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Investigation of Degradation of Endocrine Disrupting Compounds by Ozone as Indicated by Ultraviolet and Fluorescence Spectroscopy |
SI Xiu-rong1,2, JIN Jie3, FU Xu1, WU Xiao-fang1 |
1. Civil Engineering Department, North China Institute of Aerospace Engineering, Langfang 065000, China
2. Hebei Collaborative Innovation Center for Aerospace Remote Sensing Information Processing and Application, Langfang 065000, China
3. College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China |
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Abstract Wastewater treatment and reclamation are effective approaches to alleviate the serious water pollution and water shortage in China. Because of its large and stable quantity and excellent quality, secondary effluent is an excellent water source for the reclamation of wastewater. However, the widespread presence of the endocrine disrupting compounds (EDCs) in secondary effluent poses potential safety risks to its reclamation. Ozonation is an effective method to remove EDCs. However, because of the presence of many organic substances in secondary effluent, ozone also reacts with the active groups in organic mattersduring the ozonationdegradation process of EDCs, causing a certain degree of ozone attenuation, and thus, affecting the ozonation of EDCs. The change in active groups of organic matters that react with ozone is reflected in the change of their UV and fluorescence spectra. Therefore, changesin the characteristic UV and fluorescence spectra can be used to indicate the degradation effect of EDCs by ozone. In this study, we investigated the effect of three main organic matters (humic acid (HA), bovine serum albumin (BSA), and sodium alginate (SA)) present in secondary effluent on the kinetics of ozone attenuation and further analyzed the effect of organic matters on the ozonation degradation of 5 typical EDCs. Based on these results, we further investigated the relationship between the characteristic UV and fluorescence spectra and the degradation effect of EDCs by ozone, with the hope of selecting indicator parameters for the ozone-degradation of secondary effluent EDCs and establishing a quantitative relationship between these parameters and the degradation efficiency towards EDCs. Accordingly, these indicator parameters can be used to predict the ozonation degradation of EDCs, thereby simplifying the detection of EDCs. In this study, 5 target EDCs (estrone (E1), estradiol (E2), estriol (E3), 17α-ethinylestradiol (EE2), and bisphenol A (BPA)) were analyzed and quantified using ultraperformance liquid chromatography-mass spectrometry (UPLC/MS/MS). It was found through the investigation of the impact of different organic matters in secondary effluent on the kinetics of ozone attenuation and EDCs degradation that three organic matters promotedozone attenuation and inhibited the ozonation degradation of EDCs with the following descending effect: HA>BSA>SA. The characteristic spectra of these organic matters indicated that the active groups of these organic matters that could react with ozone exhibitedspecific response characteristics in the UV-Vis region. The three-dimensional excitation-emission matrix (EEM) fluorescence spectra of the three organic matters indicated that the fulvic acid-type humic acids and quinoline-type structures contributed significantly to ozone attenuation; the UV absorbance at 254, 258 and 280 nm and the fluorescence absorbance at the excitation/emission wavelengths of (Ex/Em)=240/396 nm and Ex/Em=345/436 nm were significantly correlated with the dosage of ozone. Among those, the characteristic UV absorbance (UVA280) and fluorescence absorbance (Ex/Em=240/396 nm) could be used as indicator parameters for the ozonation degradation of EDCs; specifically, as shown when the UVA280 removal efficiency was greater than 18% or the Ex/Em=240/396 nm removal efficiency was greater than 35%, 1 μmol·L-1 of the five EDCs was nearly completely degraded. The results in this study can be used to guide the optimization of ozone dosage in the removal of EDCs in wastewater plants and the removal efficiency of EDCs. In addition, the complicated detection of EDCs can be avoided.
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Received: 2017-12-21
Accepted: 2018-04-06
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