Currently, large amounts of agricultural solid wastes have caused serious environmental problems. Agricultural solid waste is made into biochar by pyrolysis, which is an effective means of its disposal. As the prepared biochar has a good adsorption capacity, it is often used to treat pollutants in water, such as heavy metals and pharmaceuticals. PRO is an emerging contaminant in the environment today. However, there are limited studies on the interaction between biochars with PRO. Thus, in this study, we investigate the adsorption of PRO onto the biochars derived from three different feedstocks. The order of adsorption capacity was corn stalk biochar (CS, 10.97 mg/g) > apple wood biochar (AW, 10.09 mg/g) > rice husk biochar (RH, 8.78 mg/g). When 2 < pH < 9, the adsorption capacity of all the biochars increased as the pH increased, while the adsorption decreased when pH > 9, 10 and 10.33 for AW, CS and RH, respectively. The adsorption of PRO on biochars was reduced with increasing Na⁺ and Ca²⁺ concentrations from 0 to 200 mg·L⁻¹. The effects of pH and coexisting ions illustrated that there exist electrostatic interaction and cation exchange in the process. In addition, when HA concentration was less than 20 mg/L, it promoted the adsorption of PRO on the biochars; however, when the concentration was more than 20 mg/L, its promoting effect was weakened and gradually changed into an inhibitory effect. The adsorption isotherm data of PRO by biochars were best fitted with the Freundlich model, indicating that the adsorption process is heterogeneous adsorption. The adsorption kinetics were fitted well with the pseudo-second-order model. All the results can provide new information into the adsorption behavior of PRO and the biochars in the aquatic environment and a theoretical basis for the large-scale application of biochar from agricultural solid wastes.

As an ideal carrier for the spread of pollutants in the aquatic environment, microplastics (MPs) can adsorb pharmaceutical β-blockers, which can affect their migration and lead to some unpredictable adverse consequences. In this paper, the sorption behaviors and mechanism of MPs (polyvinyl chloride (PVC) and polypropylene (PP)) for typical β-blocker metoprolol (MTL) were investigated. The effects of pH, salinity and humic acids (HAs) on the sorption were studied, which proved that the sorption behavior was different under different environmental conditions. Both low pH and high salinity inhibited the sorption of MTL by the MPs. Specifically, the sorption capacity of MTL increased, with pH increase from 3 to 10. When pH = 10, the sorption capacities of MTL on PVC (1.75 mg/g) and PP (3.34 mg/g) reached the maximum. After pH > 10, the amount of MTL adsorbed on PVC was slightly decreased, while that on PP was essentially the same. The addition of salt ions inhibited the sorption in the concentration range of 5–250 mg/g for both NaCl and CaCl₂, with the inhibitory effect of Ca²⁺ being stronger than that of Na⁺. Moreover, the presence of HAs promoted the sorption of MPs for MTL. In the absence of HAs, the sorption capacities of PP and PVC for MTL were 0.34 mg/g and 0.79 mg/g, respectively. When HA concentration was 100 mg/L, the highest sorption capacities of PP and PVC reached 0.79 mg/g and 1.37 mg/g, respectively. This indicated that the promoting effect of HAs on PP was stronger than that on PVC. In general, based on the study of the sorption behavior of MTL and the characterization of the MPs, the sorption mechanism was speculated to consist mainly of electrostatic interactions, cation exchange, hydrophobic interaction and halogen bonding. The sorption kinetics of MTL on the two MPs were well-fitted by the pseudo-second-order model with R² > 0.99. The sorption isotherms both fitted the Freundlich model, which substantiated that the sorption of MTL on the MPs (PVC and PP) was multilayered and heterogeneous. Collectively, these findings provided a theoretical basis for revealing the complex interactions between MPs and MTL in natural water and a new insight into the fate and migration of MPs and β-blockers in the environment.