High-sensitive determination of tetracycline antibiotics adsorbed on microplastics in mariculture water using pre-COF/monolith composite-based in-tube solid phase microextraction on-line coupled to HPLC-MS/MS

Microplastics (MPs) act as carriers for organic pollutants (e.g. antibiotics) and microorganisms (e.g. bacteria) in waters, leading to the proliferation of antibiotic resistance genes. Moreover, the antibiotics adsorbed on MPs may exacerbate this process. For further research, it is necessary to understand the types and amounts of antibiotics adsorbed on MPs. However, due to the heavy work of MPs collection and sample pretreatment, there is a lack of analytical methods and relevant data. In this study, an in-tube solid phase microextraction (IT-SPME) on-line coupled to HPLC-MS/MS method based on amorphous precursor polymer of three-dimensional covalent organic frameworks/monolith-based composite adsorbent was developed, which could efficiently capture, enrich and analyze tetracycline (TCs) antibiotics. Under the optimal extraction parameters, the developed method was capable of detecting TCs at levels as low as 0.48-1.76 pg. This method was applied to analyze the TCs adsorbed on MPs of different particle sizes in mariculture water for the first time, requiring a minimum amount of MPs of only 1 mg. Furthermore, it was observed that there could be an antagonistic relationship between algal biofilm and TCs loaded on MPs. This approach could open up new possibilities for analyzing pollutants on MPs and support deeper research on MPs.