固相萃取-超高效液相色谱-四极杆-飞行时间质谱法分析地表水中26种农药
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摘要
利用固相萃取-超高效液相色谱(UHPLC)-四极杆-飞行时间质谱(Q-TOF/MS)法建立了26种农药的快速筛查和检测方法.首先建立了包含26种农药的一级精确质量数及保留时间、二级离子谱库的数据库.通过谱库信息比对,可实现地表水中26种农药的无标准品的情况下定性鉴定.样品经过C18萃取小柱富集、净化,用乙腈-异丙醇(1∶1,V/V)洗脱.采用C18色谱柱分离,0.1%甲酸甲醇溶液(含10 mmol·L~(-1)乙酸铵)和0.1%甲酸水溶液(含10 mmol·L~(-1)乙酸铵)进行梯度洗脱,再利用UHPLC-Q-TOF/MS检测,外标法定量.结果表明,在线性范围内,26种农药的线性关系良好,线性相关系数≥0.994,加标回收率在67.74%—112.3%之间,相对标准偏差(RSD)0.45%—12.2%之间.
A rapid method for the screening and determination of 26 pesticides was developed based on solid phase extraction and ultrahigh performance liquid chromatography(UHPLC)-quadrupole time-of-flight mass spectrometry(Q-TOF/MS). Initially, a database containing the accurate mass, retention time and the MS/MS spectra of the 26 pesticides was established. Based on the above database, the qualitative identifications of the 26 pesticides in surface water were accomplished without comparison with the standard substances. The target compounds in real water samples were first enriched by solid phase extraction cartridges and then eluted out of the cartridges using acetonitrile/isopropanol solution(1∶1). The resultant samples were then loaded onto a reversed phase C18 column and subjected to separation under gradient elution using 0.1% formic acid in methanol and 0.1% formic acid in water(with 10 mmol·L~(-1) ammonium acetate) as binary mobile phases, further detected using UHPLC-Q-TOF/MS, and quantificated by external standard method. It was demonstrated that in the studied concentration range, all 26 pesticides exhibited very good linearity with the linear correlation coefficients all higher than 0.994. The recoveries ranged from 67.74% to 112.3% with the relative standard deviations(RSD) between 0.45% and 12.2%.
A rapid method for the screening and determination of 26 pesticides was developed based on solid phase extraction and ultrahigh performance liquid chromatography(UHPLC)-quadrupole time-of-flight mass spectrometry(Q-TOF/MS). Initially, a database containing the accurate mass, retention time and the MS/MS spectra of the 26 pesticides was established. Based on the above database, the qualitative identifications of the 26 pesticides in surface water were accomplished without comparison with the standard substances. The target compounds in real water samples were first enriched by solid phase extraction cartridges and then eluted out of the cartridges using acetonitrile/isopropanol solution(1∶1). The resultant samples were then loaded onto a reversed phase C18 column and subjected to separation under gradient elution using 0.1% formic acid in methanol and 0.1% formic acid in water(with 10 mmol·L~(-1) ammonium acetate) as binary mobile phases, further detected using UHPLC-Q-TOF/MS, and quantificated by external standard method. It was demonstrated that in the studied concentration range, all 26 pesticides exhibited very good linearity with the linear correlation coefficients all higher than 0.994. The recoveries ranged from 67.74% to 112.3% with the relative standard deviations(RSD) between 0.45% and 12.2%.
引文
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[17] 朱永哲,冯雅男,金正汉.超高效液相色谱-串联质谱法同时测定土壤中239种农药的残留量[J].色谱,2013,31(9):850-861.ZHU Y Z,FENG Y N,JIN Z H.Determination of 239 pesticide residues in soil by ultra performance liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Chromatography,2013,31(9):850-861(in Chinese).
[18] 诸力,王晨,陈红平,等.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[J].分析化学,2017,45(4):529-536.ZHU L,WANG C,CHEN H P,et al.Simultaneous determination of plant growth regulators and imidacloprid,acetamiprid in tea by ultra performance liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Analytical Chemistry,2017,45(4):529-536 (in Chinese).
[19] MORENO-GONZ? LEZ D,ALC? NTARA-DUR? N J,GILBERT-L?PEZ B,et al.Matrix-effect free quantitative liquid chromatography mass spectrometry analysis in complex matrices using nanoflow LC with integrated emitter tip and high dilution factors[J].Journal of Chromatography A,2017,1519:110-120.
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[21] 陈小龙,李正翔,曹赵云,等.液相色谱-串联质谱法测定蔬菜和水果中6种新型酰胺类杀菌剂的残留量[J].色谱,2013,31(10):954-960.CHEN X L,LI Z X,CAO Z Y,et al.Determination of six novel amide fungicides in vegetables and fruits by liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Chromatography,2013,31(10):954-960 (in Chinese).
[22] 朱月芳,尹燕敏,秦宏兵.直接进样-超高效液相色谱串联质谱法同时测定水源水中9种农药[J].化学分析计量,2016,25(1):19-21.ZHU H F,YIN Y M,QIN H B.Simultaneous determination of 9 pesticides in water samples by ultra performance liquid chromatography-electrospray tandem mass spectrometry with direct injection [J].Chemical Analysis and Meterace,2016,25(1):19-21 (in Chinese).
[23] 吴春英,白鹭,谷风,等.固相萃取-超高效液相色谱-串联质谱法同时测定水中27种三嗪类除草剂[J].环境化学,2016,35(1):26-34.WU C Y,BAI L,GU F,et al.Simultaneous determination of 27 triazine herbicides in water using solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry [J].Environmental Chemistry,2016,35(1):26-34 (in Chinese).
[24] SANTE/11945/2015.Guidance Document on Analytical Quality Control and Method Validation Procedures for Pesticides Residues Analysis in Food and Feed[C].European Commission Directorate-General for Health and Food Safety.
[25] 刘辉,郑超红,何艺梅,等.水果蔬菜中7种新型生物农药残留检测方法研究[J].检验检疫学刊,2018,28(4):1-9.LIU H,ZHENG C H,HE Y M,et al.Study on the determination of 7 new biopesticides residues in fruits and vegetables [J].Journal of Inspection and Quarantine,2018,28(4):1-9 (in Chinese).
[2] 顾宝根,程燕,周军英,等.美国农药生态风险评价技术[J].农药学学报,2009,11(3):283-290.GU B G,CHENG Y,ZHOU J Y,et al.Review on USA pesticide ecological risk assessment techniques [J].Chinese Journal of Pesticide Science.2009,11(3):283-290 (in Chinese).
[3] 刘加莹.不安全蔬菜的安全处理[J].企业与市场,2002,9(1):22-23.LIU J Y.Safety treatment of unsafe vegetables [J].Enterprise and Market,2002,9(1):22-23 (in Chinese).
[4] 中华人民共和国国家环境保护总局.GB 3838-2002 地表水环境质量标准[S].北京:中国标准出版社,2002.State Environment Protection Administration.GB 3838-2002 Environmental quality standards for surface water [S].Beijing:Standards Press of China,2002(in Chinese).
[5] 徐玉娥,魏远隆,左海根,等.低温富集液液萃取-气相色谱-串联质谱法测定水样中15种农药残留[J].理化检验(化学分册),2015,51(1):1-5.XU Y E,WEI Y L,ZUO H G,et al.GC-MS/MS Determination of residual amounts of 15 pesticides in water samples with low-temperature enrichment liquid-liquid extraction [J].PTCA (Part B:Chem.Anal.),2015,51(1):1-5 (in Chinese).
[6] 王新平,杨云,栾伟,等.固相微萃取-气相色谱-质朴联用分析环境水样中痕量有机磷农药[J].分析试验室,2003,22(5):5-9.WANG X P,YANG Y,LUAN W,et al.Determination of organophosphorus pesticides in environmental water by solid-phase microextraction coupled with gas chromatography- mass spectrometry [J].Chinese Journal of Analysis Laboratory.2003,22(5):5-9 (in Chinese).
[7] 吴云辉,叶江雷.环境水中农药残留检测的富集净化过程综述[J].渔业研究,2014,36(2):159-166.WU Y H,YE H L.A review of process of enrichment and purify of pesticide residues in environment water for determination [J].Journal of Fujian Fisheries,2014,36(2):159-166(in Chinese).
[8] 孙静,徐雄,李春梅,等.固相萃取-超高效液相色谱-串联质谱法同时检测地表水中的35种农药及讲解产物[J].分析化学,2015,43(8):1145-1153.SUN J,XU X,LI C M,et al.Silmultaneous determination of thirty-five pesticides and transformation products in surface water using solid phase extraction combined with ultra-performance liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Analytical Chemistry,2015,43(8):1145-1153 (in Chinese).
[9] 罗晓燕,林玉娜,周洪伟,等.反相高效液相色谱法检测水中五种拟除虫菊酯农药残留量[J].中国卫生检验杂志,2011,21(6):1371-1372.LUO X Y,LIN Y N,ZHOU H W,et al.Determination of 5 sorts of pyrethroid pesticides residue in water by RP-HPLC [J].Chinese Journal of Health Laboratory Technology.2011,21(6):1371-1372 (in Chinese).
[10] 任琳,秦忠雪,朱婧,等.固相萃取-气相色谱-串联质谱法测定水中16种有机磷和有机氯农药残留[J].中国卫生检验杂志,2017,27(10):1396-1399.REN L,QIN Z X,ZHU J,et al.Determination of 16 organophosphorus and organochlorine pesticide residues in water by solid-phase extraction and gas chromatography-tandem mass spectrometry [J].Chinese Journal of Health Laboratory Technology.2017,27(10):1396-1399 (in Chinese).
[11] 樊吉平.ECD气相色谱法同时测定多种有机氯和有机磷农药[J].中国卫生检验杂志,2012,22(6):1253-1254.FAN J P.Determination of organochlorine and organophosphorus pesticides by ECD-GC [J].Chinese Journal of Health Laboratory Technology.2012,22(6):1253-1254 (in Chinese).
[12] LUCINI L,PELLEGRINO R,CIMINO N,et al.QqQ and Q-TOF liquid chromatography mass spectrometry direct aqueous analysis of herbicides and their metabolites in water[J].International Journal of Mass Spectrometry,2015,392:16-22.
[13] 沈登辉,单晓梅,陆蓓蓓,等.固相萃取-高效液相色谱法检测水中多种拟除虫菊酯类农药[J].环境与职业医学,2013,30(1):49-52.SHEN D H,SHAN X M,LU B B,et al.Determination of five pyrethroids in water using solid phase extraction high performance liquid chromatography [J].Journal of Environment and Occupation Medicine,2013,30(1):49-52(in Chinese).
[14] KACZYNSKI P,?OZOWICKA B,JANKOWSKA M,et al.Rapid determination of acid herbicides in soil by liquid chromatography with tandem mass spectrometric detection based on dispersive solid phase extraction.[J].Talanta,2016,152:127-136.
[15] 宋伟,林姗姗,孙广大,等.固相萃取-气相色谱-质谱联用同时测定河水和海水中87种农药[J].色谱,2012,30(3):318-326.SONG W,LIN S S,SUN G D,et al.Simultaneous determination of 87 pesticides in river water and seawater using solid phase extraction-gas chromatography-mass spectrometry [J].Chinese Journal of Chromatography,2012,30(3):318-326(in Chinese).
[16] WANG J,LEUNG D.Applications of ultra-performance liquid chromatography electrospray ionization quadrupole time-of-flight mass spectrometry on analysis of 138 pesticides in fruit- and vegetable-based infant foods[J].J Agric Food Chem,2009,57(6):2162-2173.
[17] 朱永哲,冯雅男,金正汉.超高效液相色谱-串联质谱法同时测定土壤中239种农药的残留量[J].色谱,2013,31(9):850-861.ZHU Y Z,FENG Y N,JIN Z H.Determination of 239 pesticide residues in soil by ultra performance liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Chromatography,2013,31(9):850-861(in Chinese).
[18] 诸力,王晨,陈红平,等.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[J].分析化学,2017,45(4):529-536.ZHU L,WANG C,CHEN H P,et al.Simultaneous determination of plant growth regulators and imidacloprid,acetamiprid in tea by ultra performance liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Analytical Chemistry,2017,45(4):529-536 (in Chinese).
[19] MORENO-GONZ? LEZ D,ALC? NTARA-DUR? N J,GILBERT-L?PEZ B,et al.Matrix-effect free quantitative liquid chromatography mass spectrometry analysis in complex matrices using nanoflow LC with integrated emitter tip and high dilution factors[J].Journal of Chromatography A,2017,1519:110-120.
[20] 王思威,刘艳萍,孙海滨,等.高效液相色谱-串联质谱法测定荔枝花粉和花蜜中腈菌唑和苯醚甲环唑残留[J].色谱,2018,36(1):17-22.WANG S W,LIU Y P,SUN H B,et al.Determination of myclobutanil and difenoconazole residues in pollen and honey of litchi by high performance liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Chromatography,2018,36(1):17-22 (in Chinese).
[21] 陈小龙,李正翔,曹赵云,等.液相色谱-串联质谱法测定蔬菜和水果中6种新型酰胺类杀菌剂的残留量[J].色谱,2013,31(10):954-960.CHEN X L,LI Z X,CAO Z Y,et al.Determination of six novel amide fungicides in vegetables and fruits by liquid chromatography-tandem mass spectrometry [J].Chinese Journal of Chromatography,2013,31(10):954-960 (in Chinese).
[22] 朱月芳,尹燕敏,秦宏兵.直接进样-超高效液相色谱串联质谱法同时测定水源水中9种农药[J].化学分析计量,2016,25(1):19-21.ZHU H F,YIN Y M,QIN H B.Simultaneous determination of 9 pesticides in water samples by ultra performance liquid chromatography-electrospray tandem mass spectrometry with direct injection [J].Chemical Analysis and Meterace,2016,25(1):19-21 (in Chinese).
[23] 吴春英,白鹭,谷风,等.固相萃取-超高效液相色谱-串联质谱法同时测定水中27种三嗪类除草剂[J].环境化学,2016,35(1):26-34.WU C Y,BAI L,GU F,et al.Simultaneous determination of 27 triazine herbicides in water using solid phase extraction-ultra performance liquid chromatography-tandem mass spectrometry [J].Environmental Chemistry,2016,35(1):26-34 (in Chinese).
[24] SANTE/11945/2015.Guidance Document on Analytical Quality Control and Method Validation Procedures for Pesticides Residues Analysis in Food and Feed[C].European Commission Directorate-General for Health and Food Safety.
[25] 刘辉,郑超红,何艺梅,等.水果蔬菜中7种新型生物农药残留检测方法研究[J].检验检疫学刊,2018,28(4):1-9.LIU H,ZHENG C H,HE Y M,et al.Study on the determination of 7 new biopesticides residues in fruits and vegetables [J].Journal of Inspection and Quarantine,2018,28(4):1-9 (in Chinese).