百菌清在马铃薯中的最终残留及土壤中消解动态研究
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摘要
为评价百菌清在马铃薯上的使用安全性及土壤中的消解动态残留,建立了百菌清在马铃薯及土壤中的残留分析方法,2016—2017年在湖南长沙和河北石家庄两地进行了720 g/L百菌清悬浮剂在马铃薯上的施用,分析了其有效成分百菌清在马铃薯上的消解动态和最终残留。马铃薯、土壤样品用体积比为1∶1的丙酮-乙腈的混合液振荡提取,提取液经盐析、浓缩后用乙腈定容,气相色谱法检测。结果表明,在添加水平为0. 02 mg/kg、0. 20 mg/kg和2. 00 mg/kg时,马铃薯中百菌清残留量检测方法的添加回收率为81. 1%～110. 5%,相对标准偏差(RSD)为4. 4%～11. 9%;土壤中百菌清残留量检测方法的添加回收率为82. 4%～111. 6%,RSD为6. 3%～10. 9%。百菌清在马铃薯上以高剂量(3 240. 0 g/hm~2)、低剂量(2 160. 0 g/hm~2) 2个剂量分别施药3次和4次,最后一次施药后7 d、14 d、21 d的马铃薯的最大残留量均值分别为0. 084 mg/kg、0. 026 mg/kg、0. 020 mg/kg。百菌清在土壤中的残留消解动态规律符合一级动力学反应模型,其消解半衰期为3. 63～8. 35 d,在土壤环境中较易降解。
Intends to establish a residue analysis method for assessing and degratation of the chlorothalonil in the potato and the soil so as to increase the safe application of chlorothalonil in thesoil and the dynamic mechanism of the residue digestion in it,we managed to apply the digestion dynamics to the study of the final residues of chlorothalonil in the potato after 720 g/L chlorothalonil suspension in the potato in Changsha,Hunan and Shijiazhuang,Hebei,respectively,in 2016 and 2017. On the purpose,we have extracted potato and soil samples by the mixture of acetone and acetonitrile( 1: 1,V/V),and,then,filtered via the Brinell funnel. The filtrate has been collected and vibrated in a stopper container with sodium chloride,and then acetone-acetonitrile phase and water phase can be stratified. And,then,when half of the solution has been concentrated to a degree of nearly half in dry state,the mixture can be fixed to 5. 0 mL with acetonitrile and removed into the sampling bottle for observation and inspection via the gas chromatograph. The results of the test tend to show that there can be found a proper linear relation between the peak area and the mass concentration rate of chlorothalonil in a range of 0. 01-2. 0 mg/L,with the standard curve being equal to y = 10352 x-59. 5,and R~2= 0. 9996. At the additional levels of 0. 02 mg/kg,0. 20 mg/kg and 2. 00 mg/kg,the sfforementioned method for the residue determination in the potato can also be put into the categorical range of 81. 1%-110. 5%,with the relative standard deviation( RSD) being 4. 4%-11. 9%. Besides,the method for the residue determination in the soil can also be added with a recovery range being of 82. 4 %-111. 6%,and the relative standard deviation( RSD) being 6. 3%-10. 9%.Thus,the final residue testing results have revealed that chlorothalonil can also be managed to be dealt with the potato both at high( 3 240. 0 g/hm~2) and low dose( 2 160. 0 g/hm~2) 3 times and 4 times,respectively,with the maximum residue mean time length for the potato treated for a period of 7 days,14 days and21 days when it was adopted in a ratio of 0. 084 mg/kg,0. 026 mg/kg and 0. 020 mg/kg respectively,which have not been found higher than the MRL established by any other countries and regions in the world. The soil digestion dynamic testing results show that the digestion process of chlorothalonil in the soil tends to be a gradual reduction process and the dynamic regularity of the residue digestion in the soil proves consistent with the first-order kinetic reaction model. The half-life of the chlorothalonil residues prove to be 3. 63 days to 8. 35 days. And,in comparison,the half-life of the chlorothalonil residues in Changsha2016-2017 turn to be 8. 35 days and 3. 63 days and in Shijiazhuang 2016-2017,6. 33 days and 5. 64 days,respectively.Thus,it can be concluded that chlorothalonil is by nature easy to be degraded in the soil environment but not lead to the cumulative residue pollution in it.
Intends to establish a residue analysis method for assessing and degratation of the chlorothalonil in the potato and the soil so as to increase the safe application of chlorothalonil in thesoil and the dynamic mechanism of the residue digestion in it,we managed to apply the digestion dynamics to the study of the final residues of chlorothalonil in the potato after 720 g/L chlorothalonil suspension in the potato in Changsha,Hunan and Shijiazhuang,Hebei,respectively,in 2016 and 2017. On the purpose,we have extracted potato and soil samples by the mixture of acetone and acetonitrile( 1: 1,V/V),and,then,filtered via the Brinell funnel. The filtrate has been collected and vibrated in a stopper container with sodium chloride,and then acetone-acetonitrile phase and water phase can be stratified. And,then,when half of the solution has been concentrated to a degree of nearly half in dry state,the mixture can be fixed to 5. 0 mL with acetonitrile and removed into the sampling bottle for observation and inspection via the gas chromatograph. The results of the test tend to show that there can be found a proper linear relation between the peak area and the mass concentration rate of chlorothalonil in a range of 0. 01-2. 0 mg/L,with the standard curve being equal to y = 10352 x-59. 5,and R~2= 0. 9996. At the additional levels of 0. 02 mg/kg,0. 20 mg/kg and 2. 00 mg/kg,the sfforementioned method for the residue determination in the potato can also be put into the categorical range of 81. 1%-110. 5%,with the relative standard deviation( RSD) being 4. 4%-11. 9%. Besides,the method for the residue determination in the soil can also be added with a recovery range being of 82. 4 %-111. 6%,and the relative standard deviation( RSD) being 6. 3%-10. 9%.Thus,the final residue testing results have revealed that chlorothalonil can also be managed to be dealt with the potato both at high( 3 240. 0 g/hm~2) and low dose( 2 160. 0 g/hm~2) 3 times and 4 times,respectively,with the maximum residue mean time length for the potato treated for a period of 7 days,14 days and21 days when it was adopted in a ratio of 0. 084 mg/kg,0. 026 mg/kg and 0. 020 mg/kg respectively,which have not been found higher than the MRL established by any other countries and regions in the world. The soil digestion dynamic testing results show that the digestion process of chlorothalonil in the soil tends to be a gradual reduction process and the dynamic regularity of the residue digestion in the soil proves consistent with the first-order kinetic reaction model. The half-life of the chlorothalonil residues prove to be 3. 63 days to 8. 35 days. And,in comparison,the half-life of the chlorothalonil residues in Changsha2016-2017 turn to be 8. 35 days and 3. 63 days and in Shijiazhuang 2016-2017,6. 33 days and 5. 64 days,respectively.Thus,it can be concluded that chlorothalonil is by nature easy to be degraded in the soil environment but not lead to the cumulative residue pollution in it.
引文
[1] CHEN Li(陈莉),ZHU Xiaodan(朱晓丹),JIA Chunhong(贾春虹), et al. Residue and degradation of mefenoxam and chlorothalonil in cucumber and soil[J].Journal of Anhui Agricultural Science(安徽农业科学),2011,39(27):16626-16628,16647.
[2] DALY G L,LEI Y D,TEIXEIRA C,et al. Pesticides in western Canadian mountain air and soil[J]. Environmental Science&Technology,2007,41(17):6020-6025.
[3] KWON J W,ARMBRUST K L. Degradation of chlorothalonil in irradiated water/sediment systems[J]. Journal of Agricultural and Food Chemistry, 2006, 54(10):3651-3657.
[4] PASL J,MA TSER A M,BOESTEN J J,et al. Behaviour of metamitron and hydroxy chlorothalonil in low-humic sandy soils[J]. Pesticide Science, 1999, 55(9):923-934.
[5] LAWRUK T S,GUECO A M,JOURDAN S W,et al.Determination of chlorothalonil in water and agricultural products by a magnetic particle based enzyme immunoassay[J]. Journal of Agricultural and Food Chemistry,1995,43(5):1413-1419.
[6] MOZZACHIO A M,RUSIECKI J A,HOPPIN J A,et al.Chlorothalonil exposure and cancer incidence among pesticide applicator participants in the agricultural health study[J]. Environmental Research, 2008, 108(3):400-403.
[7] BRUHN J A,FRY W E. A mathematical model of the spatial and temporal dynamics of chlorothalonil residues on potato foliage[J]. Phytopathology,1982,72(10):1306-1312.
[8] VALVERDE G A,GONZALEZ P E,REAL A D,et al.Determination and degradation study of chlorothalonil residues in cucumbers,peppers and cherry tomatoes[J]. Analytica Chimica Acta,1993,276(1):15-23.
[9] TREVIZAN L R P,BAPTISTA G C D. Residues of chlorothalonil in greenhouse and field tomato crops[J]. Revista Brasileira de Toxicologia,2003,16(2):55-61.
[10] Changsha Chemical Research Institute,Hunan Province(湖南省长沙市化工研究所). Study on the method of chromatographic analysis of the bacteria[J]. Pesticide Industry(农药工业),1976,13(6):25-29.
[11] LI Jiemin(李杰敏),ZOU Tianzhi(邹天治),SONG Ming(宋鸣),et al. Test of chlorothalonil by GC/MS and GC[J]. Journal of Mass Spectrometry(质谱学报),1991,20(3):147-148.
[12] WANG Huili(王会利),CHEN Changlong(陈长龙),HU Jiye(胡继业),et al. Research on residues of chlorothalonil and thiram in mushroom[J]. Chinese Journal of Pesticide Science(农药学学报),2006,8(3):283-287.
[13] YAO Fang(姚芳),CHEN Xiaowei(陈小微),LIANG Chizhou(梁赤周),et al. Research on the residue and degradation dynamic of chlorothalonil and its metabolite(4-hydroxy chlorothalonil)in lactuca sativa and soil[J]. Journal of Food Safety and Quality(食品安全质量检测学报),2018,9(1):155-160.
[14] PUTNAM R A,NELSON J O,CLARK J M. The persistence and degradation of chlorothalonil and chlorpyrifos in a cranberry bog[J]. Journal of Agricultural and Food Chemistry,2003,51(1):170-176.
[15] GAMBACORTA G,FACCIA M,LAMACCHIA C,et al. Pesticide residues in tomato grown in open field[J].Food Control,2005,16(7):629-632.
[16] GUO Jianhui(郭建辉),CAI Enxing(蔡恩兴),CHEN Liping(陈丽萍),et al. Analysis of the residual dynamics of chlorothalonil and myclobutanil in bananas[J].Journal of Safety and Environment(安全与环境学报),2011,11(6):16-19.
[17] ZHAO Ying(赵颖),SHEN Jian(沈坚),QIN Li(秦丽),et al. Residual characteristic analysis of imidacloprid and chlorothalonil in calabash and cucumber in field and greenhouse[J]. Chinese Journal of Pesticide Science(农药学报),2012,14(6):647-653.
[18] YU Anfen(于安芬),CHE Zongxian(车宗贤),WANG Donghui(王东晖),et al. Study on natural dynamic degradation of chlorothalonil in tomato and its health risks[J]. Acta Agriculturae Boreali-Occidentalis Sinica(西北农业大学),2016,25(10):1508-1514.
[19] JI Shujuan(纪淑娟),GUO Naifei(郭乃菲),QI Xiaohui(齐小辉),et al. Determination of chlorothalonil and its metabolite residues in vegetables by HPLC[J]. Food Industry Technology(食品工业科技),2011,32(7):397-399,402.
[20] AN Xuehua(安雪花),WU Changxing(吴长兴),JI Xiaofeng(吉小风),et al. Risk assessment of human exposure to chlorothalonil during application and harvest process in strawberry greenhouse[J]. Chinese Journal of Pesticide Science(农药学学报), 2014, 16(1):84-91.
[21] DU Pengqiang(杜鹏强),GU Xiaojun(顾晓军),LIU Xingang(刘新刚),et al. Simultaneous determination of chlorothalonil and beta-cypermethrin residues in mushrooms and their substrate by gas chromatography electron capture detection[J]. Environmental Chemistry(环境化学),2014,33(3):459-463.
[22] LI Pingping(李萍萍),CHENG Jing(程景),ZHANG Zhenshan(张振山),et al. Simultaneous determination of chlorothalonil captan and hexaconazole residues in jackfruit by gas chromatography-tandem mass spectrometry[J]. Pesticide(农药),2016,55(8):593-596.
[23] LIU Xuanbin(刘宣兵),ZHANG Gaiping(张改平),LIU Qingtang(刘庆堂),et al. Development of immunoassays for the detection of sulfamethazine in swine urine[J]. Journal of Agricultural Biotechnology(农业生物技术学报),2009,17(1):18-23.
[24] LI An(李安),WANG Beihong(王北洪),PAN Ligang(潘立刚),et al. Present situation and chronic dietary exposure assessment of pesticide residues in vegetables in Beijing[J]. Journal of Food Safety and Quality(食品安全质量检测学报),2016,7(3):1164-1169.
[25] ZHANG Bo(张博),ZHANG Yueli(张悦丽),LI Yan(李彦),et al. Residue and degradation of chlorothalonil use in the protected vegetable fields in different seasons[J]. Chinese Agricultural Science Bulletin(中国农学通报),2014,30(16):312-316.
[26] WANG Yunru(王运儒),QIN Yuyan(秦玉燕),NONG Yaojing(农耀京), et al. Determination of phoxim residues in potato and soil by high performance liquid chromatography[J]. Journal of Food Safety and Quality(食品安全质量检测学报),2017,8(2):421-427.
[27] LIANG Lin(梁林),LI Wenping(李文平),LIU Wei(刘伟). Study on dissipation dynamics and residue analysis of famoxadone in potato and soil[J]. Pesticide Science and Administration(农药科学与管理),2017,38(3):34-37.
[28] WU Xingxiang(吴星祥),YANG Juan(杨娟),LI Xiaopeng(黎小鹏),et al. Determination of 8 organochlorine pesticide residues in potatoes by gas chromatography[J]. Modern Agricultural Sciences and Technology,2016(4):120-128.
[2] DALY G L,LEI Y D,TEIXEIRA C,et al. Pesticides in western Canadian mountain air and soil[J]. Environmental Science&Technology,2007,41(17):6020-6025.
[3] KWON J W,ARMBRUST K L. Degradation of chlorothalonil in irradiated water/sediment systems[J]. Journal of Agricultural and Food Chemistry, 2006, 54(10):3651-3657.
[4] PASL J,MA TSER A M,BOESTEN J J,et al. Behaviour of metamitron and hydroxy chlorothalonil in low-humic sandy soils[J]. Pesticide Science, 1999, 55(9):923-934.
[5] LAWRUK T S,GUECO A M,JOURDAN S W,et al.Determination of chlorothalonil in water and agricultural products by a magnetic particle based enzyme immunoassay[J]. Journal of Agricultural and Food Chemistry,1995,43(5):1413-1419.
[6] MOZZACHIO A M,RUSIECKI J A,HOPPIN J A,et al.Chlorothalonil exposure and cancer incidence among pesticide applicator participants in the agricultural health study[J]. Environmental Research, 2008, 108(3):400-403.
[7] BRUHN J A,FRY W E. A mathematical model of the spatial and temporal dynamics of chlorothalonil residues on potato foliage[J]. Phytopathology,1982,72(10):1306-1312.
[8] VALVERDE G A,GONZALEZ P E,REAL A D,et al.Determination and degradation study of chlorothalonil residues in cucumbers,peppers and cherry tomatoes[J]. Analytica Chimica Acta,1993,276(1):15-23.
[9] TREVIZAN L R P,BAPTISTA G C D. Residues of chlorothalonil in greenhouse and field tomato crops[J]. Revista Brasileira de Toxicologia,2003,16(2):55-61.
[10] Changsha Chemical Research Institute,Hunan Province(湖南省长沙市化工研究所). Study on the method of chromatographic analysis of the bacteria[J]. Pesticide Industry(农药工业),1976,13(6):25-29.
[11] LI Jiemin(李杰敏),ZOU Tianzhi(邹天治),SONG Ming(宋鸣),et al. Test of chlorothalonil by GC/MS and GC[J]. Journal of Mass Spectrometry(质谱学报),1991,20(3):147-148.
[12] WANG Huili(王会利),CHEN Changlong(陈长龙),HU Jiye(胡继业),et al. Research on residues of chlorothalonil and thiram in mushroom[J]. Chinese Journal of Pesticide Science(农药学学报),2006,8(3):283-287.
[13] YAO Fang(姚芳),CHEN Xiaowei(陈小微),LIANG Chizhou(梁赤周),et al. Research on the residue and degradation dynamic of chlorothalonil and its metabolite(4-hydroxy chlorothalonil)in lactuca sativa and soil[J]. Journal of Food Safety and Quality(食品安全质量检测学报),2018,9(1):155-160.
[14] PUTNAM R A,NELSON J O,CLARK J M. The persistence and degradation of chlorothalonil and chlorpyrifos in a cranberry bog[J]. Journal of Agricultural and Food Chemistry,2003,51(1):170-176.
[15] GAMBACORTA G,FACCIA M,LAMACCHIA C,et al. Pesticide residues in tomato grown in open field[J].Food Control,2005,16(7):629-632.
[16] GUO Jianhui(郭建辉),CAI Enxing(蔡恩兴),CHEN Liping(陈丽萍),et al. Analysis of the residual dynamics of chlorothalonil and myclobutanil in bananas[J].Journal of Safety and Environment(安全与环境学报),2011,11(6):16-19.
[17] ZHAO Ying(赵颖),SHEN Jian(沈坚),QIN Li(秦丽),et al. Residual characteristic analysis of imidacloprid and chlorothalonil in calabash and cucumber in field and greenhouse[J]. Chinese Journal of Pesticide Science(农药学报),2012,14(6):647-653.
[18] YU Anfen(于安芬),CHE Zongxian(车宗贤),WANG Donghui(王东晖),et al. Study on natural dynamic degradation of chlorothalonil in tomato and its health risks[J]. Acta Agriculturae Boreali-Occidentalis Sinica(西北农业大学),2016,25(10):1508-1514.
[19] JI Shujuan(纪淑娟),GUO Naifei(郭乃菲),QI Xiaohui(齐小辉),et al. Determination of chlorothalonil and its metabolite residues in vegetables by HPLC[J]. Food Industry Technology(食品工业科技),2011,32(7):397-399,402.
[20] AN Xuehua(安雪花),WU Changxing(吴长兴),JI Xiaofeng(吉小风),et al. Risk assessment of human exposure to chlorothalonil during application and harvest process in strawberry greenhouse[J]. Chinese Journal of Pesticide Science(农药学学报), 2014, 16(1):84-91.
[21] DU Pengqiang(杜鹏强),GU Xiaojun(顾晓军),LIU Xingang(刘新刚),et al. Simultaneous determination of chlorothalonil and beta-cypermethrin residues in mushrooms and their substrate by gas chromatography electron capture detection[J]. Environmental Chemistry(环境化学),2014,33(3):459-463.
[22] LI Pingping(李萍萍),CHENG Jing(程景),ZHANG Zhenshan(张振山),et al. Simultaneous determination of chlorothalonil captan and hexaconazole residues in jackfruit by gas chromatography-tandem mass spectrometry[J]. Pesticide(农药),2016,55(8):593-596.
[23] LIU Xuanbin(刘宣兵),ZHANG Gaiping(张改平),LIU Qingtang(刘庆堂),et al. Development of immunoassays for the detection of sulfamethazine in swine urine[J]. Journal of Agricultural Biotechnology(农业生物技术学报),2009,17(1):18-23.
[24] LI An(李安),WANG Beihong(王北洪),PAN Ligang(潘立刚),et al. Present situation and chronic dietary exposure assessment of pesticide residues in vegetables in Beijing[J]. Journal of Food Safety and Quality(食品安全质量检测学报),2016,7(3):1164-1169.
[25] ZHANG Bo(张博),ZHANG Yueli(张悦丽),LI Yan(李彦),et al. Residue and degradation of chlorothalonil use in the protected vegetable fields in different seasons[J]. Chinese Agricultural Science Bulletin(中国农学通报),2014,30(16):312-316.
[26] WANG Yunru(王运儒),QIN Yuyan(秦玉燕),NONG Yaojing(农耀京), et al. Determination of phoxim residues in potato and soil by high performance liquid chromatography[J]. Journal of Food Safety and Quality(食品安全质量检测学报),2017,8(2):421-427.
[27] LIANG Lin(梁林),LI Wenping(李文平),LIU Wei(刘伟). Study on dissipation dynamics and residue analysis of famoxadone in potato and soil[J]. Pesticide Science and Administration(农药科学与管理),2017,38(3):34-37.
[28] WU Xingxiang(吴星祥),YANG Juan(杨娟),LI Xiaopeng(黎小鹏),et al. Determination of 8 organochlorine pesticide residues in potatoes by gas chromatography[J]. Modern Agricultural Sciences and Technology,2016(4):120-128.