QuEChERS Pretreatment Combined with Ultra-performance Liquid Chromatography–Tandem Mass Spectrometry for the Determination of Four Veterinary Drug Residues in Marine Products
The extant methods for detecting multi-residues in aquatic products can avoid the disadvantages of complex pretreatment, long time consumption, single detection type, and low sensitivity. Therefore, developing a method that enables a multi-residue detection of veterinary drugs is very important. QuEChERS is a simple, rapid, and efficient method for detecting multi-drug residues. In this work, QuEChERS pretreatment combined with ultra-performance liquid chromatography–tandem mass spectrometry was proposed to identify sulfamide, tetracycline, quinolone, and malachite green residues in oyster, scallop, squid, and cuttlefish. The sample was extracted by using acetonitrile solution containing 0.1% acetic acid, while the extract was purified by using the QuEChERS method. The target analytes were separated on an ACQUITY UPLC BEH chromatographic column by using acetonitrile solution as a mobile phase for the gradient elution. Quantification was performed by using the internal standard method. The recovery of the 21 tested compounds was within the range of 65.26 to 113.5% and the relative standard deviation was less than 6.78%, thereby proving the good repeatability of the method. The intra- and inter-day precisions were less than 6.26% and 6.02%, respectively, while the limits of detection and quantification were less than 0.8 μg/kg and 2.5 μg/kg, respectively. The proposed method was then applied to detect residues in 150 samples of oysters, scallops, squid, and cuttlefish obtained from eight regions, including Shenzhen, Dongguan, Zhaoqing, Shantou, Maoming, Jiangmen, Shanwei, and Huizhou in Guangdong Province. No residues were detected in any of these samples. In sum, the proposed detection method has good reproducibility, high sensitivity, and reliability.
KeywordsQuEChERS Ultra-performance liquid chromatography–tandem mass spectrometry Veterinary drug residues Marine products
The authors thank professor Gui-hua Liu from Shenzhen Center for Disease Control and Prevention, for his help in this experiment.
This work was supported by oriented subject of the State Key Laboratory of Marine Resource Utilization in South China Sea (Hainan University) (DX2017005) and the Natural Science Foundation of Hainan Province (2017CXTD001).
Compliance with Ethical Standards
Conflict of Interest
Jian Chen declares that he has no conflict of interest. Zhen Wei declares that he has no conflict of interest. Xian-ying Cao declares that she has no conflict of interest.
This article does not contain any studies with human or animal subjects.
- Amelin VG, Volkova NM, Timofeev AA, Tret'yakov AV (2015) QuEChERS sample preparation in the simultaneous determination of residual amounts of quinolones, sulfanilamides, and amphenicols in food using HPLC with a diode-array detector. J Anal Chem 70:1076–1084. https://doi.org/10.1134/s1061934815090026 CrossRefGoogle Scholar
- Fernandez-Torres R, Bello Lopez MA, Olias Consentino M, Callejon Mochon M, Ramos Payan M (2011) Enzymatic-microwave assisted extraction and high-performance liquid chromatography-mass spectrometry for the determination of selected veterinary antibiotics in fish and mussel samples. J Pharm Biomed Anal 54:1146–1156. https://doi.org/10.1016/j.jpba.2010.12.002 CrossRefGoogle Scholar
- Gomez-Ramirez P, Jimenez-Montalban PJ, Delgado D, Martinez-Lopez E, Maria-Mojica P, Godino A, Garcia-Fernandez AJ (2018) Development of a QuEChERS method for simultaneous analysis of antibiotics in carcasses for supplementary feeding of endangered vultures. Sci Total Environ 626:319–327. https://doi.org/10.1016/j.scitotenv.2018.01.060 CrossRefGoogle Scholar
- Hashimoto JC, Paschoal JAR, Queiroz SCN, Ferracini VL, Assalin MR, Reyes FGR (2012) A simple method for the determination of malachite green and leucomalachite green residues in fish by a modified QuEChERS extraction and LC/MS/MS. J AOAC Int 95:913–922. https://doi.org/10.5740/jaoacint.11-140 CrossRefGoogle Scholar
- Koesukwiwat U, Lehotay SJ, Miao S, Leepipatpiboon N (2010b) High throughput analysis of 150 pesticides in fruits and vegetables using QuEChERS and low-pressure gas chromatography-time-of-flight mass spectrometry. J Chromatogr A 1217:6692–6703. https://doi.org/10.1016/j.chroma.2010.05.012 CrossRefGoogle Scholar
- Lehotay SJ, Son KA, Kwon H, Koesukwiwat U, Fu W, Mastovska K, Hoh E, Leepipatpiboon N (2010) Comparison of QuEChERS sample preparation methods for the analysis of pesticide residues in fruits and vegetables. J Chromatogr A 1217:2548–2560. https://doi.org/10.1016/j.chroma.2010.01.044 CrossRefGoogle Scholar
- Li Y, Wen S, Chen Z, Xiao Z, Ma M (2015) Ultra-high performance liquid chromatography tandem mass spectrometry for simultaneous analysis of aflatoxins B1, G1, B2, G2, zearalenone and its metabolites in eggs using a QuEChERS-based extraction procedure. Anal Methods 7:4145–4151. https://doi.org/10.1039/c5ay00124b CrossRefGoogle Scholar
- Liu S, He H, Huang X, Jin Q, Zhu G (2015) Comparison of extraction solvents and sorbents in the quick, easy, cheap, effective, rugged, and safe method for the determination of pesticide multiresidue in fruits by ultra high performance liquid chromatography with tandem mass spectrometry. J Sep Sci 38:3525–3532. https://doi.org/10.1002/jssc.201500625 CrossRefGoogle Scholar
- Liu H-Y, Lin S-L, Fuh M-R (2016) Determination of chloramphenicol, thiamphenicol and florfenicol in milk and honey using modified QuEChERS extraction coupled with polymeric monolith-based capillary liquid chromatography tandem mass spectrometry. Talanta 150:233–239. https://doi.org/10.1016/j.talanta.2015.12.045 CrossRefGoogle Scholar
- Ma S, Han P, Li A, Wang J, Feng X, Wang M (2018) Simultaneous determination of trace levels of 12 steroid hormones in soil using modified QuEChERS extraction followed by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Chromatographia 81:435–445. https://doi.org/10.1007/s10337-017-3464-2 CrossRefGoogle Scholar
- Saint-Hilaire M, Inthavong C, Bertin T, Lavison-Bompard G, Guérin T, Fournier A, Feidt C, Rychen G, Parinet J (2018) Development and validation of an HPLC-MS/MS method with QuEChERS extraction using isotopic dilution to simultaneously analyze chlordecone and chlordecol in animal livers. Food Chem 252:147–153. https://doi.org/10.1016/j.foodchem.2018.01.092 CrossRefGoogle Scholar
- Saksit S, Saranya P, Chanat C, Phanwimol T, Jana H, Mario G (2018) Multiclass analysis of antimicrobial drugs in shrimp muscle by ultra high performance liquid chromatography-tandem mass spectrometry. J Food Drug Anal 2:1–17Google Scholar
- Shendy AH, Al-Ghobashy MA, Alla SAG, 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. https://doi.org/10.1016/j.foodchem.2015.06.048 CrossRefGoogle Scholar
- Vaclavik L, Krynitsky AJ, Rader JI (2014) Quantification of aristolochic acids I and II in herbal dietary supplements by ultra-high-performance liquid chromatography-multistage fragmentation mass spectrometry Food Additives and Contaminants Part a-Chemistry Analysis. Control Exposure & Risk Assessment 31:784–791. https://doi.org/10.1080/19440049.2014.892215 CrossRefGoogle Scholar
- Vela-Soria F, Iribarne-Duran LM, Mustieles V, Jimenez-Diaz I, Fernandez MF, Olea N (2018) QuEChERS and ultra-high performance liquid chromatography-tandem mass spectrometry method for the determination of parabens and ultraviolet filters in human milk samples. J Chromatogr A 1546:1–9. https://doi.org/10.1016/j.chroma.2018.02.060 CrossRefGoogle Scholar
- Xian Y, Wu Y, Dong H, Guo X, Wang B, Wang L (2017) Dispersive micro solid phase extraction (DMSPE) using polymer anion exchange (PAX) as the sorbent followed by UPLC-MS/MS for the rapid determination of four bisphenols in commercial edible oils. J Chromatogr A 1517:35–43. https://doi.org/10.1016/j.chroma.2017.08.067 CrossRefGoogle Scholar