E-alert
An Accelerated Solvent Extraction-Solid Phase Extraction-Gas Chromatography/Mass Spectrometry Method for Determination of 18 Pesticides in Paddy
-
摘要: 建立了加速溶剂萃取-固相萃取净化-气质联用法（ASE/SPE/GC-MS）测定稻谷中18种农药残留的方法.以乙腈为溶剂，样品经加速溶剂萃取（30 mL萃取池中，10.34 MPa压力、80℃条件下，加热5 min，用乙腈静态萃取3 min，循环2次，再用池体积60%的乙腈冲洗萃取池后用氮气吹扫100 s）后，过自制固相萃取柱净化（萃取速率：1滴/秒），洗脱旋蒸后正己烷定容，使用气相色谱-质谱联用仪分析.在优化条件下，18种农药在0.05~1.0 μg/mL质量浓度范围内的相关系数R2均大于0.99，浓度与峰面积之间呈良好的线性关系.分别以3倍标准偏差和8倍标准偏差计算检出限和定量限，18种农药的检出限为0.104~0.647 mg/kg，定量限为0.276~1.724 mg/kg.以空白样品为基体进行加标回收试验，平均回收率在82.5%~105.1%之间，相对标准偏差（RSD，n=6）为1.5%~6.4%.方法适用于稻谷中18种农药残留的检测.Abstract: A gas chromatography/mass spectrometry(GC/MS) method was established for the determination of 18 pesticides in paddy based on the accelerated solvent extraction (ASE) method:in the 30 mL extraction pool under a pressure of 10.34 MPa, heating for 5 min at 80℃, and static extracting with acetonitrile for 3 min, cycling for 2 times, then washing the extraction pool with acetonitrile of 60% of the pool volume, then purging for 100 s with nitrogen. And then a solid phase extraction (SPE) column with an extraction rate of 1 drop/second was used for the purification of sample. In this method, the samples were first extracted with acetonitrile, and then purified by SPE column and evaporated to dryness in a rotary evaporator. The pretreated samples were re-dissolved in n-hexane to a constant volume for the determination by GC/MS. Linear relationships between values of peak area and mass concentration of 18 pesticides were found in the range of 0.05~1.0 μg/mL, all of their linear correlation coefficients were more than 0.99. The limits of detection were 0.104~0.647 mg/kg, and the minimum quantitative limits were 0.276~1.724 mg/kg. The spiked recoveries were between 82.5%~105.1%, and the RSDs were between 1.5%~6.4%. The method is suitable for the determination of 18 pesticides in paddy.
-
Key words:
- ASE /
- SPE /
- GC/MS /
- paddy /
- pesticides
-
图 1 18种农药标准溶液色谱图(0.5 μg/mL)
(1)禾草敌, (2)甲拌磷, (3)异稻瘟净, (4)甲基毒死蜱, (5)甲基嘧啶磷, (6)毒死蜱, (7)嘧啶磷, (8)稻瘟灵, (9)三唑磷, (10)生物苄呋菊酯, (11)联苯菊酯，(12)氯氟氰菊酯, (13)氯菊酯, (14)氟氯氰菊酯, (15)氟氰戊菊酯, (16)氰戊菊酯, (17)苯醚甲环唑, (18)溴氰菊酯
Figure 1. Total ion chromatogram of 18 pesticides in standard solution(0.5 μg/mL)
表 1 GC-MS分析的18种农药名称、保留时间及定性、定量离子参数
Table 1. Pesticide, retention time, qualitative and quantitative selected ions parameters for GC-MS analysis
峰号 化合物名称 保留时间/min 定量离子 定性离子(定性比例/%) 1 禾草敌 7.53 126 126(100) 187(15) 127(9) 2 甲拌磷 8.46 121 75(100) 121(45) 97(42) 3 异稻瘟净 9.25 204 204(100) 132(38) 122(26) 4 甲基毒死蜱 9.54 286 286(100) 288(78) 125(94) 5 甲基嘧啶磷 9.79 290 290(92) 276(100) 305(48) 6 毒死蜱 10.04 197 197(46) 199(44) 314(24) 7 嘧啶磷 10.24 333 333(100) 318(90) 304(61) 8 稻瘟灵 11.18 118 118(100) 162(95) 189(82) 9 三唑磷 12.40 161 161(100) 162(76) 172(40) 10 生物苄呋菊酯 13.20 123 123(100) 171(26) 128(28) 11 联苯菊酯 13.81 181 181(100) 166(40) 165(32) 12 氯氟氰菊酯 14.6~16.0 181 181(100) 197(73) 208(65) 13 氯菊酯 16.9~7.2 183 183(100) 16349.1 165(46) 14 氟氯氰菊酯 18.1~18.8 163 163(100) 165(88) 206(45) 15 氟氰戊菊酯 19.60 199 199(100) 157(77) 181(45) 16 氰戊菊酯 22.05 167 152(44) 125(100) 167(73) 17 苯醚甲环唑 22.7~23 265 323(100) 265(99) 325(69) 18 溴氰菊酯 23.68 181 181(97) 253(100) 255(42) 
下载: 导出CSV
表 2 18种农药化合物的线性回归方程及相关系数
Table 2. Linear regression equation and correlation coefficient(R2)of 18 pesticides
序号 化合物名称 线性回归方程 相关系数R2 1 禾草敌 y=68 514x+1 556 0.999 6 2 甲拌磷 y=15 538x+481.7 0.999 5 3 异稻瘟净 y=46 322x-597.9 0.998 6 4 甲基毒死蜱 y=18 099x-79.99 0.998 5 5 甲基嘧啶磷 y=27 900x-314.0 0.997 7 6 毒死蜱 y=23 448x+844.6 0.997 5 7 嘧啶磷 y=17 616x-187.9 0.999 2 8 稻瘟灵 y=30 942x+1 711 0.997 1 9 三唑磷 y=25 879x+640.5 0.998 5 10 生物苄呋菊酯 y=96 920x+5 587 0.998 1 11 联苯菊酯 y=159 110x+1 081 0.999 1 12 氯氟氰菊酯 y=27 938x+284.7 0.997 2 13 氯菊酯 y=97 698x+151 3 0.998 3 14 氟氯氰菊酯 y=30 885x+2 436 0.999 3 15 氟氰戊菊酯 y=35 881x-1 245 0.998 8 16 苯醚甲环唑 y=24 542x-958.5 0.999 9 17 氰戊菊酯 y=20 651x-265.2 0.997 7 18 溴氰菊酯 y=18 044x-410.0 0.999 3
下载: 导出CSV
表 3 18种农药化合物的检出限及定量限
Table 3. Detection limit and quantitative limit of 18 pesticides
/(mg/kg) 序号 化合物名称 标准偏差(STD Dev) 检出限(MDL) 定量限(MDQ) 1 禾草敌 0.035 0.104 0.276 2 甲拌磷 0.129 0.388 1.035 3 异稻瘟净 0.115 0.345 0.919 4 甲基毒死蜱 0.079 0.237 0.632 5 甲基嘧啶磷 0.071 0.213 0.569 6 毒死蜱 0.050 0.151 0.402 7 嘧啶磷 0.057 0.172 0.459 8 稻瘟灵 0.057 0.171 0.455 9 三唑磷 0.198 0.594 1.584 10 生物苄呋菊酯 0.167 0.502 1.339 11 联苯菊酯 0.040 0.121 0.321 12 氯氟氰菊酯 0.128 0.383 1.022 13 氯菊酯 0.100 0.300 0.800 14 氟氯氰菊酯 0.049 0.146 0.389 15 氟氰戊菊酯 0.099 0.297 0.792 16 苯醚甲环唑 0.053 0.158 0.421 17 氰戊菊酯 0.216 0.647 1.724 18 溴氰菊酯 0.072 0.216 0.576
下载: 导出CSV
表 4 18种农药的回收率及精密度试验结果(n=6)
Table 4. Recovery and precision test results of 18 pesticides in paddy(n=6)
序号 化合物名称 加标质量分数/(mg/kg) 平均回收率/% 相对标准偏差RSD/% 1 禾草敌 0.5 87.4 3.6 2 甲拌磷 2.0 92.7 1.5 3 异稻瘟净 1.0 89.2 2.7 4 甲基毒死蜱 1.0 105.1 2.9 5 甲基嘧啶磷 1.0 96.3 5.1 6 毒死蜱 0.5 95.7 4.3 7 嘧啶磷 0.5 91.6 3.2 8 稻瘟灵 0.5 93.5 3.9 9 三唑磷 2.0 88.4 2.8 10 生物苄呋菊酯 2.0 82.5 6.4 11 联苯菊酯 0.5 98.1 4.5 12 氯氟氰菊酯 2.0 103.2 7.5 13 氯菊酯 1.0 99.5 3.6 14 氟氯氰菊酯 0.5 96.4 2.8 15 氟氰戊菊酯 1.0 94.2 5.4 16 苯醚甲环唑 0.5 90.5 6.1 17 氰戊菊酯 2.0 102.4 5.8 18 溴氰菊酯 1.0 101.7 4.1
下载: 导出CSV
-
[1] 陈京都, 吴红军, 王龙跟, 等. QuEChERs-LC-MS/MS快速分析稻谷中12种农药残留方法初探[J].中国稻米. 2016, 22(2):54-56. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=daom201602014&dbname=CJFD&dbcode=CJFQCHEN Jing-du, WU Hong-jun, WANG Long-gen, et al. Preliminary study on QuEChERS-LC-MS/MS method for rapid detection of 12 Kinds of pesticide residues in rice[J]. China Rice, 2016, 22(2):54-56. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=daom201602014&dbname=CJFD&dbcode=CJFQ [2] 赵祥梅, 董英, 王和胜, 等. QuEChERs-气-质联用法检测大米中12种农药残留物[J].中国食品学报, 2016, 10(2):214-219. https://www.wenkuxiazai.com/doc/46cb31f7172ded630b1cb62c.htmlZHAO Xiang-mei, DONG Ying, WANG He-sheng, et al. Determination of multi-residues for 12 pesticides in rice by QuEChERS and GC-MS-SIM[J]. Journal of Chinese Institute of Food Science and Technology, 2016, 10(2):214-219. https://www.wenkuxiazai.com/doc/46cb31f7172ded630b1cb62c.html [3] 程旺大, 张国平, 姚海跟, 等.我国优质安全稻米生产的现状及发展对策[J].上海交通大学学报:自然科学版, 2003, 21(2):144-150. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=shnx200302014&dbname=CJFD&dbcode=CJFQCHENG Wang-da, ZHANG Guo-ping, YAO Hai-gen, et al. Situation and strategies for production of high quality and safe rice in China[J].Journal of Shanghai Jiaotong University (Agricultural Science), 2003, 21(2):144-150. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=shnx200302014&dbname=CJFD&dbcode=CJFQ [4] Muralidharn S, Dhananjayan V, Jayanthi P. Organochlorine pesticides in commercial marine fishes of Coimbatore, India and their suitability for human consumption[J]. Enveion Res, 2009, 109:15. doi: 10.1016/j.envres.2008.08.006 [5] 孟晓萌, 郑晓冬, 潘少香.果蔬农残检测方法的研究[J].中国果菜, 2013, 12:29-33. http://d.wanfangdata.com.cn/Periodical_zggc201312013.aspxMENG Xiao-meng, ZHENG Xiao-dong, PAN Shao-xiang. Study on the detection methods of pesticide residues in fruits and vegetables[J]. China Fruit and Vegetable, 2013, 12:29-33. http://d.wanfangdata.com.cn/Periodical_zggc201312013.aspx [6] 时磊, 陈海英, 蔡小虎, 等.超声提取-气相色谱法同时测定稻谷中18种有机氯农药和7种多氯联苯[J].理化检验-化学分册, 2016, 52:1090-1094. doi: 10.11973/lhjy-hx201609023SHI Lei, CHEN Hai-ying, CAI Xiao-hu, et al. GC determination of 18 organochlorine pesticides and 7 polychloro biphenyls in rough rice with ultrasonic extraction of samples[J]. Physical Testing and Chemical Analysis Part B:Chemical Analgsis, 2016, 52:1090-1094. doi: 10.11973/lhjy-hx201609023 [7] 陈敏, 宋君.食品中有机磷农药残留检测的前处理方法[J].山西农业科学, 2016, 44(9):1412-1415. http://d.wanfangdata.com.cn/Periodical_fxcsxb201009017.aspxCHEN Min, SONG Jun. Pretreatment methods for the determination of organophos-phorus pesticides residues in food[J]. Journal of Shanxi Agricultural Sciences, 2016, 44(9):1412-1415. http://d.wanfangdata.com.cn/Periodical_fxcsxb201009017.aspx [8] 宋文斌, 姜俊, 佟克兴, 等.测定人参中有机氯农药残留量的样品萃取方法研究[J].现代科学仪器, 2007, 6:100-104. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=xdkxyq200706028SONG Wen-bin, JIANG Jun, TONG Ke-xing, et al. The study on sample extraction method for organochlorine pesticide multi-residues in ginseng[J]. Modern Scientific Instruments, 2007, 6:100-104. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=xdkxyq200706028 [9] 李胜杰, 张慧.结球甘蓝中菊酯类农残检测前处理条件优化[J].浙江树人大学学报:自然科学版, 2015, 3:29-33. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=srzr201503007&dbname=CJFD&dbcode=CJFQLI Sheng-jie, ZHANG Hui. Optimization of preprocessing conditions for detection of pyrethroid pesticide residues in cabbage[J]. Journal of Zhejiang Shuren University(Acta Scientiarum Naturalium), 2015, 3:29-33. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=srzr201503007&dbname=CJFD&dbcode=CJFQ [10] 杨佳佳, 佟玲, 吴淑奇, 等.加速溶剂萃取-气相色谱法测定谷物中有机氯农药和多氯联苯[J].岩矿测试, 2013, 32(3):487-494. http://d.wanfangdata.com.cn/Periodical_ykcs201303023.aspxYANG Jia-jia, TONG Ling, WU Shu-qi, et al. Determination of organochlorine pesticides and polychlorinated biphenyls in grains using gas chromatography with accelerated solvent extraction[J]. Rock and Mineral Analysis, 2013, 32(3):487-494. http://d.wanfangdata.com.cn/Periodical_ykcs201303023.aspx [11] 杜晓婷, 周敏, 张剑, 等.蔬菜中甲胺磷等5种有机氯农药残留量的分散液-液微萃取/气质联用技术检测[J].分析测试学报, 2010, 29(7):751-754. http://industry.wanfangdata.com.cn/jt/Detail/Periodical?id=Periodical_fxcsxb201007022DU Xiao-ting, ZHOU Min, ZHANG Jian, et al. Determination of five organophosphorus pesticide residues in vegetables based on dispersive liquid-liquid microextraction coupled with gas chromatography mass spectrometry[J]. Journal of Instrumental Analysis, 2010, 29(7):751-754. http://industry.wanfangdata.com.cn/jt/Detail/Periodical?id=Periodical_fxcsxb201007022 [12] GB 23200. 9-2016食品安全国家标准粮谷中475种农药及相关化学品残留量测定气相色谱-质谱法[S]. 北京: 中国标准出版社. 2016.GB 23200. 9-2016 National food safety standards-determination of 475 pesticides and related chemicals residues in grains gas chromatography-mass spectrometry[S]. BeiJing: China Standard Press, 2016. [13] 梅文泉, 陈兴连, 汪禄祥, 等.固相萃取-气相色谱-质谱联用法测定葱姜蒜中12种农药残留量[J].西南农业学报, 2016, 9:2138-2143. http://www.cnki.com.cn/Article/CJFDTotal-XNYX201609022.htmMEI Wen-quan, CHEN Xing-lian, WANG Lu-xiang, et al. Determination of 12 pesticide residues in ginger and garlic in allium allium by solid phase extraction and gas chromatography mass spectrometry[J]. Southwest China Journal of Agricultural Sciences, 2016, 9:2138-2143. http://www.cnki.com.cn/Article/CJFDTotal-XNYX201609022.htm [14] 吴丽华.固相萃取-气相色谱法测定植物油中多种拟除虫菊酯类农药残留的方法探讨[J].粮食与食品工业, 2013, 20(2):62-67. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=lssp201302025&dbname=CJFD&dbcode=CJFQWU Li-hua. Study on the methods for determination of various pyrethroid residue in vegetable oil by solid phase extraction-gas chromatography[J]. Cereal and Food Industry, 2013, 20(2):62-67. http://kns.cnki.net/KCMS/detail/detail.aspx?filename=lssp201302025&dbname=CJFD&dbcode=CJFQ -
点击查看大图
图(1) / 表(4)
计量
- 文章访问数: 1007
- HTML全文浏览量: 112
- PDF下载量: 36
- 被引次数: 0
