光谱学与光谱分析, 2018, 38 (8): 2617, 网络出版: 2018-08-26  

利用紫外和荧光光谱指示臭氧降解典型内分泌干扰物的研究

Investigation of Degradation of Endocrine Disrupting Compounds by Ozone as Indicated by Ultraviolet and Fluorescence Spectroscopy
作者单位
1 北华航天工业学院建筑工程系, 河北 廊坊 065000
2 河北省航天遥感信息处理与应用协同创新中心, 河北 廊坊 065000
3 华北电力大学环境科学与工程学院, 北京 102206
摘要
污水处理和再生回用是缓解我国水污染严重和水资源紧张的有效途径。二级出水水量大、稳定且水质相对良好, 是污水再生回用的良好水源。 然而, 二级出水中广泛存在内分泌干扰物(endocrine disrupting compounds, EDCs), 对其再生回用形成了潜在的安全风险。 臭氧氧化是去除EDCs的有效方法, 但二级出水中存在着多种有机质, 臭氧降解EDCs的过程中同时和有机质中的活性基团发生反应, 引起一定程度的臭氧衰减, 从而对EDCs的臭氧氧化造成影响。 有机质中与臭氧反应的活性基团变化可反映为特征紫外和荧光光谱的变化。 因此, 可以采用特征紫外和荧光光谱变化来指示臭氧对EDCs的降解效果。 本研究通过考察二级出水中主要的三类有机质代表(腐殖酸、 牛血清蛋白和海藻酸钠)对臭氧衰减动力学的影响, 进一步解析有机质对5种典型EDCs臭氧降解规律的影响, 在此基础上考察特征紫外和荧光光谱与EDCs臭氧降解效果的关系, 以期筛选出二级出水中EDCs臭氧降解效果的指示参数, 并建立其与EDCs降解效率之间的定量关系, 从而以这些指示参数来预测EDCs的臭氧化降解情况, 简化EDCs检测。 该研究中五种目标EDCs(雌酮(E1)、 雌二醇(E2)、 雌三醇(E3)、 17α-乙炔基雌二醇(EE2)和双酚A(BPA))采用超高效液相色谱-双质谱联用技术同时分析定量。 通过考察不同种类二级出水有机质对臭氧衰减动力学和EDCs降解效果的影响发现三种有机质均可促进臭氧衰减, 对EDCs的臭氧化降解效率均有抑制作用, 顺序依次是腐殖酸>牛血清蛋白>海藻酸钠; 三种有机质的紫外-可见光谱特征谱图表明有机质中能与臭氧反应的活性基团在紫外-可见光有特定的响应特征; 三种有机质的三维荧光光谱特征谱图表明富里酸类腐殖质及喹啉类结构对臭氧消耗均有显著的贡献; 腐殖酸在254, 258和280 nm的紫外吸光度及激发波长/发射波长(Ex/Em)=240/396 nm, Ex/Em=345/436 nm的荧光吸光度去除率与臭氧投加量显著相关; 其中280 nm处的特征紫外吸光度UVA280, 特征荧光吸光度Ex/Em=240/396 nm可作为臭氧降解EDCs的指示参数, 具体为UVA280去除率大于18%或者Ex/Em=240/396 nm去除率大于35%时, 1 μmol·L-1的5种EDCs几乎被完全降解。 此研究对污水处理厂臭氧去除EDCs过程中臭氧剂量的优化及EDCs去除效果具有指导作用, 且可避免复杂的EDCs检测。
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.

司秀荣, 金洁, 付旭, 吴小芳. 利用紫外和荧光光谱指示臭氧降解典型内分泌干扰物的研究[J]. 光谱学与光谱分析, 2018, 38(8): 2617. SI Xiu-rong, JIN Jie, FU Xu, WU Xiao-fang. Investigation of Degradation of Endocrine Disrupting Compounds by Ozone as Indicated by Ultraviolet and Fluorescence Spectroscopy[J]. Spectroscopy and Spectral Analysis, 2018, 38(8): 2617.

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