超高效液相色谱-串联质谱法分析氟虫双酰胺和噻嗪酮在茭白中的残留及消解动态

徐峰; 于佳勇; 吴银良; 叶子弘

doi:10.16801/j.issn.1008-7303.2018.0049

超高效液相色谱-串联质谱法分析氟虫双酰胺和噻嗪酮在茭白中的残留及消解动态

doi: 10.16801/j.issn.1008-7303.2018.0049

徐峰^{1, 2,},
于佳勇³,
吴银良^2, ,,
叶子弘^1, ,

1.
中国计量大学生命科学学院/浙江省生物计量及检验检疫技术重点实验室，杭州 310018
2.
宁波市农业科学研究院，浙江宁波 315040
3.
通标标准技术服务有限公司宁波分公司，浙江宁波 315040

基金项目: 宁波市农业重大科技攻关项目 (2015C110004)；公益类重大专项 (2015C110018)；社发重大项目 (2016C51002)

详细信息

作者简介:
徐峰，女，硕士研究生，E-mail：344403036@qq.com

通讯作者:
吴银良，通信作者 (Author for correspondence)，男，教授级高工，研究方向为农兽药残留分析，E-mail：wupaddyfield@tom.com

叶子弘，共同通信作者 (Co-author for correspondence)，女，教授，研究方向为转基因安全评价、微生物与植物互作，E-mail：zhye@cjlu.edu.cn

中图分类号: S482.3；TQ450.263
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出版历程
- 收稿日期: 2018-02-26
- 录用日期: 2018-04-16
- 刊出日期: 2018-06-30

Residueanddissipationdynamicsofflubendiamidandbuprofezinin<italic>Zizanialatifolia</italic>byultraperformanceliquidchromatography-tandemmassspectrometry

XU Feng^{1, 2
,},
YU Jiayong³,
WU Yinliang^{2
, ,},
YE Zihong^{1
, ,}

1.
College of Life Sciences, China Jiliang University/Zhejiang Provincial Key Laboratory of Biometrology and Inspection & Quarantine, Hangzhou 310018, China
2.
The Ningbo Academy of Agricultural Sciences, Ningbo 315040, Zhejiang Province, China
3.
SGS-CSTC Standards Technical Services (Ningbo) Co., Ltd., Ningbo 315040, Zhejiang Province, China

摘要

摘要: 建立了超高效液相色谱-串联质谱 (UPLC-MS/MS) 检测氟虫双酰胺和噻嗪酮在茭白中残留的方法。样品采用乙腈提取，乙二胺-N-丙基硅烷 (PSA) 净化，0.1%甲酸-甲醇梯度洗脱，电喷雾正离子扫描，多反应监测模式，超高效液相色谱-串联质谱测定，外标法定量。结果表明：在0.005~1 mg/kg添加水平下，氟虫双酰胺和噻嗪酮在茭白植株和茭白中的平均回收率在81%~107%之间，相对标准偏差在4.2%~11%之间。消解动态规律符合一级动力学方程，氟虫双酰胺和噻嗪酮的半衰期分别为2.3 d和2.8 d，属易降解农药。最终残留试验结果表明：10% 阿维·氟酰胺悬浮剂按制剂用量450~675 g/hm²分别施药2和3次，间隔期5 d，距最后一次施药后7、14和21 d采样，氟虫双酰胺在茭白中的残留量均<0.01 mg/kg；25% 噻嗪酮可湿性粉剂按制剂用量600~900 g/hm²分别施药2和3次，间隔期5 d，距最后一次施药后7、14和21 d采样，噻嗪酮在茭白中的残留量为<0.005~0.078 mg/kg。建议10%阿维·氟酰胺悬浮剂最高制剂用量为450 g/hm²，最多施药2次，安全间隔期以7 d为宜；25%噻嗪酮可湿性粉剂最高制剂用量为675 g /hm²，最多施药2次，安全间隔期以21 d为宜。
- 超高效液相色谱-串联质谱 (UPLC-MS/MS) /
- 氟虫双酰胺 /
- 噻嗪酮 /
- 茭白 /
- 残留 /
- 消解
Abstract: A new method had been developed to determine flubendiamid and buprofezin residues in Zizania latifolia. Samples were extracted by acetonitrile, nitrogen blowing to near dry, dissolve with methanol and clean up with PSA, gradient elution with 0.1% formic acid and methanol, then positive ions electrospray scanning with multiple reaction monitoring mode, detection with ultra high performance liquid chromatography tandem mass spectrometry, external standard method of quantitative. When the spike levels of flubendiamid and buprofezin ranged from 0.005 mg/kg to 1 mg/kg, the mean recoveries varied from 81% to 107% with the coefficient of variation of 4.2%–11%, respectively. The dissipation dynamics of flubendiamid and buprofezin conformed to first order kinetics equation with the half-lives was 2.3 d and 2.8 d, respectively. Given that the half-lives was short, flubendiamid and buprofezin could be classcified as the easily degradable pesticide type. In the final residue trials, at the 7^th, 14^th and 21^th days after the last spraying, the final residues of 10% avermectin·flubendiamid SC and 25% buprofezin WP were determined after two and three applications at levels of 450–675 g/hm² and 600–900 g/hm². The results revealed that residues of flubendiamid was lower than 0.01 mg/kg and that of buprofezin varied from lower than 0.005 mg/kg to 0.078 mg/kg. In conclusion, when 10% avermectin·flubendiamid SC were sprayed on Zizania latifolia twice according to the recommended dose of 450 g/hm², the safety interval of buprofezin in Zizania latifolia could be set as 7 d．When 25% buprofezin WP were sprayed in Zizania latifolia twice according to the recommended dose of 675 g/hm², the safety interval of buprofezin in Zizania latifolia could be set as 21 d．
- ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) /
- flubendiamid /
- buprofezin /
- Zizania latifolia /
- residue /
- dissipation

HTML全文

图 1 氟虫双酰胺和噻嗪酮在茭白植株中的色谱图

a. 0.001 mg/kg 基质匹配标准溶液; b. 植株空白样品; c. 植株中添加0.01 mg/kg氟虫双酰胺和0.005 mg/kg噻嗪酮。

Figure 1. The chromatogram of flubendiamide and buprofezin in bract matrix

a. Matrix-matched standard solution of 0.001 mg/kg; b. Blank control of bract; c. Fortified 0.01 mg/kg flubendiamide and 0.005 mg/kg buprofezin in bract matrix.

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图 2 氟虫双酰胺和噻嗪酮在茭白植株中的消解曲线

Figure 2. The residue dynamic curves of flubendiamide and buprofezin in bract

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表 1 流动相及流速

Table 1. The mobile phase and the flow rate

时间 Time/min	流速 Flow/(mL/min)	流动相 Mobile phase/%
时间 Time/min	流速 Flow/(mL/min)	A	B
初始 Initial	0.3	80	20
1.00	0.3	80	20
3.00	0.3	20	80
5.00	0.3	20	80
7.10	0.3	80	20
8.00	0.3	80	20

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表 2 质谱分析参数

Table 2. MS/MS parameters

化合物 Compound	母离子 Parent ion, m/z	子离子 Daughter ion, m/z	驻留时间 Dwell time/s	锥孔电压 Cone voltage/V	碰撞电压 Collision voltage/eV
氟虫双酰胺 flubendiamide	683.16	273.81	0.310	14	31
氟虫双酰胺 flubendiamide		407.86^*	0.310	14	12
噻嗪酮 buprofezin	305.99	201.00	0.310	12	18
噻嗪酮 buprofezin		105.96^*	0.310	12	36
注 (Note)：^*为定量离子 (quantitative ion)。

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表 3 氟虫双酰胺和噻嗪酮的线性回归方程

Table 3. Equation of linear regression of flubendiamide and buprofezin

农药 Pesticide	基质 Matrix	线性方程 Linear equation	决定系数 R²
氟虫双酰胺 flubendiamide	植株 Bract	y = 2.6 × 10²x - 1.5 × 10³	0.998 1
氟虫双酰胺 flubendiamide	茭白Stem	y = 2.3 × 10²x + 3.0 × 10²	0.995 4
噻嗪酮 buprofezin	植株 Bract	y = 4.0 × 10⁴x + 6.8 × 10⁵	0.990 7
噻嗪酮 buprofezin	茭白 Stem	y = 3.9 × 10⁴x + 5.4 × 10⁵	0.990 3

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表 4 氟虫双酰胺和噻嗪酮在茭白植株和茭白中的添加回收率及相对标准偏差 (n = 5)

Table 4. Recoveries and relative standard deviation of flubendiamide and buprofezin in brcct and stem at three spiked levels (n = 5)

农药 Pesticide	添加水平 Spiked level/(mg/kg)	茭白植株 Bract		茭白 Stem
农药 Pesticide	添加水平 Spiked level/(mg/kg)	平均回收率 Mean recovery/%	相对标准偏差 RSD/%	平均回收率 Mean recovery/%	相对标准偏差 RSD/%
氟虫双酰胺 flubendiamide	0.01	81	7.3	83	9.6
	0.5	87	5.5	91	8.8
	1.0	83	6.9	93	7.6
噻嗪酮 buprofezin	0.005	99	7.1	91	11
	0.5	101	4.2	95	10
	1.0	107	9.7	100	6.5

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表 5 不同采样时间氟虫双酰胺和噻嗪酮在茭白植株中的残留量

Table 5. Residues of flubendiamide and buprofezin in bract at different sampling time

采样时间 Sampling time/d	氟虫双酰胺 flubendiamide		噻嗪酮 buprofezin
采样时间 Sampling time/d	残留量 Residue/(mg/kg)	消解率 Dissipation rate/%	残留量 Residue/(mg/kg)	消解率 Dissipation rate/%
0	0.423	/	0.956	/
1	0.316	25.3	0.846	11.5
3	0.163	61.5	0.523	45.3
5	0.096	77.3	0.225	76.5
7	0.051	87.9	0.134	86.0
14	0.012	97.2	0.076	92.1
21	< 0.01	/	0.016	98.3
28	< 0.01	/	< 0.005	/
消解动力学方程 Dissipation dynamics equation	C_t = 0.423 8e^{–0.304 6}^t		C_t = 1.004 9e^{–0.250 2}^t
R²	0.998 9		0.977 4
t_1/2/d	2.3		2.8

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表 6 不同采样时间氟虫双酰胺在茭白中的最终残留量

Table 6. Final residue of flubendiamide in stem at different sampling time

农药 Pesticide	制剂用量 Dosage/ (g/hm²)	施药次数 Application frequency	采样时间 Sampling time/d	残留量 Residue/ (mg/kg)
10% 阿维· 氟酰胺悬浮剂 10% avermectin· flubendiamid SC	450	2	7	< 0.01
			14	< 0.01
			21	< 0.01
		3	7	< 0.01
			14	< 0.01
			21	< 0.01
	600	2	7	< 0.01
			14	< 0.01
			21	< 0.01
		3	7	< 0.01
			14	< 0.01
			21	< 0.01

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表 7 不同采样时间噻嗪酮在茭白中的最终残留量

Table 7. Final residue of buprofezin in stem at different sampling time

农药 Pesticide	制剂用量 Dosage/ (g/hm²)	施药次数 Application frequency	采样时间 Sampling time/d	残留量 Residue/ (mg/kg)
25% 噻嗪酮可湿性粉剂 25% buprofezin WP	675	2	7	0.013
			14	0.007
			21	< 0.005
		3	7	0.034
			14	0.028
			21	0.019
	900	2	7	0.046
			14	0.015
			21	< 0.005
		3	7	0.078
			14	0.054
			21	0.059

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参考文献(19)

[1]	NISHIMATSU T, HIROOKA T. Flubendiamide: a new insecticide for controlling lepidopterous pests[C]//Brit Crop Prot Counciled. Proceedings of the BCPC International Congress-Crop Science Technology. Glasgow: Brit Crop Prot Council, 2005: 57-63.
[2]	KANNO H. An approach to a novel insect growth regulator buprofezin (Applaud)[J]. Pure Appl Chem, 1987, 59(8): 1027-1032.
[3]	陈新. 10%氟虫双酰胺·阿维菌素SC防治水稻二化螟田间药效试验[J]. 安徽农业通报, 2016, 22(9): 99, 138. CHEN X. Field test of 10% flubendiamide·avermection SC in control of rice stem borer[J]. J Anhui Agric Bull, 2016, 22(9): 99, 138.
[4]	吕敏, 陆玉荣, 苏建坤. 烯啶虫胺和噻嗪酮复配防治灰飞虱的增效作用[J]. 安徽农业科学, 2017, 45(10): 155-156, 158. LV M, LU Y R, SU J K. Study on synergism of nitenpyram and buprofezin to Laodelphax striatellus[J]. J Anhui Agric Sci, 2017, 45(10): 155-156, 158.
[5]	张珏锋, 陈建明, 何月平. 8种杀虫剂对茭白长绿飞虱的生物活性[J]. 浙江农业科学, 2016, 57(10): 1673-1675. ZHANG J F, CHEN J M, HE Y P. Bioactivity of 8 fungicides on Zizania latifolia of Saccharosydne procerus[J]. J Zhejiang Agric Sci, 2016, 57(10): 1673-1675.
[6]	李洋, 李淼, 柴宝山, 等. 新型杀虫剂氟虫酰胺[J]. 农药, 2006, 45(10): 697-699. LI Y, LI M, CHAI B S, et al. A new insecticide flubendiamide[J]. Agrochemicals, 2006, 45(10): 697-699.
[7]	刘金凤, 朱国念, 丁伟, 等. 超高效液相色谱-串联质谱法分析氟虫双酰胺在稻田生态系统中的消解动态[J]. 农药学学报, 2011, 13(3): 310-313. LIU J F, ZHU G N, DING W, et al. Residue decline study of flubendiamide in rice ecosyetem by UPLC-MS/MS[J]. Chin J Pestic Sci, 2011, 13(3): 310-313.
[8]	SAHOO S K, SHARMA R K, BATTU R S, et al. Dissipation kinetics of flubendiamide on chili and soil[J]. Bull Environ Contam Toxicol, 2009, 83(3): 384-387. doi: 10.1007/s00128-009-9782-9.
[9]	BATTU R S, SINGH B, KOONER R, et al. Simple and efficient method for the estimation of residues of flubendiamide and its metabolite desiodo flubendiamide[J]. J Agric Food Chem, 2008, 56(7): 2299-2302. doi: 10.1021/jf073081s.
[10]	汪芙蓉, 张家俊, 吴萍, 等. 噻嗪酮-烯啶虫胺在水稻田样品中的残留检测方法[J]. 南京农业大学学报, 2013, 36(6): 128-134. WANG F R, ZHANG J J, WU P, et al. Determination method of buprofezin and nitenpyram residues in rice field[J]. J Nanjing Agric Univ, 2013, 36(6): 128-134.
[11]	龙家寰, 李刚, 张盈, 等. 气相色谱-质谱联用快速检测杨梅中噻嗪酮残留[J]. 贵州农业科学, 2017, 45(10): 131-133. LONG J H, LI G, ZHANG Y, et al. Rapid detection of buprofezin residues in Myrica rubra by gas chromatograph-mass spectrometry[J]. Guizhou Agric Sci, 2017, 45(10): 131-133.
[12]	FENOLL J, RUIZ E, HELLÍN P, et al. Dissipation rates of insecticides and fungicides in peppers grown in greenhouse and under cold storage conditions[J]. Food Chem, 2009, 113(2): 727-732. doi: 10.1016/j.foodchem.2008.08.007.
[13]	GRIMALT S, POZO Ó J, SANCHO J V, et al. Use of liquid chromatography coupled to quadrupole time-of-flight mass spectrometry to investigate pesticide residues in fruits[J]. Anal Chem, 2007, 79(7): 2833-2843. doi: 10.1021/ac061233x.
[14]	农药残留试验准则: NY/T 788—2004[S]. 北京: 中国农业出版社, 2004. Guideline on pesticide residue trials: NY/T 788—2004[S]. Beijing: China Agriculture Press, 2004.
[15]	化学农药环境安全评价试验准则: GB/T 31270—2014[S]. 北京: 中国标准出版社, 2014. Test guidelines on environmental safety assessment for chemical pesticides: GB/T 31270—2014[S]. Beijing: Standards Press of China, 2014.
[16]	胡莲英. 噻嗪酮在水稻及土壤中的残留与消解[J]. 农药, 1990, 29(6): 37-38. HU L Y. Residue and dissipation of buprofezin in rice and soil[J]. Agrochemicals, 1990, 29(6): 37-38.
[17]	郑圣发, 周爱贤, 郑礼旺. 10%氟虫双酰胺·阿维菌素悬浮剂防治稻纵卷叶螟的效果研究[J]. 现代农业科技, 2014(10): 133, 136. ZHENG S F, ZHOU A X, ZHENG L W. The effect research of 10% flubendiamide·abamectin to control rice leaf-folder[J]. Mod Agric Sci Technol, 2014(10): 133, 136.
[18]	杨德毅. 茭白中阿维菌素和甲氨基阿维菌素苯甲酸盐的残留检测及降解规律研究[D]. 杭州: 浙江农林大学, 2015. YANG D Y. Study on residual detection and degradation rule of avermectin and emamectin benzoate in water bamboo[D]. Hangzhou: Zhejiang A&F University, 2015.
[19]	农业部农药检定所. 中国农药信息网-农药登记数据查询系统[DB/OL]. [2018-02-01]. http://www.chinapesticide.gov.cn/hysj/index.jhtml. Institute for the Control of Agrochemicals, Ministry of Agriculture. Pesticide registration data query system in China pesticide information network[DB/OL]. [2018-02-01].http://www.chinapesticide.gov.cn/hysj/index.jhtml.