噻唑磷在甘蔗和土壤中的残留消解动态及风险评估
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摘要
建立了噻唑磷在甘蔗和土壤中的残留分析方法,并在广东和广西2地进行了10%噻唑磷颗粒剂在甘蔗上残留的田间试验,研究了噻唑磷在甘蔗和土壤中的消解动态和最终残留量,并对甘蔗中噻唑磷可能产生的膳食摄入风险进行了评估。甘蔗样本用乙腈提取,氨基固相萃取小柱净化,采用气相色谱-火焰光度检测器(GC-FPD)检测。结果表明:在0.01、0.1和1 mg/kg添加水平下,噻唑磷在甘蔗中的平均回收率为83%～84%,相对标准偏差(RSD)为2.6%～3.4%;在土壤中的平均回收率为84%～86%,RSD为4.1%～6.7%。噻唑磷检出限(LOD)和定量限(LOQ)均为0.01 mg/kg。田间试验结果表明:10%噻唑磷颗粒剂在广东和广西甘蔗中的消解不符合一级反应动力学方程,没有显著的消解规律,呈现的特点是浓度由小到大再变小的趋势,施药后14～21 d甘蔗中噻唑磷的残留量达到最大值0.027 mg/kg;噻唑磷在土壤中消解符合一级反应动力学方程,半衰期为8.6～9.6 d,属易降解农药;噻唑磷在甘蔗和土壤中的最终残留量均小于0.01 mg/kg。膳食摄入风险评估结果表明:甘蔗中噻唑磷对人群的急性膳食摄入风险值为225%,急性膳食摄入风险较大,还需进一步结合噻唑磷在人体内的代谢行为等数据进行综合评估;慢性膳食摄入风险值为57%,表明按照推荐剂量施用10%噻唑磷颗粒剂,慢性膳食摄入风险较低,对消费者健康是安全的。
An effective method was developed for the determination of fosthiazate residue in sugar cane and soil. Field trials were designed to evaluate the dissipation and residue of fosthiazate in sugar cane and soil in Guangdong Province and Guangxi Province. The dietary exposure and risk assessment were also conducted. The samples were extracted by acetonitrile, cleaned up by NH2-solid phase extraction and detected by GC-FPD. The results showed that, in terms of sugar cane samples, good average recoveries of 83%-84% with relative standard deviations of 2.6%-3.4% at the spiked level of 0.01, 0.1 and 1 mg/kg were achieved. As for soil samples, recoveries of 84%-86% with RSDs 4.1%-6.7% were obtained. The limit of detection(LOD) was 0.01 mg/kg and the limit of quantification(LOQ) was 0.01 mg/kg. The results demonstrated that residue of fosthiazate in sugar cane decreased first, then increased,and finally decreased again. The maximum concentration were 0.027 mg/kg which was detected 14-21 d after the application. Dissipation of fosthiazate in soil was in accordance with the first order kinetic equation with half-lives from 8.6 to 9.6 d. The terminal residue was below 0.01 mg/kg at harvest time.The acute dietary intake risk probability of fosthiazate was 225%, which was hazardous to people. It is necessary to combine the metabolic behavior data of fosthiazate in human body for comprehensive evaluation. The chronic dietary intake risk probability of fosthiazate was 57%, which was not hazardous to people.
An effective method was developed for the determination of fosthiazate residue in sugar cane and soil. Field trials were designed to evaluate the dissipation and residue of fosthiazate in sugar cane and soil in Guangdong Province and Guangxi Province. The dietary exposure and risk assessment were also conducted. The samples were extracted by acetonitrile, cleaned up by NH2-solid phase extraction and detected by GC-FPD. The results showed that, in terms of sugar cane samples, good average recoveries of 83%-84% with relative standard deviations of 2.6%-3.4% at the spiked level of 0.01, 0.1 and 1 mg/kg were achieved. As for soil samples, recoveries of 84%-86% with RSDs 4.1%-6.7% were obtained. The limit of detection(LOD) was 0.01 mg/kg and the limit of quantification(LOQ) was 0.01 mg/kg. The results demonstrated that residue of fosthiazate in sugar cane decreased first, then increased,and finally decreased again. The maximum concentration were 0.027 mg/kg which was detected 14-21 d after the application. Dissipation of fosthiazate in soil was in accordance with the first order kinetic equation with half-lives from 8.6 to 9.6 d. The terminal residue was below 0.01 mg/kg at harvest time.The acute dietary intake risk probability of fosthiazate was 225%, which was hazardous to people. It is necessary to combine the metabolic behavior data of fosthiazate in human body for comprehensive evaluation. The chronic dietary intake risk probability of fosthiazate was 57%, which was not hazardous to people.
引文
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[5]吴兆鹏,谭文兴,蚁细苗,等.甘蔗渣的饲用价值及其作为饲料应用的研究进展[J].中国牛业科学,2016,42(5):41-45.WU Z P,TAN W X,YI X M,et al.The research progress on the feed forage value of bagasse and its application[J].China Cattle Sci,2016,42(5):41-45.
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[10]郭利丰,吴玉琴.噻唑膦的高效液相色谱分析[J].农药科学与管理,2013,34(2):40-42.GUO L F,WU Y Q.Analysis of fosthiazate in TC by HPLC[J].Pestic Sci Admin,2013,34(2):40-42.
[11]ZHU Y Z,ZHAO M A,FENG Y N,et al.Multiresidue method for the determination of 227 pesticides in hot pepper(Capsicum annuum L.)by liquid chromatography with tandem mass spectrometry[J].JSep Sci,2014,37(20):2947-2954.
[12]李丽,游向荣,孙健,等.甘蔗田间废弃物及制糖副产物综合利用研究进展[J].食品工业,2013,34(7):170-173.LI L,YOU X R,SUN J,et al.Review on utilization of sugarcane field wastes and sugar refining byproducts[J].Food Ind,2013,34(7):170-173.
[13]农作物中农药残留试验准则:NY/T 788-2018[S].北京:中国农业出版社,2018.Guideline on pesticide residue trials on crops:NY/T 788-2018[S].Beijing:China Agriculture Press,2018.
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[15]何洁,刘文锋,胡承成,等.黔东南州黄瓜农药残留膳食摄入风险评估[J].浙江农业科学,2018,59(7):1246-1250.HE J,LIU W F,HU C C,et al.Risk assessment of dietary intake of pesticides in cucumber in Qiandognnan[J].J Zhejiang Agric Sci,2018,59(7):1246-1250.
[16]赵慧宇,杨桂玲,叶贵标,等.急性膳食风险评估在农药残留限量标准制定中的应用[J].浙江农业科学,2018,59(9):1600-1602.ZHAO H Y,YANG G L,YE G B,et al.Application of acute dietary risk assessment in formulation of pesticide residue limits[J].JZhejiang Agric Sci,2018,59(9):1600-1602.
[17]张志恒,李红叶,吴珉,等.百菌清、腈菌唑和吡唑醚菌酯在草莓中的残留及其风险评估[J].农药学学报,2009,11(4):449-455.ZHANG Z H,LI H Y,WU M,et al.Residue and risk assessment of chlorothalonil,myclobutanil and pyraclostrobin in greenhouse strawberry[J].Chin J Pestic Sci,2009,11(4):449-455.
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[19]Electronic code of federal regulations.§180.596 Fosthiazate;tolerances for residues[DB/OL].[2018-08-07].https://www.ecfr.gov/cgi-bin/text-idx?SID=668ec05c5f6afda81ad3ceb061134ec6&mc true&nodese40.26.180_1596&rgndiv8.
[20]Federal Register of Legislative Instruments F2016C00057,Standard1.4.2[S].Australia:Australian Pesticides and Veterinary Medicines Authority,2016.
[21]Pesticide MRLs in Food[S].Korea:Ministry of Food and Drug Safety,2016.
[22]The Japan Food Chemical Research Foundation.Maximum residue limits(MRLs)list of agricultural chemicals in foods[DB/OL].[2018-08-07].http://www.m5.ws001.squarestart.ne.jp/foundation/search.html.
[23]马涛,袁会珠,闫晓静,等.噻唑膦在不同介质不同pH条件下热贮稳定性[J].植物保护,2017,43(1):95-98.MA T,YUAN H Z,YAN X J,et al.Heat storage stability of fosthiazate in different media and different pH[J].Plant Prot,2017,43(1):95-98.
[24]MACBEAN C.The pesticide manual:a world compendium[M].16th ed.Alton,Hampshire:British Crop Production Council,2012.
[2]中国农药信息网.农药登记数据[EB/OL].[2018-06-25].http://www.chinapesticide.org.cn/hysj/index.jhtml.China Pesticide Information Network.Pesticide register data[EB/OL].[2018-06-25].http://www.chinapesticide.org.cn/hysj/index.jhtml.
[3]European Commission.EU-Pesticides database[EB/OL].[2018-08-08].http://ec.europa.eu/food/plant/pesticides/eu-pesticides-database/public/?event=pesticide.residue.CurrentMRL&languag=EN.
[4]食品安全国家标准食品中农药最大残留限量:GB 2763―2016[S].北京:中国标准出版社,2017.National food safety standard-Maximum residue limits for pesticides in food:GB 2763―2016[S].Beijing:China Standard Press,2017.
[5]吴兆鹏,谭文兴,蚁细苗,等.甘蔗渣的饲用价值及其作为饲料应用的研究进展[J].中国牛业科学,2016,42(5):41-45.WU Z P,TAN W X,YI X M,et al.The research progress on the feed forage value of bagasse and its application[J].China Cattle Sci,2016,42(5):41-45.
[6]罗志明,李文凤,黄应昆,等.噻虫嗪及其复配制剂不同施药方法对3种甘蔗害虫的防控效果[J].植物保护,2014,40(4):166-170.LUO Z M,LI W F,HUANG Y K,et al.Control efficacies of thiamethoxam and its mixtures with different application methods on three kinds of sugarcane insect pests[J].Plant Prot,2014,40(4):166-170.
[7]张玉婷,郭永泽,刘磊,等.噻唑膦在西瓜及土壤中的残留动态研究[J].天津农业科学,2011,17(4):68-70.ZHANG Y T,GUO Y Z,LIU L,et al.Residues dynamics of fosthiazate in watermelon and soil[J].Tianjin Agric Sci,2011,17(4):68-70.
[8]WU M,HU J Y.Residue analysis of fosthiazate in cucumber and soil by QuEChERS and GC-MS[J].Chem Pap,2014,68(10):1368-1374.
[9]OSBORN R K,EDWARDS S G,WILCOX A,et al.Potential enhancement of degradation of the nematicides aldicarb,oxamyl and fosthiazate in UK agricultural soils through repeated applications[J].Pest Manage Sci,2010,66(3):253-261.
[10]郭利丰,吴玉琴.噻唑膦的高效液相色谱分析[J].农药科学与管理,2013,34(2):40-42.GUO L F,WU Y Q.Analysis of fosthiazate in TC by HPLC[J].Pestic Sci Admin,2013,34(2):40-42.
[11]ZHU Y Z,ZHAO M A,FENG Y N,et al.Multiresidue method for the determination of 227 pesticides in hot pepper(Capsicum annuum L.)by liquid chromatography with tandem mass spectrometry[J].JSep Sci,2014,37(20):2947-2954.
[12]李丽,游向荣,孙健,等.甘蔗田间废弃物及制糖副产物综合利用研究进展[J].食品工业,2013,34(7):170-173.LI L,YOU X R,SUN J,et al.Review on utilization of sugarcane field wastes and sugar refining byproducts[J].Food Ind,2013,34(7):170-173.
[13]农作物中农药残留试验准则:NY/T 788-2018[S].北京:中国农业出版社,2018.Guideline on pesticide residue trials on crops:NY/T 788-2018[S].Beijing:China Agriculture Press,2018.
[14]农业部农药检定所.农药登记残留田间试验标准操作规程[M].北京:中国标准出版社,2007:395.Institute for the Control of Agrochemicals.Standard operating procedures on pesticide registration residue field trial[M].Beijing:Standards Press of China,2007:395.
[15]何洁,刘文锋,胡承成,等.黔东南州黄瓜农药残留膳食摄入风险评估[J].浙江农业科学,2018,59(7):1246-1250.HE J,LIU W F,HU C C,et al.Risk assessment of dietary intake of pesticides in cucumber in Qiandognnan[J].J Zhejiang Agric Sci,2018,59(7):1246-1250.
[16]赵慧宇,杨桂玲,叶贵标,等.急性膳食风险评估在农药残留限量标准制定中的应用[J].浙江农业科学,2018,59(9):1600-1602.ZHAO H Y,YANG G L,YE G B,et al.Application of acute dietary risk assessment in formulation of pesticide residue limits[J].JZhejiang Agric Sci,2018,59(9):1600-1602.
[17]张志恒,李红叶,吴珉,等.百菌清、腈菌唑和吡唑醚菌酯在草莓中的残留及其风险评估[J].农药学学报,2009,11(4):449-455.ZHANG Z H,LI H Y,WU M,et al.Residue and risk assessment of chlorothalonil,myclobutanil and pyraclostrobin in greenhouse strawberry[J].Chin J Pestic Sci,2009,11(4):449-455.
[18]国际食品法典委员会(CAC).最大残留限量查询[DB/OL].(2016-01-06).http://www.fao.org/fao-who-codexalimentarius/codextexts/dbs/pestres/pesticides/en/Codex Alimentarius Commission.Intermational food standards[DB/OL].(2016-01-06).http://www.fao.org/fao-whocodexalimentarius/standards/pestres/en/.
[19]Electronic code of federal regulations.§180.596 Fosthiazate;tolerances for residues[DB/OL].[2018-08-07].https://www.ecfr.gov/cgi-bin/text-idx?SID=668ec05c5f6afda81ad3ceb061134ec6&mc true&nodese40.26.180_1596&rgndiv8.
[20]Federal Register of Legislative Instruments F2016C00057,Standard1.4.2[S].Australia:Australian Pesticides and Veterinary Medicines Authority,2016.
[21]Pesticide MRLs in Food[S].Korea:Ministry of Food and Drug Safety,2016.
[22]The Japan Food Chemical Research Foundation.Maximum residue limits(MRLs)list of agricultural chemicals in foods[DB/OL].[2018-08-07].http://www.m5.ws001.squarestart.ne.jp/foundation/search.html.
[23]马涛,袁会珠,闫晓静,等.噻唑膦在不同介质不同pH条件下热贮稳定性[J].植物保护,2017,43(1):95-98.MA T,YUAN H Z,YAN X J,et al.Heat storage stability of fosthiazate in different media and different pH[J].Plant Prot,2017,43(1):95-98.
[24]MACBEAN C.The pesticide manual:a world compendium[M].16th ed.Alton,Hampshire:British Crop Production Council,2012.