With the broadly application of antibiotics to treat infectious diseases in humans and animals, antibiotic contaminants such as tetracycline (TC) and ciprofloxacin (CIP) have been detected in soil environments, where iron oxide minerals and phosphate are ubiquitous. To date, the influence of phosphate on the adsorption behaviors of TC/CIP onto iron oxides is still poorly understood. In this study, the effects of phosphate on the adsorptions of TC and CIP onto iron oxide minerals were investigated. Adsorption isotherms showed that the adsorption affinities of TC and CIP onto the three iron oxide minerals were in the order of goethite > hematite > magnetite with or without phosphate, the trend was dominated by different surface area and amount of surface hydroxyl groups of iron oxide minerals. Meanwhile, TC contains more functional groups than CIP for bonding, which resulted in greater adsorption affinity of three iron oxides to TC than that to CIP. Interestingly, phosphate weakened TC adsorption, while enhanced CIP adsorption, on the three iron oxides. This observation was ascribed to that phosphate anion enhanced the surface negative charge of iron oxides, which reinforced the electrostatic repulsion between iron oxides and negatively charged TC, also reinforced the electrostatic attraction between iron oxides and positively charged CIP. Furthermore, the inhibitory effect of phosphate on TC adsorption was dramatically enhanced at high pH, while the promoting effect of phosphate on CIP adsorption was slightly changed with various pH. Our results highlight the importance of phosphate in exploring the environmental fate of antibiotics in natural environment.

Important properties of biochar as an effective soil amendment are its high water-holding capacity (WHC) and inhibition of water evaporation. However, the mechanism and the importance of biochar properties in controlling its own WHC and bound water evaporation remain little known. In this study, wheat straw and pine sawdust biochars were pyrolyzed in N₂-flow, CO₂-flow, and air-limitation environments at 300–750 ℃, and a series of the produced biochars’ properties were characterized to explore the dominant controlling factors of their WHC and bound water evaporation. The results have shown that with the increasing contents of hydrogen, nitrogen, and oxygen as well as such ratios as H/C, and (O + N)/C, WHC of the biochars was also increasing while the evaporation of biochar-bound water was decreasing. With an increase in the other studied factors, such as carbon content, pH, and specific surface area (SSA), WHC of the biochars was decreasing, and the evaporation of biochar-bound water was increasing. That was connected with the fact that biochar-nitrogen was mainly in pyridinic and pyrrolic forms, while oxygen was in the form of C = O and C–O bonds. These forms of nitrogen and oxygen could be the receptors of hydrogen bonds to link to H₂O molecules. Aliphatic hydrogen with a weak positive charge could be a donor of hydrogen bonds to link to H₂O molecules. However, high carbon content, as well as high SSA, indicated more exposed aromatic carbon (hydrophobic sites) that could suppress the binding of H₂O molecules. Additionally, high pH indicated that H₂O molecules were dominated by OH^–, which generated strong electrostatic repulsion with the negatively charged nitrogen- and oxygen-containing groups of biochar. It was also shown that the nitrogen-containing groups played a more important role (importance – 0.31) in WHC of the biochar than other parameters, including carbon, oxygen, hydrogen, ash contents, pH, SSA (importance from 0.02 to 0.09). Nitrogen, oxygen, and carbon contents had the most important influence on the evaporation of biochar-bound water in all studied factors. Furthermore, wheat straw biochar produced at low pyrolysis temperatures in N₂ atmosphere (with high nitrogen and oxygen contents) had the highest WHC and the lowest evaporation of biochar-bound water. Consequently, it can be suggested that biochar rich in nitrogen can be an effective water retention agent and can improve agricultural soil moisture. Graphical Abstract