Abstract
In this study, a simple and reliable method was developed for multiresidue analysis of 49 antibiotics in vegetables based on the quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure and liquid chromatography-quadrupole linear ion trap mass spectrometry determination. Premixed extraction salt packets were first used to simplify the sample extraction procedures. Different buffer systems and other parameters were optimized. Multiple reaction monitoring with information-dependent acquisition of enhanced product ion (MRM-IDA-EPI) mode was used to acquire MS/MS spectra along with MRM survey scan for library searching to prevent false positive/negative identification. The method limit of quantification (LOQs) was between 2 and 5 μg/kg for the target antibiotics. Recoveries for most of antibiotics ranged between 70 and 100% with RSD < 20%. Relative lower recoveries were observed for some of quinolones. The method was applied on quantification of 60 vegetable samples, and the obtained results revealed that 33% of the samples were found to be contaminated with antibiotics. False positive of demeclocycline was avoided benefited from the application of MS/MS library searching.
Similar content being viewed by others
References
Anastassiades M, Lehotay SJ, Stajnbaher D, Schenck FJ (2003) Fast and easy multiresidue method employing acetonitrile extraction/partitioning and dispersive solid-phase extraction for the determination of pesticide residues in produce. J AOAC Int 86(2):412–431
Bourdat-Deschamps M, Leang S, Bernet N, Daudin JJ, Nãlieu S (2014) Multi-residue analysis of pharmaceuticals in aqueous environmental samples by online solid-phase extraction-ultra-high-performance liquid chromatography-tandem mass spectrometry: optimisation and matrix effects reduction by quick, easy, cheap, effective, rugged and safe extraction. J Chromatogr A 1349:11–23
Boxall ABA, Johnson P, Smith EJ, Sinclair CJ, Stutt E, Levy LS (2006) Uptake of veterinary medicines from soils into plants. J Agric Food Chem 54(6):2288–2297
Bueno MJ, Agüera A, Gómez MJ, Hernando MD, García-Reyes JF, Fernandez-Alba AR (2007) Application of liquid chromatography/quadrupole-linear ion trap mass spectrometry and time-of-flight mass spectrometry to the determination of pharmaceuticals and related contaminants in wastewater. Anal Chem 79(24):9372–9384
Dorival-García N, Labajo-Recio C, Zafra-Gómez A, Juárez-Jiménez B, Vílchez JL (2015) Improved sample treatment for the determination of 17 strong sorbed quinolone antibiotics from compost by ultra high performance liquid chromatography tandem mass spectrometry. Talanta 138:247–257
He Z, Chen S, Wang L, Peng Y, Luo M, Wang W, Liu X (2015a) Multiresidue analysis of 213 pesticides in leek and garlic using QuEChERS-based method and gas chromatography-triple quadrupole mass spectrometry. Anal Bioanal Chem 407(9):2637–2643
He Z, Wang L, Peng Y, Luo M, Wang W, Liu X (2015b) Determination of selected polychlorinated biphenyls in soil and earthworm (Eisenia fetida) using a QuEChERS-based method and gas chromatography with tandem MS. J Sep Sci 38(21):3766–3773
He Z, Wang L, Peng Y, Luo M, Wang W, Liu X (2015c) Multiresidue analysis of over 200 pesticides in cereals using a QuEChERS and gas chromatography-tandem mass spectrometry-based method. Food Chem 169:372–380
Ho YB, Zakaria MP, Latif PA, Saari N (2012) Simultaneous determination of veterinary antibiotics and hormone in broiler manure, soil and manure compost by liquid chromatography-tandem mass spectrometry. J Chromatogr A 1262(21):160–168
Hou J, Wan W, Mao D, Wang C, Mu Q, Qin S, Luo Y (2015) Occurrence and distribution of sulfonamides, tetracyclines, quinolones, macrolides, and nitrofurans in livestock manure and amended soils of Northern China. Environ Sci Pollut Res 22(6):1–10
Hu W, Ma L, Guo C, Sha J, Zhu X, Wang Y (2012) Simultaneous extraction and determination of fluoroquinolones, tetracyclines and sulfonamides antibiotics in soils using optimised solid phase extraction chromatography-tandem mass spectrometry. Int J Environ Anal Chem 92(6):698–713
Huang Y, Cheng M, Li W, Wu L, Chen Y, Luo Y, Christie P, Zhang H (2013) Simultaneous extraction of four classes of antibiotics in soil, manure and sewage sludge and analysis by liquid chromatography-tandem mass spectrometry with the isotope-labelled internal standard method. Anal Methods 5(15):3721–3731
Lehotay SJ, Collaborators MO, Hans AVGMC, Gnter MVHTA, Mette LRFKM, Hammack EPABW, Karen JMCLA, Andr LMGMH, de Kok MHFS, Parker AWA (2007) Determination of pesticide residues in foods by acetonitrile extraction and partitioning with magnesium sulfate: collaborative study. J AOAC Int 90(2):485–520
Li XQ, Yang Z, Zhang QH, Li HM (2014a) Evaluation of matrix effect in isotope dilution mass spectrometry based on quantitative analysis of chloramphenicol residues in milk powder. Anal Chim Acta 807:75–83
Li XW, Xie YF, Li CL, Zhao HN, Zhao H, Wang N, Wang JF (2014b) Investigation of residual fluoroquinolones in a soil–vegetable system in an intensive vegetable cultivation area in Northern China. Sci Total Environ 468-469:258–264
Meng M, He Z, Xu Y, Wang L, Peng Y, Liu X (2017) Simultaneous extraction and determination of antibiotics in soils using a method based on quick, easy, cheap, effective, rugged and safe extraction and liquid chromatography with tandem mass spectrometry. J Sep Sci 40:3214–3220
Pan M, Wong CK, Chu LM (2014) Distribution of antibiotics in wastewater-irrigated soils and their accumulation in vegetable crops in the Pearl River Delta, southern China. J Agric Food Chem 62(46):11062–11069
Payá P, Anastassiades M, Mack D, Sigalova I, Tasdelen B, Oliva J, Barba A (2007) Analysis of pesticide residues using the quick easy cheap effective rugged and safe (QuEChERS) pesticide multiresidue method in combination with gas and liquid chromatography and tandem mass spectrometric detection. Anal Bioanal Chem 389(6):1697–1714
Qiao Q, Chen J, Dong QU, Yan T, Rong W (2002) Advances and characters of fertilizer application of protected field agriculture in China. J Hubei Agric Coll 22:373–376
Rajski Ł, Lozano A, Uclés A, Ferrer C, Fernández-Alba AR (2013) Determination of pesticide residues in high oil vegetal commodities by using various multi-residue methods and clean-ups followed by liquid chromatography tandem mass spectrometry. J Chromatogr A 1304:109–120
Sarmah AK, Meyer MT, Boxall AB (2006) A global perspective on the use, sales, exposure pathways, occurrence, fate and effects of veterinary antibiotics (VAs) in the environment. Chemosphere 65(5):725–759
Schlüsener MP, Bester K (2006) Persistence of antibiotics such as macrolides, tiamulin and salinomycin in soil. Environ Pollut 143(3):565–571
Shendy AH, Alghobashy MA, Gad Alla SA, Lotfy HM (2016) Development and validation of a modified QuEChERS protocol coupled to LC-MS/MS for simultaneous determination of multi-class antibiotic residues in honey. Food Chem 190:982–989
Wang J, Lin H, Sun W, Xia Y, Ma J, Fu J, Zhang Z, Wu H, Qian M (2016) Variations in the fate and biological effects of sulfamethoxazole, norfloxacin and doxycycline in different vegetable–soil systems following manure application. J Hazard Mater 304:49–57
Wang Y, Guo B, Liu Z, Jing R (2015) Development of a method for the analysis of multiclass antibiotic residues in milk using QuEChERS and liquid chromatography tandem mass spectrometry. Foodborn Pathog Dis 12(8):693–703
Zhang H, Luo Y, Wu L, Huang Y, Christie P (2015a) Residues and potential ecological risks of veterinary antibiotics in manures and composts associated with protected vegetable farming. Environ Sci Pollut Res Int 22(8):5908–5918
Zhang K, Wong JW, Yang P, Hayward DG, Sakuma T, Zou Y, Schreiber A, Borton C, Nguyen TV, Kaushik B (2012) Protocol for an electrospray ionization tandem mass spectral product ion library: development and application for identification of 240 pesticides in foods. Anal Chem 84(13):5677–5684
Zhang QQ, Ying GG, Pan CG, Liu YS, Zhao JL (2015b) Comprehensive evaluation of antibiotics emission and fate in the river basins of China: source analysis, multimedia modeling, and linkage to bacterial resistance. Environ Sci Technol 49(11):6772–6782
Zhang Z, Li X, Ding S, Jiang H, Shen J, Xia X (2016) Multiresidue analysis of sulfonamides, quinolones, and tetracyclines in animal tissues by ultra-high performance liquid chromatography-tandem mass spectrometry. Food Chem 204:252–262
Funding
This work was supported by the subproject of the national key research and development plan (grant number 2016YFD0201203).
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of Interest
Zeying He declares that he has no conflict of interest. Yuehua Wang declares that he has no conflict of interest. Yaping Xu declares that she has no conflict of interest. Xiaowei Liu declares that he has no conflict of interest.
Ethical Approval
This article does not contain any studies with human or animal subjects.
Informed Consent
Not applicable
Electronic Supplementary Material
ESM 1
(DOCX 753 kb)
Rights and permissions
About this article
Cite this article
He, Z., Wang, Y., Xu, Y. et al. Determination of Antibiotics in Vegetables Using QuEChERS-Based Method and Liquid Chromatography-Quadrupole Linear Ion Trap Mass Spectrometry. Food Anal. Methods 11, 2857–2864 (2018). https://doi.org/10.1007/s12161-018-1252-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s12161-018-1252-8