State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences , P.O. Box 2871, Beijing 100085, China.
School of Environmental and Municipal Engineering, Xi'an University of Architecture and Technology , Xi'an 710055, China.
Environ Sci Technol. 2016 Oct 18;50(20):11034-11040. doi: 10.1021/acs.est.6b03054. Epub 2016 Sep 28.
Antibiotics pollution has become a critical environmental issue worldwide due to its high ecological risk. In this study, rapid degradation of enrofloxacin (ENR) was observed on goethite in the presence of Shewanella oneidensis MR-1 during the transition from anaerobic to aerobic conditions. The abiotic reactions also demonstrated that over 70% with initial concentration of 10 mg L ENR was aerobically removed within 5 min by goethite with adsorbed Fe(II), without especial irradiation and strong oxidants. The results of spin trap electron spin resonance (ESR) experiments provide evidence that Fe(II)/Fe(III) complexes facilitate the generation of •OH. The electrophilic attack by •OH opens the quinolone ring of ENR and initiates further transformation reactions. Five transformation products were identified using high performance liquid chromatography-quadrupole time-of-flight mass spectrometry and the ENR degradation process was proposed accordingly. The identification of ENR transformation products also revealed that both the surface adsorption and the electron density distribution in the molecule determined the reactive site and transformation pathway. This study highlights an important, but often underappreciated, natural process for in situ degradation of antibiotics. With the easy migration of the goethite-MR-1 complex to the anaerobic/aerobic interface, the environmental fates of ENR and other antibiotics need to be seriously reconsidered.
由于其高生态风险,抗生素污染已成为全球范围内的一个关键环境问题。在本研究中,在从厌氧到需氧条件转变的过程中,希瓦氏菌(Shewanella oneidensis MR-1)存在于针铁矿上时,观察到恩诺沙星(ENR)的快速降解。非生物反应还表明,在初始浓度为 10 mg L 的情况下,超过 70%的 ENR 可以在没有特殊辐射和强氧化剂的情况下,通过吸附 Fe(II)的针铁矿在 5 分钟内被需氧去除。自旋捕获电子自旋共振(ESR)实验的结果提供了证据,证明 Fe(II)/Fe(III) 配合物有助于生成•OH。•OH 的亲电攻击打开了 ENR 的喹诺酮环,并引发了进一步的转化反应。使用高效液相色谱-四极杆飞行时间质谱鉴定了 5 种转化产物,并相应地提出了 ENR 降解过程。ENR 转化产物的鉴定还表明,表面吸附和分子中的电子密度分布决定了反应位点和转化途径。本研究强调了一种重要的但往往被低估的抗生素在原位降解的自然过程。由于针铁矿-MR-1 复合物容易迁移到厌氧/好氧界面,ENR 和其他抗生素的环境命运需要重新认真考虑。