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Development of a UHPLC-MS/MS method for the measurement of chlortetracycline degradation in swine manure

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Abstract

An ultra-high-performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed capable of simultaneously measuring chlortetracycline (CTC), epi-chlortetracycline, and isochlortetracycline (ICTC), as well as other structurally related tetracyclines in swine manure. A simple sample preparation was used consisting of extraction, dilution, centrifugation, and ultrafiltration. The concentrations of analyte were calculated using d6-tetracycline as an internal standard in the matrix-matched standard curve. A solvent gradient resolved the compounds in 3.5 min with an additional 1.5 min of re-equilibration allowing the analyses of a large number of samples in a short period of time. MS/MS was used as the detection method giving analyte confirmation in addition to a large dynamic range and low detection limit. The UHPLC-MS/MS method successfully resolved multiple degradation products of CTC from the complex manure matrix. The method detection limits ranged from 1.9 pg/μL for CTC to 7.3 pg/μL for ICTC, and the calibration curve was linear from 1 to 10,000 pg/μL. The method was tested by measuring CTC and its degradation products as a function of time in incurred swine manure that had been incubated at three different temperatures (22 °C, 38 °C, and 55 °C). CTC concentration at 22 °C decreased 44% after 25 days; greater percentage decreases were observed when the manure was stored at elevated temperatures (96% and 98% for 38 °C and 55 °C, respectively). The concentration of the microbiologically inactivate isomer, ICTC, increased over the incubation period. At 22 °C, ICTC continued to increase through 25 days of incubation; at 38 °C, ICTC concentration plateaued on day 14 while at 55 °C ICTC concentration plateaued on day 7, with concentration increases of 198%, 374%, and 282% for 22 °C, 38 °C, and 55 °C, respectively.

Fate of chlortetracycline in swine manure digesters

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Acknowledgment

The authors wish to acknowledge Amy McGarvey for technical assistance and Jason Holthusen for LC-MS/MS operation.

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Authors and Affiliations

  1. USDA-Agricultural Research Service, Biosciences Research Laboratory, 1605 Albrecht Boulevard, Fargo, ND, 58102, USA

    Weilin L. Shelver

  2. USDA-Agricultural Research Service, U.S. Meat Animal Research Center, P. O. Box 166, Clay Center, NE, 68933, USA

    Vincent H. Varel

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  1. Weilin L. Shelver
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  2. Vincent H. Varel
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Correspondence to Weilin L. Shelver.

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Names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by USDA implies no approval of the product to the exclusion of others that may also be suitable. USDA is an equal-opportunity provider and employer.

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Shelver, W.L., Varel, V.H. Development of a UHPLC-MS/MS method for the measurement of chlortetracycline degradation in swine manure. Anal Bioanal Chem 402, 1931–1939 (2012). https://doi.org/10.1007/s00216-011-5637-4

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  • DOI: https://doi.org/10.1007/s00216-011-5637-4

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