Simultaneous detection of pesticides and pharmaceuticals in three types of bio-based fertilizers by an improved QuEChERS method coupled with UHPLC-q-ToF-MS/MS

The interactions of oxytetracycline with model clay adsorbents were investigated as a function of suspension pH. The clay adsorbents used were native montmorillonite (SWy-2), Na-montmorillonite (Na-SWy-2), and hexadecyl trimethylammonium-montmorillonite (HDTMA-montmorillonite). The adsorption of oxytetracycline to the clay could be described by Freundlich-type adsorption isotherms. It was observed that the adsorption of oxytetracycline in the native and sodium forms of montmorillonite decreases with increasing pH in the order pH 1.5 > 5.0 > 8.7 > 11.0. This trend is consistent with cationic exchange interactions that are dominant at lower pH values when oxytetracycline has a net positive charge. On the other hand, hydrophobic interactions when oxytetracycline is zwitterionic (at pH 5.0) are predominant over other mechanisms, as evident from the FT-IR spectrum of the HDTMA-montmorillonite and humic acid-montmorillonite adsorbed with oxytetracycline. The presence of a large amount of dissolved organic matter (DOM) was also found to decrease the sorption of oxytetracycline to clay, suggesting that DOM may increase its mobility in the natural environment. Several mechanisms of interaction of oxytetracycline in clay are proposed based on the adsorption isotherms and the results from X-ray diffraction (XRD) and Fourier transform-infrared (FT-IR) analyses.