呋虫胺及其代谢物在水稻生态系统中的残留检测与消解动态
|
摘要
为评价呋虫胺在水稻生态系统中的残留与消解行为,分别在海南、湖南和黑龙江省3地进行了规范残留试验。建立了超高效液相色谱-串联质谱(UPLC-MS/MS)检测呋虫胺(DNF)及其代谢物1-甲基-3-[(3-四氢呋喃)甲基]脲(UF)与1-甲基-3-[(3-四氢呋喃)甲基]二氢胍盐(DN)在水稻稻株、土壤、田水、糙米和稻壳中残留的分析方法。样品经含体积分数为1%的乙酸水溶液或乙腈溶液提取,QuEChERS方法净化,以甲醇-水混合溶液为流动相梯度洗脱,多反应监测(MRM)模式扫描,外标法定量。结果表明:3种分析物的进样浓度与其峰面积之间呈良好线性相关,R2>0.999。DNF、UF和DN在稻株、土壤、田水、糙米和稻壳中的平均回收率在71%～102%之间,在稻株、土壤、田水和糙米中的相对标准偏差(RSD)在1.2%～8.3%之间,在稻壳中的RSD在4.4%～20%之间。3种分析物在稻株、土壤、田水、糙米和稻壳中的最低检测浓度(LOQ)分别为0.1 mg/kg、0.02 mg/kg、0.01 mg/L、0.02 mg/kg和0.1 mg/kg。DNF、UF和DN的最小检出量分别为1、0.4和4 pg。3种分析物的消解半衰期分别为:DNF在稻株上为0.41～2.7 d,土壤中为1.6～4.2 d,田水中为0.90～2.2 d;DN在稻株上为2.9～13 d,土壤中为64～65 d,田水中为4.2 d;UF在稻株上为0.43～3.1 d。20%呋虫胺悬浮剂以有效成分120～180 g/hm2的剂量于水稻抽穗期施用2～3次,施药间隔期21 d,分别于距末次施药后14 d与21 d采收,呋虫胺在糙米中的残留最大值为0.11 mg/kg,低于中国制定的其在糙米上的最大残留限量标准1 mg/kg。
To evaluate the residue and dissipation behavior of dinotefuran in rice ecosystem, the residual trial of dinotefuran in rice were carried out in Hainan, Hunan and Heilongjiang. A new method for the residue determination of dinotefuran(DNF) and its metabolites 1-methyl-3-(tetrahydro-3-furylmethyl)urea(UF) and 1-methyl-3-(tetrahydro-3-furylmethyl)guanidine(DN) in soil, paddy water,rice plant, brown rice, and rice husk was developed using ultra performance liquid chromatographytandem mass spectrometry(UPLC-MS/MS). The samples were extracted by acetonitrile or water containing 1% acetic acid, purified by QuEChERS method, gradiently eluted in aqueous solution containing methnol and water, and quantified by external standard method. Results showed that there was a good linear correlation between the concentrations of the three analytes and their peak areas with R~2 higher than 0.999. The limits of detection(LOD) of DNF, UF and DN were 1, 0.4, and 4 pg,respectively. The limits of quantification(LOQ) of dinotefuran and its metabolites in rice plant, soil,paddy water, brown rice and rice husk were 0.1 mg/kg, 0.02 mg/kg, 0.01 mg/L, 0.02 mg/kg, and 0.1 mg/kg, respectively. The average recoveries of the three analytes varied from 71% to 102% with the relative standard deviation(RSD) ranged from 1.2% to 8.3%. However, the RSD in rice husk was from 4.4% to 20%. For the dissipation half-lives, DNF in rice plant was 0.41-2.7 d, DNF in soil was 1.6-4.2 d, DNF in paddy water was 0.90-2.2 d; DN in rice plant was 2.9-13 d, DN in soil was 64-65 d, DN in paddy water was 4.2 d; and UF in rice plant was 0.43-3.1 d. The 20% suspension concentrate of dinotefuran was evenly sprayed at 120-180 g a.i./hm~2 for 2 to 3 times in the heading stage of rice with a21-day interval between sprays. The highest residue of dinotefuran in brown rice sampled at day 14 and 21 after the last pesticide application was 0.11 mg/kg, which is below the maximum residue limit1 mg/kg of brown rice set by China.
To evaluate the residue and dissipation behavior of dinotefuran in rice ecosystem, the residual trial of dinotefuran in rice were carried out in Hainan, Hunan and Heilongjiang. A new method for the residue determination of dinotefuran(DNF) and its metabolites 1-methyl-3-(tetrahydro-3-furylmethyl)urea(UF) and 1-methyl-3-(tetrahydro-3-furylmethyl)guanidine(DN) in soil, paddy water,rice plant, brown rice, and rice husk was developed using ultra performance liquid chromatographytandem mass spectrometry(UPLC-MS/MS). The samples were extracted by acetonitrile or water containing 1% acetic acid, purified by QuEChERS method, gradiently eluted in aqueous solution containing methnol and water, and quantified by external standard method. Results showed that there was a good linear correlation between the concentrations of the three analytes and their peak areas with R~2 higher than 0.999. The limits of detection(LOD) of DNF, UF and DN were 1, 0.4, and 4 pg,respectively. The limits of quantification(LOQ) of dinotefuran and its metabolites in rice plant, soil,paddy water, brown rice and rice husk were 0.1 mg/kg, 0.02 mg/kg, 0.01 mg/L, 0.02 mg/kg, and 0.1 mg/kg, respectively. The average recoveries of the three analytes varied from 71% to 102% with the relative standard deviation(RSD) ranged from 1.2% to 8.3%. However, the RSD in rice husk was from 4.4% to 20%. For the dissipation half-lives, DNF in rice plant was 0.41-2.7 d, DNF in soil was 1.6-4.2 d, DNF in paddy water was 0.90-2.2 d; DN in rice plant was 2.9-13 d, DN in soil was 64-65 d, DN in paddy water was 4.2 d; and UF in rice plant was 0.43-3.1 d. The 20% suspension concentrate of dinotefuran was evenly sprayed at 120-180 g a.i./hm~2 for 2 to 3 times in the heading stage of rice with a21-day interval between sprays. The highest residue of dinotefuran in brown rice sampled at day 14 and 21 after the last pesticide application was 0.11 mg/kg, which is below the maximum residue limit1 mg/kg of brown rice set by China.
引文
[1]WAKITA T,KINOSHITA K,YAMADA E,et al.The discovery of dinotefuran:a novel neonicotinoid[J].Pest Manag Sci,2003,59(9):1016-1022.
[2]唐振华,陶黎明,李忠.新烟碱类杀虫剂选择作用的分子机理[J].农药学学报,2006,8(4):291-298.TANG Z H,TAO L M,LI Z.Molecular mechanisms for selective action of neonicotinoid insecticides[J].Chin J Pestic Sci,2006,8(4):291-298.
[3]余兵,何木兰,石丙楼,等.20%呋虫胺悬浮剂防治水稻稻飞虱田间药效试验[J].安徽农学通报,2016,22(3-4):65.YU B,HE M L,SHI B L,et al.Field efficacy test of 20%furotefuran suspension controlling rice planthopper[J].Anhui Agric Sci Bull,2016,22(3-4):65.
[4]Food and Agriculture Organization of the United Nations.JMPRdinotefuran 2012 report[EB/OL].[2019-03-13].http://www.fao.org/fileadmin/templates/agphome/documents/Pests_Pesticides/JMPR/Report12/Dinotefuran.pdf.
[5]刘纪松,胡存中,陆凡,等.呋虫胺在土壤中的降解及移动性研究[J].生态环境学报,2015,24(6):1063-1068.LIU J S,HU C Z,LU F,et al.Studies on the degradation and mobility of dinotefuran in soil[J].Ecol Environ Sci,2015,24(6):1063-1068.
[6]WATANABE E,BABA K,MIYAKE S.Analytical evaluation of enzyme-linked immunosorbent assay for neonicotinoid dinotefuran for potential application to quick and simple screening method in rice samples[J].Talanta,2011,84(4):1107-1111.
[7]RAHMAN M M,PARK J H,ABD EL-ATY A M,et al.Feasibility and application of an HPLC/UVD to determine dinotefuran and its shorter wavelength metabolites residues in melon with tandem mass confirmation[J].Food Chem,2013,136(2):1038-1046.
[8]董旭,段劲生,王梅,等.呋虫胺及其代谢物在稻田环境中的残留规律[J].农药,2016,55(10):753-756.DONG X,DUAN J S,WANG M,et al.Residue dynamics of dinotefuran and its metabolites in rice and paddy field[J].Agrochemicals,2016,55(10):753-756.
[9]吴延灿,蒋冰心,施艳红,等.QuPPe-超高效液相色谱-串联质谱法测定蔬菜中呋虫胺及其代谢物残留[J].食品科学,2018,39(18):262-266.WU Y C,JIANG B X,SHI Y H,et al.Simultaneous determination of dinotefuran and its metabolites in vegetables by QuPPe-UPLC-MS/MS[J].Food Sci,2018,39(18):262-266.
[10]彭敏,陈武瑛,陈武荣,等.呋虫胺及其代谢物在甘蓝和土壤中的消解规律[J].农药,2018,57(2):124-126.PENG M,CHEN W Y,CHEN W R,et al.Degradation dynamics of dinotefuran and its metabolites in cabbage and soil[J].Agrochemicals,2018,57(2):124-126.
[11]YANG Z H,ZHANG K K,CHEN L Z,et al.Determination of dinotefuran and its metabolites in orange pulp,orange peel,and whole orange using liquid chromatography-tandem mass spectrometry[J].JAOAC Int,2017,100(5):1551-1558.
[12]ZHANG Y,WU X H,DUAN T T,et al.Ultra high performance liquid chromatography with tandem mass spectrometry method for determining dinotefuran and its main metabolites in samples of plants,animal-derived foods,soil,and water[J].J Sep Sci,2018,41(14):2913-2923.
[13]RAHMAN M M,ABD EL-ATY A M,CHOI J H,et al.Consequences of the matrix effect on recovery of dinotefuran and its metabolites in green tea during tandem mass spectrometry analysis[J].Food Chem,2015,168:445-453.
[14]RAHMAN M M,ABD EL-ATY A M,KABIR M H,et al.A quick and effective methodology for analyzing dinotefuran and its highly polar metabolites in plum using liquid chromatography-tandem mass spectrometry[J].Food Chem,2018,239:1235-1243.
[15]Guidance document on analytical quality control and method validation procedures for pesticide residues analysis in food and feed:DG SANCO/11945/2015[S].Sweden:European Commission,2015.
[16]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.Maximum residue limit of pesticides in food:GB 2763-2016[S].Beijing:China Standard Press,2017.
[17]JACOBSEN R E,FANTKE P,TRAPP S.Analysing half-lives for pesticide dissipation in plants[J].SAR QSAR Environ Res,2015,26(4):325-342.
[18]孙明娜,董旭,王梅,等.呋虫胺在水稻中的残留消解及膳食风险评估[J].农药学学报,2016,18(1):86-92.SUN M N,DONG X,WANG M,et al.Dissipation,residues and dietary risk assessment of dinotefuran in rice[J].Chin J Pestic Sci,2016,18(1):86-92.
[19]YU W W,HUANG M,CHEN J J,et al.Risk assessment and monitoring of dinotefuran and its metabolites for Chinese consumption of apples[J].Environ Monit Assess,2017,189(10):521.
[20]LI R J,LIU T J,CUI S H,et al.Residue behaviors and dietary risk assessment of dinotefuran and its metabolites in Oryza sativa by a new HPLC-MS/MS method[J].Food Chem,2017,235:188-193.
[2]唐振华,陶黎明,李忠.新烟碱类杀虫剂选择作用的分子机理[J].农药学学报,2006,8(4):291-298.TANG Z H,TAO L M,LI Z.Molecular mechanisms for selective action of neonicotinoid insecticides[J].Chin J Pestic Sci,2006,8(4):291-298.
[3]余兵,何木兰,石丙楼,等.20%呋虫胺悬浮剂防治水稻稻飞虱田间药效试验[J].安徽农学通报,2016,22(3-4):65.YU B,HE M L,SHI B L,et al.Field efficacy test of 20%furotefuran suspension controlling rice planthopper[J].Anhui Agric Sci Bull,2016,22(3-4):65.
[4]Food and Agriculture Organization of the United Nations.JMPRdinotefuran 2012 report[EB/OL].[2019-03-13].http://www.fao.org/fileadmin/templates/agphome/documents/Pests_Pesticides/JMPR/Report12/Dinotefuran.pdf.
[5]刘纪松,胡存中,陆凡,等.呋虫胺在土壤中的降解及移动性研究[J].生态环境学报,2015,24(6):1063-1068.LIU J S,HU C Z,LU F,et al.Studies on the degradation and mobility of dinotefuran in soil[J].Ecol Environ Sci,2015,24(6):1063-1068.
[6]WATANABE E,BABA K,MIYAKE S.Analytical evaluation of enzyme-linked immunosorbent assay for neonicotinoid dinotefuran for potential application to quick and simple screening method in rice samples[J].Talanta,2011,84(4):1107-1111.
[7]RAHMAN M M,PARK J H,ABD EL-ATY A M,et al.Feasibility and application of an HPLC/UVD to determine dinotefuran and its shorter wavelength metabolites residues in melon with tandem mass confirmation[J].Food Chem,2013,136(2):1038-1046.
[8]董旭,段劲生,王梅,等.呋虫胺及其代谢物在稻田环境中的残留规律[J].农药,2016,55(10):753-756.DONG X,DUAN J S,WANG M,et al.Residue dynamics of dinotefuran and its metabolites in rice and paddy field[J].Agrochemicals,2016,55(10):753-756.
[9]吴延灿,蒋冰心,施艳红,等.QuPPe-超高效液相色谱-串联质谱法测定蔬菜中呋虫胺及其代谢物残留[J].食品科学,2018,39(18):262-266.WU Y C,JIANG B X,SHI Y H,et al.Simultaneous determination of dinotefuran and its metabolites in vegetables by QuPPe-UPLC-MS/MS[J].Food Sci,2018,39(18):262-266.
[10]彭敏,陈武瑛,陈武荣,等.呋虫胺及其代谢物在甘蓝和土壤中的消解规律[J].农药,2018,57(2):124-126.PENG M,CHEN W Y,CHEN W R,et al.Degradation dynamics of dinotefuran and its metabolites in cabbage and soil[J].Agrochemicals,2018,57(2):124-126.
[11]YANG Z H,ZHANG K K,CHEN L Z,et al.Determination of dinotefuran and its metabolites in orange pulp,orange peel,and whole orange using liquid chromatography-tandem mass spectrometry[J].JAOAC Int,2017,100(5):1551-1558.
[12]ZHANG Y,WU X H,DUAN T T,et al.Ultra high performance liquid chromatography with tandem mass spectrometry method for determining dinotefuran and its main metabolites in samples of plants,animal-derived foods,soil,and water[J].J Sep Sci,2018,41(14):2913-2923.
[13]RAHMAN M M,ABD EL-ATY A M,CHOI J H,et al.Consequences of the matrix effect on recovery of dinotefuran and its metabolites in green tea during tandem mass spectrometry analysis[J].Food Chem,2015,168:445-453.
[14]RAHMAN M M,ABD EL-ATY A M,KABIR M H,et al.A quick and effective methodology for analyzing dinotefuran and its highly polar metabolites in plum using liquid chromatography-tandem mass spectrometry[J].Food Chem,2018,239:1235-1243.
[15]Guidance document on analytical quality control and method validation procedures for pesticide residues analysis in food and feed:DG SANCO/11945/2015[S].Sweden:European Commission,2015.
[16]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.Maximum residue limit of pesticides in food:GB 2763-2016[S].Beijing:China Standard Press,2017.
[17]JACOBSEN R E,FANTKE P,TRAPP S.Analysing half-lives for pesticide dissipation in plants[J].SAR QSAR Environ Res,2015,26(4):325-342.
[18]孙明娜,董旭,王梅,等.呋虫胺在水稻中的残留消解及膳食风险评估[J].农药学学报,2016,18(1):86-92.SUN M N,DONG X,WANG M,et al.Dissipation,residues and dietary risk assessment of dinotefuran in rice[J].Chin J Pestic Sci,2016,18(1):86-92.
[19]YU W W,HUANG M,CHEN J J,et al.Risk assessment and monitoring of dinotefuran and its metabolites for Chinese consumption of apples[J].Environ Monit Assess,2017,189(10):521.
[20]LI R J,LIU T J,CUI S H,et al.Residue behaviors and dietary risk assessment of dinotefuran and its metabolites in Oryza sativa by a new HPLC-MS/MS method[J].Food Chem,2017,235:188-193.