基于分散固相萃取-超高效液相色谱串联质谱法同时测定蔬菜中多种除草剂残留的方法

doi:10.3864/j.issn.0578-1752.2017.21.010

摘要/Abstract

摘要：

【目的】研究吸附填料不同添加量对除草剂回收率的影响，以建立蔬菜中24种除草剂残留的分散固相萃取-超高效液相色谱串联质谱（UPLC-MS/MS）检测方法。【方法】蔬菜样品加入乙腈振荡提取，将净化填料N-丙基乙二胺（PSA）（不同添加量0.05 g、0.10 g、0.20 g）加入提取液中净化。采用UPLC-MS/MS测定，对液相色谱柱、流动相条件和质谱条件（锥孔电压、碰撞能量）进行优化，电喷雾电离，多反应监测模式检测。【结果】以0.1%的甲酸水-乙腈为流动相进行梯度洗脱，各化合物峰形尖锐，灵敏度高，UPLC-MS/MS上机10 min内完成了24种除草剂的检测。添加0.10 g和0.20 g PSA时，三氟羧草醚、2,4-滴、唑嘧磺草胺、噻吩磺隆、苯磺隆、氯嘧磺隆6种除草剂回收率明显降低；其余除草剂随着PSA添加量的增加回收率没有明显的变化，在75.5%—114.7%之间；吸附填料PSA添加量为0.05 g时，24种除草剂回收率为65.6%—114.7%。24种除草剂在1.0—250 µg·L^-1质量浓度范围内线性关系良好，相关系数为0.9946—0.9998。蔬菜中24种除草剂的方法检出限在1.2—160.8 µg·kg^-1，定量限在4.0—536.0 µg·kg^-1，可以满足定量分析的要求。在空白蔬菜样品中添加50、100、200 µg·kg^-1 3个质量分数的24种除草剂的混合标准溶液，24种除草剂的回收率在66.5%—116%，相对标准偏差在2.3%—9.7%。采用建立的测定方法，对38份蔬菜样本进行检测发现，所有蔬菜样品中仅检出阿特拉津残留，检出率为57.9%，检出范围为未检出—0.84 µg·kg^-1，其余23种除草剂均未检出。【结论】该方法简便、快速、节省溶剂、灵敏度高，可用于大批量蔬菜中除草剂残留快速检测。

关键词: 超高效液相色谱串联质谱法, 蔬菜, 除草剂, 分散固相萃取

Abstract: 【Objective】 To study the purification efficiency of different amount of absorption on the recovery of the herbicides, the ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) with dispersive solid phase extraction method was developed for the determination of 24 herbicides in vegetables．【Method】 The vegetable samples were extracted with acetonitrile and purified by primary-secondary amine (PSA) with different dosage of 0.05 g, 0.10 g and 0.20 g. UPLC-MS/MS method was performed with electrospray ionization (ESI) source under the multiple reaction monitoring (MRM) mode．【Result】0.1% formic acid water-acetonitrile was chosen as mobile phase in gradient elution, and the peaks of all the compounds were sharp with high sensitivity under this conditions. 24 kinds of herbicides were detected by UPLC-MS/MS within 10 min. Adding 0.10 g and 0.20 g PSA, the recovery rate of acifluorfen, 2,4-Dicholrophenoxyacetic acid, flumetsulam, thifensulfuron methyl, tribenuron methyl, and chlorimuron ethyl was decreased significantly, and the rest of the herbicides recovery did not change significantly, ranging from 75.5% to 114.7%. When adding 0.05 g PSA, 24 herbicides recovery rate was 65.6%-114.7%. Standards concentration ranged from 1.0 µg·L^-1 to 250 µg·L^-1 had a good linear relationship, and the correlation coefficient was 0.9946-0.9998. Limits of detection of 24 herbicides in vegetables ranged from 1.2 to 160.8 µg·kg^-1, and limit of quantitative between 4.0 and 536.0 µg·kg^-1, which can satisfy the requirement of quantitative analysis. The mixed standard solution of 24 herbicides were spiked in the blank vegetable samples at three levels 50, 100, 200 µg·kg^-1, and the recovery of 24 kinds of herbicides at the rate of 66.5%-116%, the relative standard deviation between 2.3%-9.7%, which can meet the requirements. Using the established determination method, 38 vegetable samples were detected, and only atrazine was detected in all vegetable samples with the detection rate of 57.9% and the detection range from not detected to 0.84 µg·kg^-1. The other remaining 23 kinds of herbicides were not detected.【Conclusion】The UPLC-MS/MS method is simple, rapid, solvent saving and sensitive, which is suitable for the determination of herbicides in a large number of vegetable samples.

Key words: ultra-high performance liquid chromatography-tandem mass spectrometry, vegetables, herbicides, dispersive solid phase extraction

平华，李杨，李冰茹，何昭颖，刘继培，马智宏. 基于分散固相萃取-超高效液相色谱串联质谱法同时测定蔬菜中多种除草剂残留的方法[J]. 中国农业科学, 2017, 50(21): 4159-4169.

PING Hua, LI Yang, LI BingRu, HE ZhaoYing, LIU JiPei, MA ZhiHong. Simultaneous Determination of Multi Herbicides Residues in Vegetables by Dispersive Solid Phase Extraction and Ultra-High Performance Liquid Chromatography-Tandem Mass Spectrometry[J]. Scientia Agricultura Sinica, 2017, 50(21): 4159-4169.

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参考文献

[1] 储晓刚. 大豆中除草剂残留定性定量检测技术研究[D]. 无锡: 江南大学, 2007.

CHU X G. Study on qualitative and quantitative analysis technology for herbicide residues in soybean[D]. Wuxi: Jiangnan University, 2007. (in Chinese)

[2] 李继革, 施家威, 王玉飞. 固相萃取-气相色谱-串联质谱法测定大米中10种除草剂. 中国卫生检验杂志, 2016 (10): 1388-1392.

LI J G, SHI J W, WANG Y F. Determination of 10 herbicides in rice by solid-phase extraction-gas chromatography-tandem mass spectrometry method. Chinese Journal of Health Laboratory Technology, 2016(10): 1388-1392. (in Chinese)

[3] ZHANG L, YU R,WANG Z, LI N, ZHANG H, YU A. Determination of triazine herbicides in vegetables by ionic liquid foam floatation solid phase extraction high performance liquid chromatography. Journal of Chromatography B, 2014, 953-954(1): 132-137.

[4] YANG M. Determination of 25 pesticides in vegetables and fruits by QuEchERS. Pesticide Science and Administration, 2011, 32(11): 35-39.

[5] BERRADA H, FONT G, MOLTÓ J C. Application of solid-phase microextraction for determining phenylurea herbicides and their homologous anilines from vegetables. Journal of Chromatography A, 2004, 1042(1/2): 9-14.

[6] SANNINO A. Determination of phenylurea herbicide residues in vegetables by liquid chromatography after gel permeation chromatography and Florisil cartridge cleanup. Journal of Aoac International, 1998, 81(5): 1048-1053.

[7] ZHI J, MOU R, CHEN M, ZHU Z. Multi-residue determination of 15 phenylurea herbicides in vegetables using solid phase extraction and online post-column ultraviolet decomposition-fluorescent derivatiztion- high performance liquid chromatography. Chinese Journal of Chromatography, 2008, 26(1): 93-97.

[8] PASDAR Y, PIRSAHEB M, Akramipour R, Ahmadi- Jouibari T, FATTAHI N, SHARAFI K, GHAFFARI H R. Assessment of triazine herbicides residual in fruit and vegetables using ultrasound assisted extraction-dispersive liquid-liquid microextraction with solidification of floating organic drop. Journal of the Brazilian Chemical Society,2017, 28(7): 1247-1255.

[9] 曾正宏, 陈勇, 杨瑞章, 王太全, 张丹, 曹军. 分散固相萃取-气相色谱-质谱法测定水果和蔬菜中扑草净和禾草丹残留量. 理化检验:化学分册, 2010, 46(9): 1046-1048.

ZENG Z H, CHEN Y, YANG R Z, WANG T Q, ZHANG D, CAO J. GC-MS determination of residual amounts of prometryne and thioencarb in fruits and vegetables with dispersive solid phase extraction. Physical Testing and Chemical analysis Part B:Chemical Analysis, 2010, 46(9): 1046-1048. (in Chinese)

[10] 田宏哲, 白雪松, 苑馨方, 杜芳, 徐静. 气相色谱-电子捕获检测器同时测定瓜果类蔬菜中15种除草剂残留. 农药学学报, 2016, 18(5): 625-632.

TIAN H Z, BAI X S, YUAN X F, DU F, XU J. Simultaneous determination of fifteen herbicides in cucurbitaceous andsolanaceous vegetables by gas chromatography with electron caption detector. Chinese Journal of Pesticide Science, 2016, 18(5): 625-632. (in Chinese)

[11] 支建梁, 牟仁祥, 陈铭学, 朱智伟. 柱后紫外光解荧光衍生液相色谱法测定蔬菜中残留的15种苯脲除草剂. 色谱, 2008, 26(1): 93-97.

ZHI J L, MOU R X, CHEN M X, ZHU Z W. Multi-residue determinationof 15 phenylurea herbicides in vegetables using solid phase extraction and online post-column ultraviolet decomposition- fluorescent derivatization high performance liquid chromatography. Chinese Journal of Chromatography, 2008, 26(1): 93-97. (in Chinese)

[12] 金雁, 姚家彪, 赵颖, 郭隽, 蒋施, 潘伟, 刘宁, 钟钰. 高效液相色谱法测定蔬菜中磺酰脲类除草剂多残留量的研究. 检验检疫科学, 2008, 18(6): 7-10.

JIN Y, YAO J B, ZHAO Y, GUO J, JIANG S, PAN W, LIU N, ZHONG Y. Simultaneous determination of sulfonylurea herbicide residues in vegetables by HPLC. Inspection and Quarantine Science, 2008, 18(6): 7-10. (in Chinese),

[13] 杜晓林, 荫硕妍, 李荷丽, 苗虹, 吴永宁. 气相色谱-质谱法测定蔬菜中65种除草剂的残留量. 中国食品卫生杂志, 2013, 25(3): 241-245.

DU X L, YIN S Y, LI H L, MIAO H, WU Y N. Determination of 65 herbicides in vegetables by gas chromatography-mass spectrometry. Chinese Journal of Food Hygiene, 2013, 25(3): 241-245. (in Chinese)

[14] 刘海林, 耿安静, 陆晓宇, 朱将伟. LC-MS/MS测定蔬菜中残留的磺酰脲类除草剂. 江苏农业科学, 2015, 43(7): 325-327.

LIU H L, GENG A J, LU X Y, ZHU J W. Determination of sulfonylurea herbicides in vegetables by LC-MS/MS. Jiangsu Agricultural Sciences, 2015, 43(7): 325-327. (in Chinese)

[15] 俞志刚, 丁为民, 何敬, 徐义, 车成彬, 由君, 杨照地. MSPD- RRLC-UV/MS法同时检测果蔬中9种三嗪类除草剂残留量. 分析试验室, 2009, 28(9):38-42.

YU Z G, DING W M, HE J, XU Y, CHE C B, YOU J, YANG Z D. Determination of nine triazine herbicides residues in fruits and vegetables by MSPD-RRLC-UV/MS. Chinese Journal of Analysis Laboratory, 2009, 28(9): 38-42. (in Chinese)

[16] LEE J K, AHN K C, PARK O S, KO Y K, KIM D W. Development of an immunoassay for the residues of the herbicide Bensulfuron- Methyl. Journal of Agricultural and Food Chemistry, 2002, 50(7): 1791-1803.

[17] 王晓春, 王广, 焦杏春. 三嗪类除草剂分析方法研究进展. 农药, 2011, 50(5): 320-324.

WANG X C, WANG G, JIAO X C. Developments of the determination methods for triazine herbicides. Agrochemicals, 2011, 50(5): 320-324. (in Chinese)

[18] LACINA O, ZACHARIASOVA M, URBANOVA J, VACLAVIKOVA M, CAJKA T, HAJSLOVA J. Critical assessment of extraction methods for the simultaneous determination of pesticide residues and mycotoxins in fruits, cereals, spices and oil seeds employing ultra- high performance liquid chromatography–tandem mass spectrometry. Journal of Chromatography A, 2012, 1262(4): 8-18.

[19] DONG X, LIANG S X, SHI Z H, SUN H. Development of multi-residue analysis of herbicides in cereal grain by ultra- performance liquid chromatography-electrospray ionization-mass spectrometry. Food Chemistry, 2016, 192: 432-440.

[20] KACZY?SKI P, ?OZOWICKA B, JANKOWSKA M, HRYNKO I. Rapid determination of acid herbicides in soil by liquid chromatography with tandem mass spectrometric detection based on dispersive solid phase extraction. Talanta, 2016, 152: 127-136.

[21] KACZY?SKI P. Clean-up and matrix effect in LC-MS/MS analysis of food of plant origin for high polar herbicides. Food chemistry, 2017, 230: 524-531.

[22] 诸力, 王晨, 陈红平, 张颖彬, 周苏娟, 王国庆, 刘新. 超高效液相色谱-串联质谱法同时测定茶叶中 11种植物生长调节剂及吡虫啉, 啶虫脒的残留. 分析化学, 2017, 45(4): 529-536.

ZHU L, WANG C, CHEN H P, ZHANG Y B, ZHOU S J, WANG G Q, LIU X. Simultaneous determination of plant growth regulators and imidacloprid, acetamiprid in tea by ultra performance liquid chromatography-tandem mass spectrometry. Chinese Journal of Analytical Chemistry, 2017, 45(4): 529-536. (in Chinese)

[23] ANASTASSIADES M, LEHOTAY S J, STAJNBAHER D, SCHENCK F J. Fast and easy multiresidue method employing acetonitrile extraction/partitioning and “dispersive solid-phase extraction” for the determination of pesticide residues in produce. Journal of AOAC International, 2003, 86(2): 412.

[24] WILKOWSKA A, BIZIUK M. Determination of pesticide residues in food matrices using the QuEChERS methodology. Food Chemistry, 2011, 125(3): 803-812.

[25] SINHA S N, VASUDEV K, RAO M V V. Quantification of organophosphate insecticides and herbicides in vegetable samples using the “Quick Easy Cheap Effective Rugged and Safe”(QuEChERS) method and a high-performance liquid chromatography-electrospray ionization-mass spectrometry (LC-MS/MS) technique. Food chemistry, 2012, 132(3): 1574-1584.

[26] 周瑶敏, 熊艳, 袁林峰, 胡丽芳, 罗林广. 分散固相萃取法快速测定大米中的酰胺类除草剂. 中国粮油学报, 2010, 25(8): 113-116.

ZHOU Y M, XIONG Y, YUAN L F, HU L F, LUO L G. QuECHERS and gas chromatography determination of amid herbicides in rice. Journal of the Chinese Cereals and Oils Association, 2010, 25(8): 113-116. (in Chinese)

[27] 邱世婷, 侯雪, 杨晓凤, 韩梅, 刘炜, 易盛国. 凝胶渗透色谱-分散固相萃取-气相色谱法测定大豆中的多种除草剂. 西南农业学报, 2016, 29(3): 566-569.

QIU S T, HOU X, YANG X F, HAN M, LIU W, YI S G. Determination of herbicide residues in soybean by gel permeation chromatography(GPC) -dispersive solid phase extraction(d-SPE) - gas chromatography. Southwest China Journal of Agricultural Sciences, 2016, 29(3): 566-569. (in Chinese)

[28] 蒋振晖, 扎乌拉, 应铁进. 高效液相色谱-串联质谱法测定草莓中的4-氯苯氧乙酸和2,4-二氯苯氧乙酸. 中国食品学报, 2015, 15(11): 192-198.

JIANG Z H, ZHA W L, YING T J. Determination of 4- chlorophenoxyacetic acid and 2,4-dichlorophenoxyacetic acid in strawberry by Liquid Chromatography-Tandem Mass Spectrometry. Journal of Chinese Institute of Food Science and Technology, 2015, 15(11): 192-198. (in Chinese)

[29] JI F, ZHAO L X, YAN W, FENG Q Z, LIN J M. Determination of triazine herbicides in fruits and vegetables using dispersive solid-phase extraction coupled with LC-MS. Journal of Separation Science, 2008, 31(6-7): 961-968.

[30] 王玉健, 黄慧玲, 李华平, 梁振纲. 高效液相色谱-串联质谱法测定果蔬中6种三嗪类除草剂的残留量. 理化检验:化学分册, 2013, 49(10): 1223-1227.

WANG Y J, HUANG H L, LI H P, LIANG Z G. HPLC-MS/MS determination of residual amounts of 6 triazine herbicides in fruits and vegetables. Physical Testing and Chemical analysis Part B:Chemical Analysis, 2013, 49(10): 1223-1227. (in Chinese)

[31] 任传博, 田秀慧, 张华威, 刘云, 孙岩, 徐英江, 宫向红, 王茂剑. 固相萃取-超高效液相色谱-串联质谱法测定海水中13种三嗪类除草剂残留量. 质谱学报, 2013, 34(6): 353-361.

REN C B, TIAN X H, ZHANG H W, LIU Y, SUN Y, XU Y J, GONG X H, WANG M J. Determination of triazine herbicides in seawater using solid phase extraction- UPLC-MS/MS. Journal of Chinese Mass Spectrometry Society, 2013, 34(6): 353-361. (in Chinese)