Determination of Tetracyclines and Their Epimers in Agricultural Soil Fertilized with Swine Manure by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry

doi:10.1016/S1671-2927(00)8646

摘要/Abstract

摘要： A rapid, sensitive and specific ultra-high-performance liquid chromatography tandem mass spectrometry (UPLC-MS) method was developed for the analysis of tetracycline antibiotics, including tetracycline (TC), oxytetracycline (OTC), chlortetracycline (CTC) and their 4-epimers (4-epiTCs) in agricultural soil fertilized with swine manure. Soil samples were extracted and cleaned-up with 10 mL EDTA-McIlvaine buffer solution (pH 4.0), then cleaned-up and pre-concentrated using the Oasis MAX cartridge and then eluted with 1 mL solution by mixing formic acid, methanol and water at a ratio of 2:15:83 (v/v/v). The purified samples were separated by an ACQUITY UPLC BEH C18 column using acetonitrile and water containing 0.1% formic acid mobile phase and detected by a single quadrupole MS. The limits of detection for the soil extraction method (LODsoil) ranged from 0.6-2.5 μg kg-1 with recoveries from 23.3-159.2%. Finally, the method was applied to an agricultural field in an area with intensive pig-fattening farming. Tetracyclines were detected in soil from 2.8 to 42.4 μg kg-1 soil. These results demonstrate that soil from swine farms can become severely contaminated with tetracycline antibiotics and their metabolites.

关键词: tetracyclines, epimers, ultra performance liquid chromatography, soil, solid phase extraction

Abstract: A rapid, sensitive and specific ultra-high-performance liquid chromatography tandem mass spectrometry (UPLC-MS) method was developed for the analysis of tetracycline antibiotics, including tetracycline (TC), oxytetracycline (OTC), chlortetracycline (CTC) and their 4-epimers (4-epiTCs) in agricultural soil fertilized with swine manure. Soil samples were extracted and cleaned-up with 10 mL EDTA-McIlvaine buffer solution (pH 4.0), then cleaned-up and pre-concentrated using the Oasis MAX cartridge and then eluted with 1 mL solution by mixing formic acid, methanol and water at a ratio of 2:15:83 (v/v/v). The purified samples were separated by an ACQUITY UPLC BEH C18 column using acetonitrile and water containing 0.1% formic acid mobile phase and detected by a single quadrupole MS. The limits of detection for the soil extraction method (LODsoil) ranged from 0.6-2.5 μg kg-1 with recoveries from 23.3-159.2%. Finally, the method was applied to an agricultural field in an area with intensive pig-fattening farming. Tetracyclines were detected in soil from 2.8 to 42.4 μg kg-1 soil. These results demonstrate that soil from swine farms can become severely contaminated with tetracycline antibiotics and their metabolites.

Key words: tetracyclines, epimers, ultra performance liquid chromatography, soil, solid phase extraction

ZHENG Wen-li, ZHANG Li-fang, ZHANG Ke-yu, WANG Xiao-yang, XUE Fei-qun. Determination of Tetracyclines and Their Epimers in Agricultural Soil Fertilized with Swine Manure by Ultra-High-Performance Liquid Chromatography Tandem Mass Spectrometry[J]. Journal of Integrative Agriculture, 2012, 12(7): 1189-1198.

参考文献

[1]Aga D S, O’Connor S, Ensley S, Payero J O, Snow D, Tarkalson D. 2005. Determination of the persistence of tetracycline antibiotics and their degradates in manureamended soil using enzyme-linked immunosorbent assay and liquid chromatography-mass spectrometry. Journal of Agricultural Food Chemistry, 53, 7165-7171.

[2]Anderson C R, Rupp H S, Wu W H. 2005. Complexities in tetracycline analysis-chemistry, matrix extraction, cleanup, and liquid chromatography. Journal of Chromatography (A), 1075, 23-32.

[3]Ben W W, Qiang Z M, Adams C, Zhang H Q, Chen L P. 2008. Simultaneous determination of sulfonamides, tetracyclines and tiamulin in swine wastewater by solidphase extraction and liquid chromatography-mass spectrometry. Journal of Chromatography (A), 1202, 173-180.

[4]Bendahl L, Stürup S, Gammelgaard B, Hansen S H. 2005. UPLC-ICP-MS-a fast technique for speciation analysis. Journal of Analytical Atomic Spectrometry, 20, 1287-1289.

[5]Blackwell P A, Holten Lützhøft H C, Ma H P, Halling-Sørensen B, Boxall A B A, Kay P. 2004. Ultrasonic extraction of veterinary antibiotics from soils and pig slurry with SPE clean-up and LC-UV and fluorescence detection. Talanta, 64, 1058-1064.

[6]Cherlet M, Schelkens M, Croubels S, Backer P D. 2003. Quantitative multi-residue analysis of tetracyclines and their 4-epimers in pig tissues by high-performance liquid chromatography combined with positive-ion electrospray ionization mass spectrometry. Analytica Chimica Acta, 492, 199-213.

[7]Christian T, Schneider R J, Färber H A, Skutlarek D, Goldbach H E. 2003. Determination of antibiotic residues in manure, soil and surface waters. Acta Hydrochim Hydrobiol, 31, 36-44.

[8]Cooper A D, Stubbings G W F, Kelly M, Tarbin J A, Farrington W H H, Shearer G. 1995. Improved method for the on-line metal chelate affinity chromatography-high-performance liquid chromatographic determination of tetracycline antibiotics in animal products. Journal of Chromatography (A), 812, 312-326.

[9]De A J, Dong M Z, Yu J W, Hao W Z, Jin L C. 2008. Adsorption and cosorption of Cu (II) and tetracycline on two soils with different characteristics. Geoderma, 146, 224-230.

[10]Hamscher G, Sczesny S, Höper H, Nau H. 2002. Determination of persistent tetracycline residues in soil fertilized with liquid manure by high-performance liquid chromatography with electrospray ionization tandem mass spectrometry. Analytical Chemistry, 74, 1509-1518.

[11]Hamscher G, Pawelzick H T, Höper H, Nau H. 2005. Different behavior of tetracyclines and sulfonamides in sandy soils after repeated fertilization with liquid manure. Environmental Toxicology and Chemistry, 24, 861-872.

[12]Jacobsen A M, Halling-Sorensen B, Ingerslev F, Hansen S H. 2004. Simultaneous extraction of tetracycline, macrolide and sulfonamide antibiotics from agricultural soils using pressurized liquid extraction, followed by solid-phase extraction and liquid chromatographytandem mass spectrometry. Journal of Chromatography (A), 1038, 157-170.

[13]Jin H, Kumar A P, Paik D H, Ha K C, Yoo Y J, Lee Y I. 2010. Trace analysis of tetracycline antibiotics in human urine using UPLC-QToF mass spectrometry. Microchemical Journal, 94, 139-147.

[14]Jia A, Xiao Y, Hu J Y, Asami M, Kunikane S. 2009. Simultaneous determination of tetracyclines and their degradation products in environmental waters by liquid chromatography-electrospray tandem mass spectrometry. Journal of Chromatography (A), 1216, 4655-4662.

[15]Karci A, Balcioglu I A. 2009. Investigation of the tetracycline, sulfonamide, and fluoroquinolone antimicrobial compounds in animal manure and agricultural soils in Turkey. Science of the Total Environment, 407, 4652-4664.

[16]de Liguoro M, Cibin V, Capolongo F, Halling-Sørensen B, Montcsissa C. 2003. Use of oxytetracycline and tylosin in intensive calf farming: evaluation of transfer to manure and soil. Chemosphere, 52, 203-212.

[17]Lindsey M E, Meyer M, Thurman E M. 2000. Analysis of trace levels of sulfonamide and tetracycline antimicrobials in groundwater and surface water using solid-phase extraction and liquid chromatography/mass spectrometry. Analytical Chemistry, 73, 4640-4646.

[18]O’Connor S, Aga D S. 2007. Analysis of tetracycline antibiotics in soil: advances in extraction, clean up ,and quantification. Trends in Analytical Chemistry, 26, 456-462.

[19]O’Connor S, Locke J, Aga D S. 2007. Addressing the challenges of tetracycline analysis in soil: extraction, clean-up, and matrix effects in LC-MS. Journal of Environmental Monitoring, 9, 1254-1262.

[20]Oka H, Ito Y, Ikai Y, Kagami T, Harada K. 1998. Mass spectrometric analysis of tetracycline antibiotics in foods. Journal of Chromatography (A), 812, 309-319.

[21]Oka H, Ito Y, Matsumoto H. 2000. Chromatographic analysis of tetracycline antibiotics in foods. Journal of Chromatography A, 882, 109-133.

[22]Rabølle M, Spliid N H. 2000. Sorption and mobility of metronidazole, olaquindox, oxytetracycline and tylosin in soil. Chemosphere, 40, 715-722.

[23]Revert S, Borrull F, Plcurull E, Marc R M. 2003. Determination of antibiotic compounds in water by solid-phase extraction high-performance liquid chromatography (electrospray) mass spectrometry. Journal of Chromatography (A), 1010, 225-232.

[24]Schenck F J, Callery P S. 1998. Chromatographic methods of analysis of antibiotics in milk. Journal of Chromatography (A), 812, 99-109.

[25]Tereza T, Jana O, Petr N, Miroslav F. 2010. High-throuthput analysis of tetracycline antibiotics and their epimers in liquid manure using ultra performance liquid chromatography with UV detection. Chemosphere, 78, 353-359.

[26]Xu J Z, Ding T, Wu B, Yang W Q, Zhang X Y, Liu Y, Shen C Y, Jiang Y. 2008. Analysis of tetracycline residues in royal jelly by liquid chromatography-tandem mass spectrometry. Journal of Chromatography (B), 868, 42-48.

[27]de Zan M M, García M D Gil, Culzoni M J, Siano R G, Goicoechea H C, Galera M M. 2008. Solving matrixeffects exploiting the second order advantage in the resolution and determination of eight tetracycline antibiotics in effluent wastewater by modeling liquid chromatography data with multivariate curve resolutionalternating least squares and unfolded-partial least squares followed by residual bilinearization algorithms I. effect of signal pre-treatment. Journal of Chromatography (A), 1179, 106-114.