Metamifop EC was applied at 120-240g.ai/ha one time, and the interval between harvest and the last pesticide application was 83-90 days, the final residual quantities of Metamifop and its three major metabolites in soil, rice straw,rice hulls and unpolished grain samples were both lower than the minimum detectable concentration. And 10% Metamifop EC was safe at this recommended dosage in the early growth of rice.
4. An analytical method for determining Profenofos residues in water and soil by GC was described.The samples were extracted with acetonitrile, detected by GC with FPD detector. The results showed that the linear range of Profenofos was from 0.2 to 20mg/L, the correlation coefficient was 0.9999; the minimum detectable concentration in soil and water samples were 0.05mg/kg,0.005mg/kg, respectively; average recoveries were 87.2 to 103.6%, and the coefficient of variation ranged from 4.8 to 9.9%. The results of test have met the requirement of pesticide residue analysis.
5. The adsorption and mobility of Profenofos in three kinds of soils were studied using batch equilibrium technique and soil thin layer chromatography. The results showed that absorption constant (Kd) of Profenofos in sand,1oam and clay is 12.70, 33.65 and 74.92, respectively. The soil adsorption capacity of Profenofos is positively related with the contents of soil organic matter. The mobility of Profenofos in three soils was shown that Profenofos don't easily move in 1oam and sand, don't move in clay.
1.建立了高效液相色谱(HPLC)法同时测定水稻及环境中噁唑酰草胺及其3种代谢物残留量的分析方法。以乙腈和水的混合液作为提取溶剂,硅胶层析柱净化,采用高效液相色谱法以乙腈-水作为流动相,梯度洗脱,紫外检测器224nm检测。结果表明噁唑酰草胺及其3种代谢物HFMPA、HPFMPA、6-CBO在0.5-20mg/L范围内,色谱峰面积与农药浓度呈良好的线性关系,相关系数达0.9993-0.9999,最小检出量分别为0.432ng、0.502ng、0.268ng、0.317ng。4种化合物在土壤、水稻植株、稻米和稻壳中的最低检测浓度均为0.1 mg/kg,在田水中的最低检测浓度为0.02 mg/kg,平均回收率在78.2-106.9%之间,变异系数为2.0-11.7%。该方法能同时提取、净化和检测噁唑酰草胺及其3种代谢物,且重现性好,方法的灵敏度、准确度均能达到农药残留分析的要求,适用于对实际样品中噁唑酰草胺及其代谢物残留量的分析与检测。
2.研究了10%噁唑酰草胺乳油中噁唑酰草胺及其代谢物在水稻植株、稻田土壤和田水中两年的消解动态。结果表明,噁唑酰草胺在稻田水、土壤、水稻植株中的降解过程符合一级动力学方程Ct=Coe"kt。(?)噁唑酰草胺在稻田水、土壤和水稻植株中的消解半衰期分别为3.3-7.4天,9.1-14.3天和1.5-2.2天。而噁唑酰草胺的三种代谢物HFMPA、HPFMPA和6-CBO的残留量很低,并且消长的规律性不明显。
3.根据噁唑酰草胺及其代谢物在水稻上的最终残留试验研究,在水稻生长初期以10%噁唑酰草胺乳油120-240克(有效成分)/公顷施药1次,最后一次施药距采收间隔天数为83-90天,土壤、水稻植株、稻米和稻壳样品中的噁唑酰草胺及其代谢物的残留量均小于最低检测浓度。说明10%噁唑酰草胺乳油按照推荐剂量在水稻生长初期使用,对水稻和环境是安全的。
4.采用气相色谱法建立了丙溴磷在水和土壤中的残留分析方法。以乙腈进行振荡提取,用气相色谱FPD检测器测定。结果表明在0.2-20mg/L范围内,丙溴磷浓度与色谱峰面积呈良好的线性关系,相关系数为0.9999；丙溴磷在水和土壤中的平均回收率在87.2%-103.6%之间,变异系数为4.8%-9.9%；丙溴磷在水中的最低检测浓度为0.005mg/kg,在土壤中的最低检测浓度为0.05mg/kg,符合农药残留分析要求。
5.采用平衡吸附法和薄层层析法研究了丙溴磷在砂土、壤土和粘土中的吸附和迁移特性。结果表明：丙溴磷在砂土、壤土和粘土中的吸附常数Kd分别为12.70、33.65和74.92,土壤对丙溴磷的吸附能力与土壤有机质含量呈正相关,而丙溴磷在3种土壤中的Rf值由大到小的顺序为砂土>壤土>粘土,与Kd值成负相关关系。丙溴磷的移动性分别表现为在砂土、壤土中不易移动,在粘土中不移动。说明了丙溴磷在3种类型土壤中的吸附性和移动性的试验结果相一致。
In this paper, it was studied that the residue analysis of Metamifop and its three major metabolites and the residue dynamics and final residues in rice plant, paddy water, and soil. Under laboratory conditions, the adsorption and mobility of profenofos in three kinds of soils were also studied using batch equilibrium technique and soil thin layer chromatography. The results could be summarized as followings:
1. The high performance liquid chromatographic method was developed for the simultaneous determination of Metamifop and its three major metabolites in rice and environment. Residues were extracted with a mixture of acetonitrile and water, followed by cleanup with a silica gel column, and determinationed by HPLC with a linear gradient elution program of acetonitrile and water as the mobile phase and ultraviolet detection at 224 nm.The results showed that the linear range of Metamifop and its metabolites were from 0.5 to 20mg/L, the correlation coefficients were 0.9993 to 0.9999, the limit of detection were 0.432ng,0.502ng,0.268ng,0.317ng, respectively. The minimum detectable concentration of the 4 analytes in soil, rice straw,rice hulls and unpolished grain samples were all O.lmg/kg, and 0.02mg/kg in paddy water samples.Average recoveries were 78.2 to 106.9%,and the coefficient of variation ranged from 2.0 to 11.7%. Under the same operation condition, good chromatographic separation of the 4 analytes was achieved. The Sensitivity, accuracy and repeatability of the method were fitted for the requirement of pesticide residue analysis and detection, and it was easy to perform in practice.
2. Degradation dynamic of 10% Metamifop EC and its metabolites in rice and environment was studied by a two-year field experiment. The results showed that the degradation procedure of Metamifop in paddy water, soil and rice straw all accorded with the one-level dynamic equation Ct=Coe-kt; the half-life of Metamifop in paddy water, soil and rice straw were 3.3-7.4d,9.1-14.3d and 1.5-2.2d, respectively. The degradation of its three major metabolites (HFMPA, HPFMPA and 6-CBO) was irregular.
3. Terminal residue of Metamifop and its metabolites in rice plant and soil was studied by a two-year field experiment. The results showed that when 10% Metamifop EC was applied at 120-240g.ai/ha one time, and the interval between harvest and the last pesticide application was 83-90 days, the final residual quantities of Metamifop and its three major metabolites in soil, rice straw,rice hulls and unpolished grain samples were both lower than the minimum detectable concentration. And 10% Metamifop EC was safe at this recommended dosage in the early growth of rice.
4. An analytical method for determining Profenofos residues in water and soil by GC was described.The samples were extracted with acetonitrile, detected by GC with FPD detector. The results showed that the linear range of Profenofos was from 0.2 to 20mg/L, the correlation coefficient was 0.9999; the minimum detectable concentration in soil and water samples were 0.05mg/kg,0.005mg/kg, respectively; average recoveries were 87.2 to 103.6%, and the coefficient of variation ranged from 4.8 to 9.9%. The results of test have met the requirement of pesticide residue analysis.
5. The adsorption and mobility of Profenofos in three kinds of soils were studied using batch equilibrium technique and soil thin layer chromatography. The results showed that absorption constant (Kd) of Profenofos in sand,1oam and clay is 12.70, 33.65 and 74.92, respectively. The soil adsorption capacity of Profenofos is positively related with the contents of soil organic matter. The mobility of Profenofos in three soils was shown that Profenofos don't easily move in 1oam and sand, don't move in clay.
引文
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