Co-adsorption of tetracycline and copper by the thiourea-modified porous sodium alginate microspheres

The gradual increase of antibiotics and heavy metals in aquatic environments poses a serious threat to human health and ecosystems, and finding effective methods for simultaneous removal of antibiotics and heavy metals has attracted increasing concern. In this study, a novel porous structure of thiourea-modified sodium alginate microspheres (UA-Ca) was synthesized by modification with thiourea, epichlorohydrin, and calcium chloride, and was applied for the simultaneous removal of tetracycline (TC) and Cu(II) from water. The results indicated that the UA-Ca material with 1:2 mass ratio of thiourea and sodium alginate showed the highest removal of TC and Cu(II) under the reaction condition of pH= 7. The removal process of both TC and Cu(II) follows the pseudo-second-order adsorption model and Langmuir isotherm model. UA-Ca had a high adsorption capacity toward TC and Cu(II) with the maximum value of 1.099 mmol/g and 2.793 mmol/g based on the Langmuir model at 298 K, respectively. Thermodynamical parameters revealed that TC and Cu(II) adsorption is spontaneous with endothermic nature. Competing ionic cations (Ca2+、Mg2+、NH4+) and organics (sulfamethoxazole, hygromycin) had a certain inhibitory effect on the removal of TC and Cu(II) by UA-Ca, whereas the anionic ions (CO32-、PO43-、SO42-) all had little effect on its removal. Fourier transform infrared spectra and X-ray photoelectron spectroscopy analyses showed that the removal of TC and Cu(II) by UA-Ca was mainly due to electrostatic adsorption and surface complexation. This work provides a promising UA-Ca material for the effective removal of TC and Cu(II) in contaminated water.