Jiang Ying-Ying, Chen Zi-Wen, Li Man-Man, Xiang Qiu-Hong, Wang Xi-Xi, Miao Heng-Feng, Ruan Wen-Quan
School of Environmental and Civil Engineering, Jiangnan University, Wuxi 214122, PR China.
School of Environmental and Civil Engineering, Jiangnan University, Wuxi 214122, PR China; Jiangsu Key Laboratory of Anaerobic Biotechnology, Jiangnan University, Wuxi 214122, PR China; Water Treatment Technology and Material Innovation Center, Suzhou University of Science and Technology, Suzhou 215009, PR China; Jiangsu Engineering Laboratory of Biomass Energy and Carbon Reduction Technology, Jiangnan University, Wuxi 214122, PR China.
Sci Total Environ. 2021 Jun 15;773:144801. doi: 10.1016/j.scitotenv.2020.144801. Epub 2021 Jan 27.
A nano-calcium peroxide (nCaO) powder with a purity of 89.1% was prepared using an improved traditional method. Then, the as-prepared nCaO was used as the source of hydrogen peroxide (HO) for the Fenton-like degradation of diclofenac sodium (DCF). The results showed that nCaO performed better for DCF removal when compared to nCaO prepared by a conventional method and commercial calcium peroxide (CaO). Further experimental results indicated that 97.5% of DCF could be removed in 180 min at a nCaO/Fe-EDTA/DCF molar ratio of 16/8-8/1, which was more efficient than in the HO/EDTA-Fe/DCF and nCaO/Fe/DCF systems. The best removal rate of DCF was at pH 6.0, unlike previous claims that stated that the lower the pH in the buffer system, the better the degradation of DCF. In addition, the influence of water quality parameters, such as Cl, NO, SO, HCO, and humic acid (HA), on DCF removal were evaluated. A free radical masking experiment revealed the existence of hydroxyl radical (OH), superoxide radical (O) and singlet oxygen (O), and indicated that the degradation of DCF was mainly due to oxidation caused by OH. Electron paramagnetic resonance (EPR) studies for different systems and different active oxygen species were carried out, and it was further confirmed that OH radicals have high intensity in the Fenton-like system based on nCaO. EPR results also showed that the addition of EDTA can promote the production of OH. According to the identification of the dominant reactive species and GC-MS, the possible theoretical DCF degradation pathways were proposed.
采用改进的传统方法制备了纯度为89.1%的纳米过氧化钙(nCaO)粉末。然后,将制备好的nCaO用作过氧化氢(HO)的来源,用于双氯芬酸钠(DCF)的类芬顿降解。结果表明,与传统方法制备的nCaO和市售过氧化钙(CaO)相比,nCaO对DCF的去除效果更好。进一步的实验结果表明,在nCaO/Fe-EDTA/DCF摩尔比为16/8 - 8/1时,180分钟内可去除97.5%的DCF,这比HO/EDTA-Fe/DCF和nCaO/Fe/DCF体系更有效。DCF的最佳去除率是在pH 6.0时,这与之前声称缓冲体系中pH越低DCF降解效果越好的说法不同。此外,还评估了水质参数如Cl、NO、SO、HCO和腐殖酸(HA)对DCF去除的影响。自由基掩蔽实验揭示了羟基自由基(OH)、超氧自由基(O)和单线态氧(O)的存在,并表明DCF的降解主要是由于OH引起的氧化作用。对不同体系和不同活性氧物种进行了电子顺磁共振(EPR)研究,进一步证实了基于nCaO的类芬顿体系中OH自由基具有高强度。EPR结果还表明,添加EDTA可以促进OH的产生。根据主要反应物种的鉴定和GC-MS,提出了可能的DCF理论降解途径。