【作者】 皮运清；

【导师】 孙剑辉；

【作者基本信息】 河南师范大学 ， 环境科学， 2013， 博士

【摘要】 PPCPs是医药品和个人护理品（Pharmaceuticals and personal care products）的简称，包括人们在日常生活中广泛使用的多种处方和非处方药品如抗生素、抗肿瘤药、抗焦虑药、抗惊厥药、激素类药、阻滞剂与类交感神经药、消炎药、减肥药等，这些PPCPs在生产和使用过程中大部分以原药或代谢产物的形式排入水环境，具有排放面广、浓度低、成分复杂、生物毒性大、难降解等特点，是一类对水生态环境及人类健康潜在危害较大的新兴微污染物。目前，传统污水处理工艺对PPCPs的去除效果较差。因此，研究开发高效去除PPCPs的新技术，是国内外水处理领域的重要前沿课题。高级氧化技术（Advanced oxidation processes，AOPs）是去除污水中难生物降解污染物的有效方法，具有极大的开发潜力和良好的应用前景。本文选择城市污水厂出水中检出率高、危害性大的抗生素类药品磺胺间甲氧基嘧啶（sulfamonomethoxine，SMM）和氧氟沙星（Ofloxacin，OFL）作为目标污染物，系统地研究了UV/Oxone体系处理磺胺间甲氧基嘧啶模拟污水、Fenton和UV/Oxone/Co2+体系处理氧氟沙星模拟污水的性能、工艺条件和反应动力学；通过对降解过程中间产物（transformation products，TPs）的分析，重点研究了3种高级氧化技术降解目标污染物的机理，为应用高级氧化技术处理磺胺间甲氧基嘧啶、氧氟沙星实际废水提供了理论依据。论文主要研究内容和成果如下：1．UV/Oxone氧化体系对磺胺间甲氧基嘧啶的降解效果及反应机理的研究。结果表明：UV可以使Oxone产生硫酸根自由基（SO4-），能够高效降解磺胺间甲氧基嘧啶；反应体系在进水SMM浓度为5mg L-1、紫外光全程照射、pH值为中性、温度为20°C、SMM:Oxone=0.0107:1、反应时间为90min的优化条件下，磺胺间甲氧基嘧啶的降解率为96.36%，溶液的TOC去除率为89.01%；降解反应呈假一级动力学反应，表观速率常数为0.038min-1。依据LC-MS检测出的6种中间产物，推测出了UV/Oxone氧化体系降解磺胺间甲氧基嘧啶的路径，表明磺胺间甲氧基嘧啶能够被硫酸根自由基彻底氧化分解为二氧化碳和水。2．Fenton氧化体系对氧氟沙星的降解效果及反应机理的研究。结果表明：反应体系在进水OFL浓度为9mg L-1、，pH=4.0、温度为25°C、[H2O2]=1.5mmol L-1、[Fe2+]=0.03mmol L-1、[H2O2]:[Fe2+]=50:1、反应时间为80min的优化条件下，氧氟沙星的降解率为98.84%，溶液的TOC去除率为73.7%；降解反应呈假一级动力学反应，表观速率常数为0.65min-1。通过对LC-MS检测出的8种中间产物的分析，推测出了Fenton氧化体系降解氧氟沙星的路径；依据红外色谱的检测结果，确定该反应体系中羟基自由基（OH）对氧氟沙星的降解是从脱羧开始；离子色谱检测到反应结束后的溶液中含有氟离子，说明羟基自由基可以将氟从氧氟沙星的分子中剥离出来。3．UV/Oxone/Co2+氧化体系对氧氟沙星的降解效果及反应机理的研究。结果表明：反应体系在进水OFL浓度为9mg L-1、紫外光全程照射、pH=5.0、[Oxone]/[Co2+]为1000:1、[Oxone]=0.6mmol L-1、温度为25℃、反应时间为60min的优化条件下运行，氧氟沙星能够被全部降解，溶液的TOC去除率为87%；降解反应呈一级动力学方程，表观速率常数为0.67min-1。在相同工艺条件下，Oxone/Co2+体系对氧氟沙星的降解率为91.3%，溶液TOC的去除率为65.8%，说明有紫外光照射的UV/Oxone/Co2+体系的氧化能力较Oxone/Co2+体系更强；通过对LC-MS检测出的13种中间产物的分析，推测出了硫酸根自由基降解氧氟沙星的路径。实验发现硫酸根自由基对氧氟沙星的进攻位点受pH值影响较大，中性pH溶液中降解主要进行喹诺酮的脱羧反应，降解哌嗪基多发生在pH=3左右。4． Fenton氧化体系和UV/Oxone/Co2+氧化体系对氧氟沙星降解效果的比较。通过对2种氧化体系降解同浓度氧氟沙星污染物的降解时间，降解效果、降解路径的比较发现：UV/Oxone/Co2+氧化体系的氧化能力比Fenton氧化体系强；硫酸根自由基可以多路径同时降解水样中的氧氟沙星。更多还原

【Abstract】 Pharmaceuticals and personal care products (PPCPs) are a group of compounds whichinclude prescription and over-the-counter (OTC) drugs, such as antibiotic, antineoplastic,antianxiety and anticonvulsion, harmonic, retardant, sympathomimetic, anti-inflammatory andantiobesity drugs, etc. These PPCPs are discharged into aquatic environment in the form ofintact and metabolites during the process of the production and usage, which are characterizedby wide distribution, low residual level, complicated chemical composition, high toxicity andrefractory. PPCPs are considered as emerging contaminants, with potential risks to waterecological system and human health. The low efficiency in the removal of PPCPs bytraditional wastewater treatment technology has resulted in the recent emergence of concernsabout the development of new technique for PPCPs removal, which become an importanttopic in the field of water treatment technology all over the world.Advanced oxidation processes (AOPs) have been considered as effective methods for thedegradation of refractory pollutant within aquatic environments. Due to their high detectionrate and high damage in discharging of urban sewage plant, sulfamonomethoxine (SMM) andOfloxacin (OFL) were chosen as the typical target pollutants in this study. A series of study onthe performance, operating condition and reaction kinetics of SMM-contained simulatedwastewater by UV/Oxone oxidation system, OFL-contained simulated wastewater by Fentonand UV/Oxone/Co2+oxidation system were carried out. The degradation mechanisms ofSMM and OFL were proposed based on the identification of transformation products duringthe oxidation processes. This work could offer a fundamental understanding towards thedegradation of SMM and OFL by AOPs. The main conclusions in the paper are as follows:1. Research on the degradation efficiency and reaction mechanism of SMM-contained simulated wastewater by UV/Oxone oxidation system. The results showed that UV urges theproduction of SO4-from Oxone, which could degrade SMM efficiently. The optimaloperating parameters for degradation of SMM by UV/Oxone oxidation system were:[SMM]=5mg L-1, UV irradiation throughout the experiment, neutral pH, reaction temperature=20°C, SMM:Oxone=0.0107and reaction time=90min. Under the optimal conditions, thedegradation efficiency of SMM and removal efficiency of TOC achieved96.78%and89.01%,respectively. The degradation reaction followed the pseudo-first-order kinetics and theapparent rate constant was0.038min-1. Six transformation products were detected with theaid of high performance liquid chromatography combined with mass spectroscopy (LC-MS).Based on this, the reaction mechanism of SMM by UV/Oxone was proposed. The resultsindicated that SMM could ultimately be mineralized to CO2and H2O by SO4-.2. Research on the degradation efficiency and reaction mechanism of OFL-containedsimulated wastewater by Fenton oxidation system. The results showed that the optimaloperating parameters for degradation of OFL by Fenton oxidation system were: pH=4.0,[OFL]=9mg L-1,[H2O2]=1.5mmol L-1,[Fe2+]=0.03mmol L-1,[H2O2]:[Fe2+]=50:1,reaction temperature=25°C and reaction time=80min. The degradation efficiency andTOC removal of OFL were achieved98.84%and73.7%under the optimal condition,respectively. The degradation reaction was obeyed the pseudo-first-order kinetics and theapparent rate constant was0.65min-1. Eight transformation products were detected with theaid of high performance liquid chromatography combined with mass spectroscopy (LC-MS)and the reaction mechanism of OFL-contained simulated wastewater by Fenton oxidationsystem were proposed. Results from infrared spectrum confirmed that the degradation of OFLwas initiated from the decarboxylation by OH radicals. The F ions which were detected withIon Chromatography could be released from Ofloxacin with the assistance OH radicals.3. Research on the degradation efficiency and reaction mechanism of OFL-contained simulated wastewater by UV/Oxone/Co2+oxidation system. The results showed that theoptimal operating parameters for degradation of OFL by UV/Oxone/Co2+oxidation systemwere:[OFL]=9mg L-1, UV light irradiation, pH=5.0,[Oxone]:[Co2+]=1000:1,[Oxone]=0.6mmol L-1, reaction temperature=25°C, and reaction time=60min. OFL could bedegrade completely and the TOC removal was achieved87%under the optimal condition.The degradation reaction was obeyed the pseudo-first-order kinetics and the apparent rateconstant was0.67min-1. The degradation efficiency and TOC removal of Ofloxacin byOxone/Co2+oxidation system achieved91.3%and65.8%under the identical condition,respectively. The results indicated that UV/Oxone/Co2+oxidation system which possessed UVlight displayed stronger oxidizing ability than Oxone/Co2+oxidation system.13kinds oftransformation products were detected with the aid of high performance liquidchromatography combined with mass spectroscopy (LC-MS), where the reaction mechanismof OFL-contained simulated wastewater by SO4-radicals were proposed based on theidentification. The results indicated that the pH value had important effect on the attack sitesof OFL by SO4-radicals, the destruction of the carboxyl of the quinolone moiety wasdominant under the neutral pH conditions, while the SO4-attack at the piperazinyl substituentwas preferable near pH=3.4. The degradation efficiency of OFL-contained simulated wastewater between Fentonand UV/Oxone/Co2+oxidation system was compared. It could be found that UV/Oxone/Co2+oxidation system displayed stronger oxidizing ability than Fenton oxidation system. The SO4-radicals could degrade OFL in multipath at the same time.更多还原