基于硫酸根自由基（SO_4^(?-)）—高级氧化技术（AOPs）已被较多研究报道所证实其可有效降解多种难降解有机化合物，且相对羟基自由基，SO_4^(?-)在降解某些难降解有机污染污染物时表现出更优的降解能力。关于借助过硫酸盐（Persulfate, PS）或过一硫酸盐（Permonsulfate, PMS）结合活化方法（金属催化与能量激发等）产SO_4^(?-)降解有机污染物的研究在进入21世纪后迅猛发展，然而目前使用SO_4^(?-)去除复杂体系中难降解有机污染污染物研究较少。 本研究中将选用基于SO_4^(?-)-AOPs去除二级出水出水有机物质（Efluent Organic Matter, EfOM）。使用不同方法活化前体物质产SO_4^(?-)。验证不同催化激发方法与不同前体物质结合体系对EfOM降解效果。这亦是国内外首先系统探索SO_4^(?-)对EfOM去除效果。同时借助多分析方法深入分析EfOM组分特性及硫酸根自由基处理对EfOM组分特性影响。本研究发现单独硫酸根自由基难以有效去除水中氨氮，羟基自由基亦如此，因此本研究中亦探索基于SO_4^(?-)引发复合高级氧化技术去除水中氨氮。主要研究内容与结论如下： 第一部分主要试验能量激发（加热与UV）和金属催化（Ag(I)、Co(II)和ZVI（Zero Vanlce Iron））方法活化PS或PMS处理二级出水。选用溶解性有机碳（Dissolved Organic Carbon, DOC）作为评价指标以比较不同体系对EfOM去除效果。Ag(I)/PS体系DOC去除效果最佳且去除率高达90 %，ZVI/PS体系效果次之，但其在较低体系浓度（5 mM）获得最佳降解效果（60 %），而Co(II)/PMS体系处理效果去除较差（43 %），且DOC去除效果随时间变化反应揭示Co(II)/PMS体系难以在反应初始阶段（0-2 h）表现出DOC去除效果，然而其余体系均在反应初始阶段去除绝大部分DOC。能量激发体系对DOC去除效果整体优于金属催化体系。加热（40°C, 60°C, 80°C）温度对EfOM去除效果起到决定性作用且随加热温度升高DOC去除率显著上升。然而UV激发体系中UV强度并未对DOC去除效果起决定性作用，亦可能本研究中使用UV辐射强度已比较高。不同能量激发体系中最佳反应对DOC去除率在85-90%范围。 第二部分部分主要研究硫酸根自由基处理对EfOM组分特性影响，通过引入O3、?OH，对比研究 SO_4^(?-)对EfOM去除效果与借助多种辅助分析方法（三维荧光光谱、紫外-可见光谱与分子量分布）揭示硫酸根自由基对EfOM降解特点。DOC去除效果以SO_4^(?-)效果最佳，?OH次之，O3最差。不同辅助分析方法均显示三种AOPs对EfOM组分特性有不同影响。O3在三种分析放法中均显示出快速改变（前5 min）EfOM组成特性的特点，而其余反应则显缓慢。O3趋向于改变激发波长小于380 nm区域有机物质的荧光特性，而SO_4^(?-)对有机物质荧光特性改变无趋向性且 SO_4^(?-)对整体荧光特性去除较为彻底，亦与SO_4^(?-)对DOC良好去除效果相吻合。紫外-可见光谱结果表明三种AOPs主要降低240-440 nm区域的光谱吸收值，SO_4^(?-)却于320-440 nm范围获得更佳吸收值降低效果，但整体吸收值去除速率远慢于O3上一部分研究结果表明340-400 nm范围光谱吸收值下降与DOC降低存在较好联系。分子量分布结果揭示EfOM中有机物质分子量分布广泛（0.5-90 KDa）且集中于2-10 KDa范围。O3整个反应过程仅大幅度降低整体分子量范围内吸收值而较少生成新低分子量中间产物。SO_4^(?-)对所有分子量范围有机物质均显示出高选择性，而?OH对高分子量有机物质选择性较差。SO_4^(?-)反应过程则持续生成新低分子量中间产物，且降解反应广泛发生使种类众多的低分子中间产物生成，与其较好DOC去除效果相适应。 第三部分主要探究SO_4^(?-)对液相氨氮氧化效果及探寻新型高效AOPs去除水中氨氮。单独SO_4^(?-)对液相氨氮去除效果较差，?OH亦如此，甚至更差。而结合不同无机离子（CO_3^(2-)、HCO_3^-和Cl^-）后的新体系（UV/PS+Cl^-、UV/PS+CO_3^(2-)和UV/H2O2+CO_3^(2-)）可获得较好氨氮氧化效果，且离子浓度对氨氮氧化效果发挥重要影响，UV/PS+Cl^-体系能够几乎完全去除液相氨氮（10 mg/L），而UV/PS+CO_3^(2-)最高去除率亦超80 %，UV/H2O2+CO_3^(2-)效果较为一般且仅有约50 %。三个反应中氧化产物主要为NO_2^--N、NO_3^--N和N2。依据N质量平衡，UV/PS+Cl^-中气态氧化产物产率最高，约95%，UV/H2O2+CO_3^(2-)次之（90 %），UV/PS+CO_3^(2-)生成较多NO_3^--N导致气态产物产率（40 %）最低。反应初始pH值改变将影响反应速率及氧化产物，强酸（pH=2）或强碱（pH=12）可大幅度降低UV/PS+Cl^-氧化氨氮的速率，且使反应中液相产物（NO_2^--N和NO_3^--N）产率显著提高，尤其强碱条件导致氧化产物几乎全为硝酸盐氮。弱酸（pH=5）、中性与弱碱（pH=9）均有提高反应速率，以弱碱条件下速率常数最优，但酸性环境下气态产物产率却优于碱性环境。自由基捕获（MeOH、t-BuOH和酚）实验结果表明SO_4^(?-)与?OH对反应氨氮去除效果发挥重要作用，可能反应需要SO_4^(?-)或?OH驱动CO_3^(2-)和Cl^-生成新自由基对氨氮发挥氧化作用。Cl˙捕获剂（苯亚甲基特丁基氮氧化物）亦对含氯反应中氨氮产生绝对抑制作用，表明Cl˙在反应氧化氨氮中发挥直接重要作用。CO_3^(?-)捕获剂（对硝基苯胺与抗坏血酸）同样大幅度降低含CO_3^(2-)反应对氨氮去除率。所以CO_3^(?-)亦在含CO_3^(2-)反应氧化氨氮时发挥直接氧化作用。

The advanced oxidation processes (AOPs) based sulfate radical (SO_4^(?-)) have been reported by numerous researches to prove that they can degrade a variety of refractory organic compounds. And compared to hydroxyl radical, SO_4^(?-) has an advantage in oxidative capacity when degradation of resistant organic pollutants. Research on production of SO_4^(?-) degrading organic contaminants by means of persulfate (PS) or permonosulfate (PMS) combined activation methpds (metal catalysis and energy activation) has developed rapidly since the 21st century, however, the use of SO_4^(?-) to remove refractory organic matter pollutants in complex systems is less studied now. In this study, the based on SO_4^(?-)-AOPs was selected to remove Effluent Organic matter (EfOM) in the secondary effluents. Different methods were used to activate the precursor for producing SO_4^(?-). The systems combine with different catalytic- activated methods and various precursors was veriftied for the effects of EfOM degradation. This is also the systematic exploration of SO_4^(?-)on EfOM removal effect at home and abroad first. Simultaneously, the multi-analytical methods were applied thoroughly analyse characterization of EfOM, and characterization of various AOPs treated EfOM. There was also trying to explore a new advanced oxidation technology based on SO_4^(?-)or ?OH for removal liquid ammonia. The main research contents and conclusions are as follow: The first part mainly tested energy activation (heating and UV) and metal catalysis (Ag(I), Co(II) and ZVI (Zero Vanlce Iron)) methods to activate PS or PMS on treating secondary effluents. Selected Dissolved Organic Matter (DOC) as the evaluation index for comparing the effects of various systems treatment on EfOM。The removal efficiency of DOC in Ag(I)/PS was the best and the removal rate was as high as 90 %. The effect of ZVI/PS obtained the second efficiency, however, the best degradation effect was gained at lower concentration of PS (5 mM), while the effects of Co(II)/PMS was terrible and the reaction of DOC removal rate changed with time revealed that Co(II)/PMS was difficult to obtained and apparent DOC removal in the initial step (0-2 h) of reaction, while the orther systems both expressed the remarkable removal rate of DOC in this step. The systems of energy activation had a better overall effect on the DOC removal than the system of metal catalysis. The heating (40°C, 60°C, 80°C) temperature played a decisive role in the removal effect of EfOM and the DOC removal rate increased significantly as the rising heating temperature. However, the UV intensity in UV activation system did not play a decisive role in the effect of DOC removal. It was also possible that the intensity of UV radiation applied in this study had been relatively high. The best reaction in various energy activation systems had a DOC removal rate in the range of 85-90 %. The secondary part mainly studied the treatment of sulfate radical on the characteristic of EfOM compenents. Via leading in O3, ?OH, the comparative study of sulfate radical on the removal efficiency of EfOM and applied mul-analysis methods(hree-dimensional fluorescence spectroscopy, UV-Vis spectroscopy and distribution of molecular weight) revealed the adegraded characterizations of EfOM. The DOC removal rate was the best for SO_4^(?-), ?OH was the second, and O3 was the worst. Various assisted analysis methods showed that different AOPs had various effects on characterization of EfOM. O3 exhibited rapid change (first 5 min) EfOM composition characteristics in the three analytic methods while the remaining reactions were slow. O3 tends to degrade the fluorescence characteristics of organic matter witn an excitation wavelength less than 380 nm, however, ?SO_4^(?-) had no tendency to change the fluorescene characteristics of organic substance, and it had the most thorough removal of the overall characteristics, and this observation also consistented with SO_4^(?-) obtaining the best removal effect of DOC. The results of UV-Vis spectra showed that the three AOPs mainly reduced the spectral absorption in the 240-440 nm region, while ?OH and SO_4^(?-) gained an better absorption reduction in the 320-440 nm region, however, the vaule removal speed was much lower than O3. The consequences of distribution of molecular weight revealed the range of molecular weight of organic matter in EfOM was huge broad (0.5-90 KDa). The entire reaction process of O3 only greatly reduced the adsorption value in the whole molecular weight range and produced less new low molecular weight intermediate products. The reaction process of ?OH and SO_4^(?-) was continued to generate low molecular weight intermediates, and this phenomenon was more pronounced under the treatment of SO_4^(?-). The third part mainly explored the effect of SO_4^(?-) on the oxidation of liquid ammonia and seeked new efficient AOPs for removal amoonia in water. Alone SO_4^(?-) had a poor effect on the remocal of liquid ammonia, and the same observation was also in ?OH. However, combined with various inorganic ions (CO_3^(2-), HCO_3^- and Cl^-) could significantly enhance the removal efficiency of ammonia, and three reactions (UV/PS+Cl^-, UV/PS+CO_3^(2-) and UV/H2O2+CO_3^(2-)) showed relatively high performance. The impact of ion concentration on effect of ammnia removal was significant, UV/PS+Cl^- system could almost completely remove liquid ammonia (10 mg/L). And the best removal efficiency in UV/PS+CO_3^(2-) was more than 80 %, however, the efficiency in UV/H2O2+CO_3^(2-) was common and removal rate only approximately 50 %. The oxidation products in the three reactions were mainly NO_2^--N、NO_3^--N and N2. According to the mass balance of nitrogen, UV/PS+Cl^- had the highest productivity of gaseous oxidation products (95%), followed by UV/H2O2+CO_3^(2-)(90 %) and UV/PS+CO_3^(2-)(40 %) generateed more nitrate led to the lowest yield of gaseous products. Strong acid (pH=2) or base (pH=12) copuld greatly reduce the rate speed constant of UV/PS+Cl^- oxidation ammonia and made the liquid phase products (NO_2^--N、NO_3^--N) were significantly increasd, and especially strong alkali condition resulted in the almost complete oxidation products being nitrate. The weak acid (pH=5), neutral and weak base (pH=9) all increased the reaction rate, and the rate constant was optimal under weak base condition, however, the yield of gaseous products under acidic condition was better than basic environment. The results of three radical trapping experiments (MeOH, t-BuOH and phenol) showed that ?OH or SO_4^(?-) played a decisive role in the removal effect of ammonia. It indicated that the reactions might require ?OH or SO_4^(?-) to react withCO_3^(2-) and Cl^- for generating new radical on oxidizing ammonia. The scanvenger of chloride radical (benzylidene tert-butyl nitrogen oxide) also had an absolute inhibitory effect on ammonia oxidation, it indicated that chloride radical played a direct role in the reaction of oxidizing ammonia. The caputuring agent (p-nitroanoline and ascorbic) of carbonate radical also significantly reduced the removal rate of ammonia in containing carbonate reactions. Therefore, carbonate radical also played a dirent role in the oxidation of ammoniaThe advanced oxidation processes (AOPs) based sulfate radical (SO_4^(?-)) have been reported by numerous researches to prove that they can degrade a variety of refractory organic compounds. And compared to hydroxyl radical, SO_4^(?-) has an advantage in oxidative capacity when degradation of resistant organic pollutants. Research on production of SO_4^(?-) degrading organic contaminants by means of persulfate (PS) or permonosulfate (PMS) combined activation methpds (metal catalysis and energy activation) has developed rapidly since the 21st century, however, the use of SO_4^(?-) to remove refractory organic matter pollutants in complex systems is less studied now.