Antibiotics and ammonia are generally co-existed in aquaculture tailwater; moreover, ammonia would also be produced from during ozonation, and should be simultaneously removed before discharge or reuse. In this study, catalyst Cu-Co/γ-Al2O3 was screened from a variety of metal oxides and applied in catalytic ozonation of three kinds of antibiotics and NH+4-N. Factors that affected their removal, including catalyst dosages, O3 concentration, initial pH as well as co-existing ions, were investigated. Moreover, the mechanisms were probed by exploring free radicals’ role as well as intermediates identification; and the characteristics of catalysts before and after use were evaluated using SEM, EDS, XRD, XPS, and BET. Results demonstrated that Cu-Co/γ-Al2O3 could significantly stimulate the degradation of the selected antibiotics and NH+4-N during ozonation. The degradation efficiencies of ciprofloxacin (CIP), tetracycline (TC), sulfamethoxazole (SMX) and NH+4-N can reach up to 95.0 %, 100.0 %, 96.2 %, and 75.7 %, respectively. Plenty of oxygen vacancy (Ovs) and sufficient alkaline sites on the surface of catalyst facilitated the adsorption of pollutants. Furthermore, the transformation of metal ions Cu+/Cu2+ and Co2+/Co3+ enhanced the electron transfer capacity and favored the formation of reactive oxygen species (ROS) during catalytic ozonation reaction, and their roles in catalytic ozonation has also been verified. The radical quenching experiments demonstrated that ·OH was the main contributor for enhancing pollutants removal. The results of Gaussian calculation coincided with those intermediates detected by UPLC-Q-TOF-MS, the pollutants’ removal mechanisms by catalytic ozonation were proposed basing on them. The overall toxicities were compared for ozone only/catalytic ozonation by zebrafish embryo experiment. The results of this study would provide new a feasible way for treating antibiotics and NH+4-N simultaneously in aquaculture wastewater.

中文翻译：

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Cu-Co/γ-Al2O3催化臭氧化性能及机理实现水产养殖废水中抗生素和氨同时脱除


抗生素和氨通常共存于水产养殖尾水中;此外，氨也会在臭氧化过程中产生，应在排放或再利用之前同时去除。本研究从多种金属氧化物中筛选出催化剂 Cu-Co/γ-Al2O3，并应用于三种抗生素和 NH+4-N 的催化臭氧化反应，研究了影响其去除的因素，包括催化剂用量、O3 浓度、初始 pH 值以及共存离子。此外，通过探索自由基的作用以及中间体鉴定来探索机制;以及使用 SEM、EDS、XRD、XPS 和 BET 评估催化剂使用前后的特性。结果表明，Cu-Co/γ-Al2O3 可以显着刺激臭氧化过程中所选抗生素和 NH+4-N 的降解。环丙沙星 （CIP）、四环素 （TC）、磺胺甲噁唑 （SMX） 和 NH+4-N 的降解效率分别可达 95.0 %、100.0 %、96.2 % 和 75.7 %。催化剂表面充足的氧空位 （Ovs） 和充足的碱性位点有利于污染物的吸附。此外，金属离子 Cu+/Cu2+ 和 Co2+/Co3+ 的转变增强了电子转移能力，有利于催化臭氧反应中活性氧 （ROS） 的形成，它们在催化臭氧化中的作用也得到了验证。自由基猝灭实验表明 ·OH 是加强污染物去除的主要贡献者。高斯计算结果与UPLC-Q-TOF-MS检测的中间体相吻合，在此基础上提出了催化臭氧去除污染物的机制。 通过斑马鱼胚胎实验比较仅臭氧/催化臭氧化的总体毒性。本研究结果为同时处理水产养殖废水中的抗生素和 NH+4-N 提供了一种新的可行方法。