6 3 Vol. 6 No. 3 2015 3 Journal of Food Safety and Quality Mar., 2015 李增梅, 邓立刚 *, 赵善仓, 张树秋, 郭长英, 梁京芸, 董燕婕 (,, 250100) 摘要 : 目的,, (HPLC), 方法 / (v:v, 60:40), PCX, Waters Atlantis C 18 (3.6 mm 250 mm, 5 µm) 结果 (LOQ) 0.01 mg/kg; 0.02~10 µg/ml, R=0.9999 71.5%~94.5%, RSD 2.9%~6.5%, 2.8~5.1, 2.1~4.3 ;, 结论,, 关键词 : ; ; ; ; Residue decline study of nitenpyram in cotton and soil LI Zeng-Mei, DENG Li-Gang *, ZHAO Shan-Cang, ZHANG Shu-Qiu, GUO Chang-Ying, LIANG Jing-Yun, DONG Yan-Jie (Key Laboratory of Test Technology on Food Quality and Safety of Shandong Province, Institute of Agricultural Quality Standards and Testing Technology Research, Shandong Academy of Agricultural Sciences, Jinan 250100, China) ABSTRACT: Objective To establish a method for the determination of nitenpyram in cotton leaves and soil by high performance liquid chromatography (HPLC). Degradation of nitenpyramin cotton and soil using this HPLC method was studied. Methods Samples were extracted by methanol/water (60:40, v:v), and then purified by PCX extraction column. The analysis were separated on a Waters Atlantis C 18 (3.6 mm 250 mm, 5 µm)and detected by HPLC. Results This method provided a high linearity of the working curve for calibration as well as repeatability and reproducibility. The limits of quantification (LOQ) were 0.01 mg/kg in cotton and soil. The correlation coefficient of the working curve for calibration was 0.9999 for the nitenpyram in the concentration range from 0.02 to 10 µg/ml. The recoveries of nitenpyram in cotton, seed and soil were 71.5%~94.5%, and RSD were 2.9%~6.5%. The results showed the half-lives of nitenpyram were 2.8~5.1 d at cotton, and 2.1~4.3 d in soil. The final residues of nitenpyram were undetectable. Conclusion The method is simple and accurate for the determination of nitenpyram. Nitenpyram was an easily degradable insecticide. KEY WORDS: high performance liquid chromatography; nitenpyram; cotton; soil; residues * 通讯作者 :,, E-mail: deng_ligang@163.com *Corresponding author: DENG Li-Gang, Research Associate, Institute of Agricultural Quality Standards and Testing Technology Research, Shandong Academy of Agricultural Sciences, Jinan 250100, China. E-mail: deng_ligang@163.com
3, : 1001 1 引言 (nitenpyram),,,, [1-4] [5,6],, [7], [8] MRL, 0.05 mg/kg, 0.5 mg/kg; 0.03 mg/kg, 0.5 mg/kg [9,10], [11-14] [14,15], [12] -; [13],,,,,,, [12],,, ; [7],,,,,,,, 2 材料与方法 2.1 仪器设备 Waters (2695, Waters ), (2487, Waters ); (IKA-WERLE T25BS2, IKA ); Heidolph (L4000, Heidolph ); (3K30, Sigma ); (KQ-500E, ); (IKA-MS3, IKA ); (SE202F, ); (10~100 µl, 100~1000 µl, Eppendorf ) (OA-SYS, Organomation ) 2.2 试剂 (>99%, Sigma ); (, Sigma ); (, ); (, ); (, ) 2.3 田间试验 2.3.1 试验设计, 30 m 2, 3,,, 67.5 g/hm 2 (), 45 g/hm 2 ( ),, 2010 2011 2.3.2 消解动态试验,, 1, 2 h 1 3 5 7 10 14 21 30 35 d, : 500 g, 25 ; : 0~10 cm 1 kg, 1 mm, 25 2.3.3 最终残留试验 2,, 2 3,, 7 14 21 d :, 1 kg,,, 25 : 0~15 cm 1 kg, 1 mm, -25 2.4 分析方法 2.4.1 标准溶液的配制 10.0 mg 100 ml
1002 6,, 100.0 µg/ml; 10.0 µg/ml, 0.10 0.25 0.50 1.00 5.00 10.00 µg/ml, 2.4.2 样品制备 : 5.0 g( 5.0 g), 25 ml ; (v:v, 60:40), 10 ml, PCX : 10.0 g, 25 ml, 2.4.3 净化 PCX(60 mg, 3 ml) 5 ml, 5 ml,, 3 ml, 10 ml, 3 ml (5%),, ; (v:v, 20:80)( 1 ml, 2 ml), 2.4.4 添加回收试验 0.01 0.03 0.10 mg/kg 3, 5 2.4.5 分析条件 : Atlantis C 18 (3.6 mm 250 mm, 5 µm); : 30 ; : :(90:10); : 1.0 ml/min; : 260 nm; : 10 µl 15.0 min 2.4.6 结果计算,,, : Cst Pi Vsti V R m Vi Psti : R: (mg/kg); Cst: (µg/ml); V sti : (µl); Pi: ; V: (ml); Vi: (µl); Psti: ; m: (g) 3 结果与分析 3.1 方法灵敏度 准确度和精密度 0.02~10 µg/ml, 10 µl 0.1~10 µg/ml, Y (µv*sec) X (µg/g) ( 1, A), Y=2370.5X-608.08, R 0.999994 0.01 mg/kg, (0.05 mg/kg),, 71.5%~93%, 76.5%~93.3%, 77.5%~94.5%, ( RSD ) 2.9% 6.5%, ( 1, B~K) 3.2 净化方法优化,,, PSA MgSO 4,,, PCX,,,, 3.3 烯啶虫胺在棉叶和土壤中的消解动态 1, 10 d, 2010 88.3%, >90%,, C=C 0 e -kt ( 1) 2010 2011 5.1 d 2.8 d, 2.9 d 2.9 d, 4.3 d 2.7 d, 4.4 d 2.1 d 3.4 烯啶虫胺在棉籽和土壤中的最终残留 ( 2),, (0.01 mg/kg):, ; ;,,,,
3, : 1003 1 HPLC Fig. 1 Chromatograms of blank sample and samples spiked with nitenpyram A: ; B: (1.0 μg/ml); C: ; D: (0.1 mg/kg); E: ; F: ; G: (0.1 mg/kg); H: ; I: ; J: (0.1 mg/kg); K: A: standard curve; B: nitenpyram standard spectrum (1.0 μg/ml); C: soil blank spectrum; D:soils map (0.1mg/kg); E: soil sample spectrum; F: cotton leaf blank spectrum; G: cotton leaves add maps (0.1mg/kg); H: cotton leaf sample spectrum; I: cottonseed blank spectrum; J: cottonseed adding spectrum (0.1 mg/kg); K: cottonseed sample spectrum.
1004 6 Table 1 表 1 烯啶虫胺在棉叶和土壤中的消解代谢规律 Dynamic degradation equation of nitenpyram in cotton leaves and soil (mg/kg) 1 (R) (d) (mg/kg) 1 (R) (d) 2010 2.8 C=2.1529e -0.1353t 0.9663 5.1 0.99 C=0.4551e -0.1607t 0.8398 4.3 2011 1.3 C= 0.8166e -0.2508t 0.9434 2.8 0.37 C=0.4161e -0.2535t 0.9767 2.7 2010 2.9 C= 0.7488e -02373t 0.9142 2.9 0.52 C= 2.9592e -01586t 0.9497 4.4 2011 2.2 C= 1.4613e -0.2424t 0.9634 2.9 0.43 C=0.4098e -0.3266t 0.9888 2.1 1) C t =C 0 e -kt, C t : t, mg/kg; C 0 : mg/kg; : ; t:, d Table 2 表 2 烯啶虫胺在棉叶 棉籽和土壤中的添加回收率 (n=5) The recoveries of nitenpyram in cotton, soil and cotton seed (n=5) (mg/kg) (%) 1 2 3 4 5 (%) RSD(%) 0.01 81.5 71.5 78 84.2 75.5 78.1 6.4 0.03 90.6 82 79.8 80 87.1 83.9 5.7 0.1 91.7 93 86.4 88.2 85.1 88.9 3.8 0.01 77.5 88.2 78.3 80.8 87.4 82.4 6.1 0.03 82.6 88 77.2 89.3 83.5 84.1 5.7 0.1 88 94.5 92.4 91.3 85.6 90.4 3.9 0.01 78.6 82.5 79.2 85 87.7 82.6 4.7 0.03 86 79 76.5 90.1 83.2 83.0 6.5 0.1 93.3 89.6 86.7 88 91.1 89.7 2.9 参考文献 [1]. [J]., 2011(3): 20 20. Cao DH. Nitenpyram [J]. Hunan Agric, 2011(3): 20 20. [2],. [J]., 2009(11): 16 18. Sun H, Yang CH. New insecticides Nitenpyram [J]. Fine Specialty Chem, 2009(11): 16 18. [3],,,. [J]., 2012, 16(2): 1 5. Li M, Cheng SX, Li HP, et al. Neonicotinoids nitenpyram review [J]. Agrochem Res Appl, 2012, 16(2): 1 5. [4]. [J]., 2010, 34: 018. Wang X. New pesticides-nitenpyram [J]. Agr Knowl, 2010, 34: 018. [5],,,. [J]., 2010, 22(9): 89 90 Shu ZL, Sun TD, Zhang F, et al. Control effect of nitenpyram against nilaparvata lugens in rice field [J]. Jiangxi J Agr Sci, 2010, 22 (9): 89 90 [6],,,. [J]., 2011, 42(8): 906 909 Ling Y, Zhong Y, Wei SD, et al. Toxicity of nitenpyram, ethofenprox and their mixtures on nilaparvatalugens [J]. J South Agric, 2011, 42(8): 906 909 [7],,. 10% 60% [J]., 2014, 35(1): 31 34 Tang XL, Chen WG, Sun HY. 10% Nitenpyram agent and 60% nitenpyram wettable powder toxicity determination under silkworm acute food [J]. China Sericult, 2014, 35(1): 31 34 [8],,,. 3 [J]., 2010, 49(1): 74 77. Xie HP, Song QA, Jin LH, et al. Toxicity measure of buprofezin,
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