Determination of 35 Antibiotics in Surface Water by High Performance Liquid Chromatography-Tandem Mass Spectrometry with Online Solid-Phase Extraction and Large-Volume Injection

LI Chaoqun; LI Lixiang; REN Yingjun; ZHAO Jinhua; HUANG Gang; ZHOU Shiyang; LIU Liping; JIANG Jingsi; LIANG Feng

doi:10.15898/j.ykcs.202404050076

Rock and Mineral Analysis > 2024 > 43(6): 945-956. > DOI: 10.15898/j.ykcs.202404050076

LI Chaoqun，LI Lixiang，REN Yingjun，et al. Determination of 35 Antibiotics in Surface Water by High Performance Liquid Chromatography-Tandem Mass Spectrometry with Online Solid-Phase Extraction and Large-Volume Injection[J]. Rock and Mineral Analysis，2024，43（6）：945−956. DOI: 10.15898/j.ykcs.202404050076

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Determination of 35 Antibiotics in Surface Water by High Performance Liquid Chromatography-Tandem Mass Spectrometry with Online Solid-Phase Extraction and Large-Volume Injection

1.
Hunan Geological Experimental and Testing Center, Changsha 410014, China
2.
Changsha Natural Resources Comprehensive Survey Center, China Geological Survey, Changsha 410600, China
3.
Analytical Applications Center, Shimadzu (China) Co., Ltd., Guangzhou Branch, Guangzhou 510656, China

More Information

Received Date: April 04, 2024
Revised Date: September 17, 2024
Accepted Date: September 26, 2024
Available Online: November 13, 2024
Published Date: November 13, 2024

Abstract

HIGHLIGHTS
(1) The sample pretreatment of the online SPE-HPLC-MS/MS method is simple, fast and convenient, which ensures the consistency of the detection process. The detection method meets the requirements of antibiotic detection in surface water with high accuracy and low detection limit.

(2) The developed method only required a 10mL sample. When the acidic and basic injection volume were both 3mL, the total sample run time was only 30min including sample uptake, injection, online preconcentration, and detection.

(3) A method for continuous determination of 35 antibiotics by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established..

ABSTRACT

Antibiotics are one of the emerging pollutants of concern in the world. Fast and efficient analytical methods for potential analysis of these pollutants are required, in order to control water quality and assure the safety of its use as a source of drinking water. However, there are few comprehensive methods to test multiple types of antibiotics in surface water. An online solid-phase extraction (SPE) of large-volume injection coupled with the high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method was used for the simultaneous determination of 35 antibiotics in surface water, including 9 sulfonamides, 16 quinolones, 4 macrolides, 4 tetracyclines and 2 other classes. According to compound retention in SPE column and pH condition experiments, moxifloxacin and danofloxacin were confirmed as alkaline injection (0.1% ammonia solution), while the remaining 33 antibiotics were acidic injection (0.1% formic acid solution). The analytes were detected by multiple reaction monitoring (MRM) mode and were quantified by an internal standard method. The correlation coefficients of 35 antibiotics were greater than 0.995 with the calibration concentration range from 1−500ng/L. The method limits of detection (MLD) were low, ranging between 0.1−5.2ng/L. At 3 spiked concentrations of 5ng/L, 50ng/L, and 200ng/L, the relative standard deviation (RSD) of matrix labeling (n=6) were 1.65%−12.3%, 0.2%−10.4% and 0.05%−9.92%, respectively. The recovery rate of target compounds spike in the water samples were 62.1%−93.1%, 65.4%−127% and 65.9%−124%, respectively. The developed method only required a small sample volume (10mL) and simple pretreatment. When the acidic and basic injection volume were both 3mL, the total sample run time was only 30min including sample uptake, injection, online preconcentration, and detection. The developed method was applied to the analysis of 35 antibiotics in 21 surface waters, of which the detection rate of lincomycin reached 90.5%, and the highest content of ofloxacin reached 98.2ng/L. Compared with the conventional offline detection method, the detection results of the two methods were consistent, but the online detection method was simple, sensitive, accurate and fast, and capable of the real-time detection of water samples, making it suitable for residual analysis of trace antibiotics in surface water.
- antibiotics,
- surface water,
- online solid-phase extraction,
- large-volume injection,
- HPLC-MS/MS

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References (38)

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