[1]潘波,姜蕾,王冰洁,等.直接进样和柱前衍生2种方法检测水中草甘膦及其降解产物的残留[J].南京农业大学学报,2020,43(5):853-861.[doi:10.7685/jnau.201911031]
 PAN Bo,JIANG Lei,WANG Bingjie,et al.Determination of glyphosate and its main metabolite aminomethyl phosphonic acid in water by two methods:direct injection and pre-column derivatization[J].Journal of Nanjing Agricultural University,2020,43(5):853-861.[doi:10.7685/jnau.201911031]
点击复制

直接进样和柱前衍生2种方法检测水中草甘膦及其降解产物的残留()
分享到:

《南京农业大学学报》[ISSN:1000-2030/CN:32-1148/S]

卷:
43卷
期数:
2020年5期
页码:
853-861
栏目:
植物科学
出版日期:
2020-09-15

文章信息/Info

Title:
Determination of glyphosate and its main metabolite aminomethyl phosphonic acid in water by two methods:direct injection and pre-column derivatization
作者:
潘波 姜蕾 王冰洁 林勇
中国热带农业科学院环境与植物保护研究所/农业农村部热带作物病虫害综合治理重点实验室, 海南 海口 571101
Author(s):
PAN Bo JIANG Lei WANG Bingjie LIN Yong
Environment and Plant Protection Institute, Chinese Academy of Tropical Agricultural Sciences/Key Laboratory of Integrated Pest Management of Tropical Crops, Ministry of Agriculture and Rural Affairs, Haikou 571101, China
关键词:
草甘膦氨甲基膦酸直接进样法柱前衍生法
Keywords:
glyphosateaminomethyl phosphonic aciddirect injectionpre-column derivatization
分类号:
O657.63
DOI:
10.7685/jnau.201911031
摘要:
[目的] 本文旨在建立不衍生直接通过液相色谱质谱联用(HPLC-MS/MS)检测水中草甘膦和氨甲基膦酸的方法,并对传统柱前衍生HPLC-MS/MS检测水中草甘膦和氨甲基膦酸的方法进行优化,进而对2种方法进行系统比较。[方法] 直接进样法:样品过0.22 μm水系滤膜后直接进样检测,以乙腈和16 mmol·L-1氨水为流动相,HSS T3色谱柱梯度洗脱,负离子源模式,HPLC-MS/MS检测;柱前衍生法:样品经过9-芴基甲基三氯甲烷(FMOC-Cl)柱前衍生后过0.22 μm水系滤膜,以乙腈和1%甲酸+10 mmol·L-1乙酸铵为流动相,BEH C18色谱柱梯度洗脱,正离子源模式,HPLC-MS/MS检测。[结果] 直接进样法:草甘膦和氨甲基膦酸在0.5~200 μg·L-1线性关系良好,检出限(以3倍信噪比计)分别为0.104和0.072 μg·L-1,定量限(以10倍信噪比计)分别为0.348和0.241 μg·L-1,空白水样2种物质5个浓度水平的添加回收率为81.98%~111.24%,相对标准偏差(RSD)为2.18%~16.52%。柱前衍生法:草甘膦和氨甲基膦酸在0.5~200 μg·L-1线性关系良好,检出限(以3倍信噪比计)分别为0.019和0.024 μg·L-1,定量限(以10倍信噪比计)分别为0.063和0.078 μg·L-1,空白水样2种物质5个浓度水平的添加回收率为85.56%~110.32%,RSD为0.44%~8.44%。[结论] 柱前衍生法和直接进样法都能满足水中草甘膦和氨甲基膦酸的检测要求,前者具有更好的灵敏度,但是需要复杂的衍生步骤,且衍生时间需4 h以上;而直接进样法省去衍生步骤,易于操作,方便快捷。
Abstract:
[Objectives] In order to quickly and accurately detect glyphosate and its main degradation products in water,a direct injection method was established,and systematically compared with commonly used the pre-column derivatization method which was optimized in this study.[Methods] Direct injection method:samples were injected directly after passing through 0.22 μm water-based filter membrane,and the chromatographic separation was performed on waters HSS T3 column with gradient elution using acetonitrile and 16 mmol·L-1 ammonia as mobile phases. Mass spectrometric acquisitions were carried out by means of multiple reaction monitoring (MRM) in the electrospray negative ionization mode. Pre-column derivatization method:before injection,the samples were firstly derivated by 9-fluorenyl methyl trichloromethane (FMOC-Cl),and then passed through 0.22 μm water system filter membrane. The chromatographic separation was performed on waters BEH C18 column with gradient elution using acetonitrile and 10 mmol·L-1 ammonium acetate in water +1% formic acid as mobile phases. Mass spectrometric acquisitions were carried out by means of multiple reaction monitoring in the electrospray positive ionization mode.[Results] Direct injection method:the calibration curve of glyphosate and AMPA was linear within the range of 0.5-200 μg·L-1,the limits of detection (S/N=3) were 0.104 and 0.072 μg·L-1,respectively,and the limits of quantification (S/N=10) were 0.348 and 0.241 μg·L-1,respectively. The recoveries in different samples at five spiked levels ranged from 81.98% to 111.24% with the relative standard deviations from 2.18% to 16.52%. Pre-column derivatization method:the calibration curve of glyphosate and AMPA was linear within 0.5-200 μg·L-1,the limits of detection (S/N=3) were 0.019 and 0.024 μg·L-1,respectively,and the limits of quantification (S/N=10) were 0.063 and 0.078 μg·L-1,respectively. The recoveries in different samples at five spiked levels ranged from 85.56% to 110.32% with the relative standard deviations from 0.44% to 8.44%.[Conclusions] The results showed that the methods of pre-column derivation and direct injection could both fulfil the requirements quantitative detection of glyphosate and aminomethyl phosphonic acid in water. Although pre-column derivation method was a little more sensitive,it required complex derivations operations and therefore took about 4 hours more. In contrast,direct injection did not need complex derivation steps,easier to operate,more convenient,time-saving and efficient.

参考文献/References:

[1] Safarpour H,Asiaie R. Determination of glyphosate as cross-contaminant in a commercial herbicide by capillary electrophoresis-electrospray ionization-mass spectrometry[J]. Electrophoresis,2010,26(7/8):1562-1566.
[2] Goodwin L,Startin J R,Goodall D M,et al. Tandem mass spectrometric analysis of glyphosate,glufosinate,aminomethylphosphonic acid and methylphosphinicopropionic acid[J]. Rapid Communications in Mass Spectrometry,2003,17(9):963-969.
[3] 卢信,赵炳梓,张佳宝,等. 除草剂草甘膦的性质及环境行为综述[J]. 土壤通报,2005,36(5):785-790. Lu X,Zhao B Z,Zhang J B,et al. Property and environmental behavior of herbicide glyphosate[J]. Chinese Journal of Soil Science,2005,36(5):785-790(in Chinese with English abstract).
[4] Sheals J,Sjoberg S,Persson P. Adsorption of glyphosate on goethite:molecular characterization of Surface complexes[J]. Environmental Science & Technology,2002,36(14):3090-3095.
[5] Gimsing A L,Borggaard O K. Effect of KCl and CaCl2 as background electrolytes on the competitive adsorption of glyphosate and phosphate on goethite[J]. Clays and Clay Minerals,2001,49(3):270-275.
[6] Bento C P M,Yang X,Gort G,et al. Persistence of glyphosate and aminomethylphosphonic acid in loess soil under different combinations of temperature,soil moisture and light/darkness[J]. Science of the Total Environment,2016,572:301-311.
[7] Bento C P M,van der Hoeven S,Yang X M,et al. Dynamics of glyphosate and AMPA in the soil surface layer of glyphosate-resistant crop cultivations in the loess Pampas of Argentina[J]. Environmental Pollution,2019,244:323-331.
[8] Coupe R H,Kalkhoff S J,Capel P D,et al. Fate and transport of glyphosate and aminomethylphosphonic acid in surface waters of agricultural basins[J]. Pest Management Science,2012,68(1):16-30.
[9] Stempvoort D R V,Roy J W,Brown S J,et al. Residues of the herbicide glyphosate in riparian groundwater in urban catchments[J]. Chemosphere,2014,95:455-463.
[10] Lopes F M,Sandrini J Z,Souza M M. Toxicity induced by glyphosate and glyphosate-based herbicides in the zebrafish hepatocyte cell line(ZF-L)[J]. Ecotoxicology and Environmental Safety,2018,162:201-207.
[11] Kwiatkowska M,Reszka E,Wozniak K,et al. DNA damage and methylation induced by glyphosate in peripheral blood mononuclear cells(in vitro study)[J]. Food and Chemical Toxicology,2017,105:93-98.
[12] 杨治峰,张振玲. 草甘膦生殖发育毒性的研究进展[J]. 环境与职业医学,2013,30(2):154-156. Yang Z F,Zhang Z L. Research progress on reproductive and developmental toxicity of glyphosate[J]. Journal of Environmental & Occupational Medicine,2013,30(2):154-156(in Chinese with English abstract).
[13] 周垂帆,李莹,张晓勇,等. 草甘膦毒性研究进展[J]. 生态环境学报,2013,22(10):1737-1743. Zhou C F,Li Y,Zhang X Y,et al. Research advance in ecotoxicity of glyphosate[J]. Ecology and Environmental Sciences,2013,22(10):1737-1743(in Chinese with English abstract).
[14] Richard S,Moslemi S,Sipahutar H,et al. Differential effects of glyphosate and roundup on human placental cells and aromatase[J]. Environmental Health Perspectives,2005,113(6):716-720.
[15] 郑和辉,卞战强,田向红,等. 正相色谱串联质谱法直接进样测定水体中的草甘膦和2,4-滴残留[J]. 环境卫生学杂志,2014,4(4):395-397. Zheng H H,Bian Z Q,Tian X H,et al. Detection of glyphosate and 2,4-D in water by normal-phase chromatography electrospray ionization tandem mass spectrometry[J]. Journal of Environmental Hygiene,2014,4(4):395-397(in Chinese with English abstract).
[16] 王聪,刘颖超,庞民好,等. 高效液相色谱柱后衍生法测定农田沟渠水中草甘膦残留[J]. 植物保护,2012,38(5):96-99. Wang C,Liu Y C,Pang M H,et al. Determination of glyphosate in the water of farmland ditch by high performance liquid chromatography-post column derivation[J]. Plant Protection,2012,38(5):96-99(in Chinese with English abstract).
[17] 刘拉平,武瑜,王玉堂,等. 柱前衍生高效液相色谱-串联质谱法测定土壤中草甘膦及其主要代谢物氨甲基膦酸[J]. 农药学学报,2015,17(4):439-446. Liu L P,Wu Y,Wang Y T,et al. Determination of glyphosate and its main metabolites aminomethylphosphonic acid in soil sample by high performance liquid chromatography-tandem mass spectrometry with pre-column derivatization[J]. Chinese Journal of Pesticide Science,2015,17(4):439-446(in Chinese with English abstract).
[18] 诸力,陈红平,周苏娟,等. 超高效液相色谱-串联质谱法测定不同茶叶中草甘膦、氨甲基膦酸及草铵膦的残留[J]. 分析化学,2015,43(2):271-276. Zhu L,Chen H P,Zhou S J,et al. Determination of glyphosate,aminomethyl phosphonic acid and glufosinate in different teas by ultra performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Analytical Chemistry,2015,43(2):271-276(in Chinese with English abstract).
[19] 叶美君,陆小磊,刘相真,等. 柱前衍生-超高效液相色谱-串联质谱测定茶叶中草甘膦、草铵膦及主要代谢物氨甲基膦酸残留[J]. 色谱,2018,36(9):873-879. Ye M J,Lu X L,Liu X Z,et al. Determination of glyphosate,glufosinate,and main metabolite aminomethylphosphonic acid residues in dry tea using ultra-high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography,2018,36(9):873-879(in Chinese with English abstract).
[20] 成婧,王美玲,龚强,等. 液相色谱-串联质谱法检测植物源食品中草甘膦及其代谢物的残留量[J]. 食品安全质量检测学报,2016,7(1):138-144. Cheng J,Wang M L,Gong Q,et al. Determination of glyphosate and aminomethylphosphonic acid residues inplant-derived foodstuff by high performance liquid chromatography-tandem mass spectrometry[J]. Journal of Food Safety and Quality,2016,7(1):138-144(in Chinese with English abstract).
[21] 李波,邓晓军,郭德华,等. 高效液相色谱-串联质谱法检测食品中的草甘膦及其主要代谢物氨甲基膦酸残留[J]. 色谱,2007,25(4):486-490. Li B,Deng X J,Guo D H,et al. Determination of glyphosate and aminomethyl phosphonic acid residues in foods using high performance liquid chromatography-mass spectrometry/masss spectrometry[J]. Chinese Journal of Chromatography,2007,25(4):486-490(in Chinese with English abstract).
[22] 中华人民共和国生态环境部南京环境科学研究所. 土壤和沉积物草甘膦的测定高效液相色谱法:HJ 1055-2019[S]. 北京:中国环境出版集团,2019. Nanjing Institute of Environmental Sciences,Ministry of Environmental Protection,PRC. Soil and sediment-determination of glyphosate:high performance liquid chromatography:HJ 1055-2019[S]. Beijing:China environment publishing group,2019(in Chinese).
[23] 中华人民共和国上海出入境检验检疫局. 植物性产品中草甘膦残留量的测定气相色谱-质谱法:GB/T 23750-2009[S]. 北京:中国标准出版社,2009. Shanghai Entry-exit Inspection and Quarantine Bureau,PRC. Determination of glyphosate residues in plant products:GC-MS method:GB/T 23750-2009[S]. Beijing:China Standards Press,2009(in Chinese).
[24] 中华人民共和国上海出入境检验检疫局. 进出口食品中草甘膦残留量的检测方法液相色谱-质谱/质谱法:SN/T 1923-2007[S]. 北京:中国标准出版社,2007. Shanghai Entry-exit Inspection and Quarantine Bureau,PRC. Determination of glyphosate residues in food for import and export:HPLC-MS/MS method:SN/T 1923-2007[S]. Beijing:China Standards Press,2007(in Chinese).
[25] 高俊海,宋桂雪,宋薇. 柱前衍生-液相色谱法测定土壤中草甘膦和氨甲基膦酸[J]. 现代科学仪器,2016(6):114-119. Gao J H,Song G X,Song W. Determination of glyphosate and aminomethyl phosphonic acid in soil samples by high performance liquid chromatography with pre-column derivatization[J]. Modern Scientific Instruments,2016(6):114-119(in Chinese with English abstract).
[26] 马建明,龚文杰,邬晨阳,等. 水中草甘膦的柱前衍生-固相萃取-高效液相色谱荧光法测定[J]. 中国卫生检验杂志,2014,24(18):2599-2601. Ma J M,Gong W J,Wu C Y,et al. Determination of glyphosate in water by high-performance liquid chromatography-fluorescence detection with pre-column derivatization and solid-phase extraction[J]. Chinese Journal of Health Laboratory Technology,2014,24(18):2599-2601(in Chinese with English abstract).
[27] 杨华梅,杭莉. 柱前衍生-固相萃取-高效液相色谱法测定饮用水中草甘膦和氨甲基膦酸[J]. 理化检验(化学分册),2015,51(4):474-477. Yang H M,Hang L. Determination of glyphosate and aminomethyl phosphonic acid in drinking water by SPE-HPLC combined with pre-column derivatization[J]. Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2015,51(4):474-477(in Chinese with English abstract).

相似文献/References:

[1]李小艳,许晅,李桂俊,等.赤霉素对草甘膦的增效作用及其作用机制[J].南京农业大学学报,2013,36(3):36.[doi:10.7685/j.issn.1000-2030.2013.03.006]
 LI Xiaoyan,XU Xuan,LI Guijun,et al.Synergism of gibberellin A3 to glyphosate and their mechanisms of action[J].Journal of Nanjing Agricultural University,2013,36(5):36.[doi:10.7685/j.issn.1000-2030.2013.03.006]

备注/Memo

备注/Memo:
收稿日期:2019-11-25。
基金项目:海南省重点研发计划项目(ZDYF2018056);中国热带农业科学院基本科研业务费专项资金(1630042017018);海南省重大科技项目(ZDKJ2017003)
作者简介:潘波,助理研究员。
通信作者:姜蕾,副研究员,研究方向为农药环境毒理和现代施药技术,E-mail:tina266045@126.com。
更新日期/Last Update: 1900-01-01