针对合成制药园区废水成分复杂、毒性高，难以处理达标等问题，以东北某制药园区生化处理厂出水（SPW，synthetic pharmaceutical park tail wastewater, SPW）为研究对象，开展SPW深度处理过程中难降解有机物变化特征研究。基于SPW的水质特征和有机物类型，甄选混凝、高级氧化和吸附单元工艺，构建了混凝-UV/H2O2-生物活性炭（BAC）组合深度处理工艺，研究了单元工艺和组合工艺对SPW中不同类型有机组分的去除效果，全过程评估了废水急性毒性变化。运用光谱分析方法，分析废水有机物荧光组分特征；利用化学计量学方法，评估废水有机物组分去除效果；应用数理统计方法，辨识SPW深度处理的主控因子，识别有机组分降解时序，揭示SPW处理过程中难降解有机物变化特征与降解机制。 SPW的基本特征是含有大量的烷烃类、苯胺类、吡啶类以及其它类型的杂环化合物，具有较强的生物毒性从而可生化性差等特点，需要深度处理才能进入综合污水处理厂处理。经优选，聚合硫酸铁（PFS）为SPW预处理最佳混凝剂，其投加量为0.4 g/L、废水初始pH值为7.0。混凝处理后，废水中的疏水性有机物得到有效去除；但亲水物质的去除效果较差，去除率仅为12.0%。利用平行因子（PARAFAC）法对SPW的荧光光谱成分进行进一步分析，解析出5类荧光组分，其去除效果排序为：类富里酸Ⅰ>类富里酸Ⅱ>类蛋白物质>异型生物质>类胡敏酸。类富里酸Ⅰ和类富里酸Ⅱ分别与DOC、UV254呈现显著相关（R2 = 0.9652和0.8817、R2= 0.8851和0.8270），因此，类富里酸Ⅰ和类富里酸Ⅱ可有效表征SPW处理过程中水质变化，可作为废水水质监测的重要指标。 混凝-臭氧（O3）或混凝-UV/O3氧化处理，均能有效去除具有紫外吸收的有机物，在反应60 min后，SUVA[UV254与溶解性有机碳（Dissolved Organic Carbon，DOC）浓度之比]值的去除率分别达到55.1%和69.9%；UV/O3氧化对DOC的去除率达55.8%，明显优于单独O3氧化的43.3%。利用同步二维荧光光谱（Two-dimensional correlation）与主成分分析（PCA）方法，识别出类色氨酸荧光物质（TRLF）、类酪氨酸荧光物质（TYLF）、微生物胡敏酸荧光物质（MHLF）、类富里酸荧光物质（FLF）和类腐殖酸荧光物质（HLF）。MHLF和FLF为SPW中溶解性有机物（Dissolved Organic Matter，DOM）的主要组分，在氧化过程中转化为TRLF；在UV/O3处理中其降解次序为HLF→FLF→MHLF→TRLF→TYLF。 利用混凝-UV/H2O2去除SPW中的4类有机组分?疏水酸、非酸疏水物、弱疏水物和亲水物质，发现低分子量的亲水性物质是UV/H2O2处理出水的主要组分。在混凝剂（PFS）投加量为0.4 g/L，废水初始pH值为7.0、H2O2投加量为250 mg/L、UV功率为15W的优化工艺条件下，DOC的去除率为75.1%，而单独的UV/H2O2处理工艺对DOC去除率仅为35.9%。应用PARAFAC方法，探讨混凝-UV/H2O2处理工艺中荧光有机物成分的变化特征，其中类富里酸Ⅱ组分去除率最大，为70.8%，异型生物质和类富里酸Ⅰ组分则难以降解。异型生物质与疏水酸和非酸疏水物之间呈现显著的相关性（R2＞0.8），表明荧光光谱法是研究混凝-UV/H2O2体系中DOM组分去除的有效手段。SPW经混凝-UV/H2O2组合工艺处理后，费希尔弧菌的光损失率由88.0%降低至47.0%，BOD5/COD比由0.1升高至0.52，表明废水的毒性降低和可生化提高，有利于后续生化处理。 混凝-UV/H2O2-BAC耦合处理是去除难以生化降解、有毒有害的SPW中有机物的有效技术。处理后，SPW的疏水性酸组分（HPOA）、疏水性中性组分（HPON）、弱疏水酸组分（TPHA）、弱疏水中性组分（TPHN）和亲水组分（HPI）的去除率分别为86.6%、92.9%、70.0%、78.7%和40.1%。费希尔弧菌的光损失率由混凝-UV/H2O2处理后的47.0%降低至15.0%，废水毒性进一步降低。利用典型关联分析（CCA），分析有机组分与水质指标之间的关联性，类胡敏酸和异型生物质与HPI显著正相关，表明类胡敏酸和异型生物质为SPW的特征污染物组分。利用CCA分析各工艺段典型有机组分变化特征，发现混凝主要去除类富里酸Ⅰ和类富里酸Ⅱ，间接验证该工艺段主要去除具有较大分子量的疏水性有机物；UV/H2O2主要去除类胡敏酸和异型生物质，表明该工艺段能有效降解废水毒性；BAC工艺段主要去除HPI组分，表明小分子亲水组分被活性炭吸附和生物降解。

Aiming at the problems in synthetic pharmaceutical park wastewater with complex components of high toxicity and difficulty to meet the treatment standard, the effluent (synthetic pharmaceutical park tail wastewater, SPW) from a biochemical wastewater treatment plant of a pharmaceutical park in Northeast China was studied. Research was conducted on the transformation characteristics of refractory organic matters during the advanced treatment process of SPW. The integrated advanced treatment technique of Coagulant-UV/H2O2-Bioactive Carbon (BAC) was established, based on the water quality characteristics of SPW and the organic pollutant types, with selection of coagulation, advanced oxidation and adsorption unit technique. The removal effect of different types of organic compounds in the wastewater by both single process and combined process was studied, with whole process assessment of acute toxicity change of the SPW. The spectral analysis method was used to analyze the characteristics of organic matter fluorescence components in wastewater. The removal efficiency of organic components in wastewater was evaluated by chemometrics method. The main controlling factors of SPW advanced treatment were identified by mathematical statistics method to identify the organic components’ degradation time sequence and to reveal the transformation characteristics and degrading mechanism of refractory organic matters in the process of SPW treatment. The basic characteristics of SPW are of a large number of alkanes, aniline, pyridine, and other types of heterocyclic compounds, with strong biological toxicity and poor biodegradability, which need to be treated in depth so as to enter the comprehensive sewage treatment plant. After optimization, the best coagulant for pretreatment of SPW was found to be the Polymerized Ferric Sulfate (PFS), at dosage of 0.4 g/L and the initial wastewater pH value of 7.0. After the coagulation treatment, the hydrophobic organic matters in the wastewater were removed effectively, but the removal efficiency of the hydrophilic substances was poor with only 12% of removal rate. Further analysis of the fluorescence spectral composition of the SPW was conducted by Parallel Factor Analysis (PARAFAC), with 5 fluorescent components distinguished. The removal effect was fulvic acidⅠ > fulvic acidⅡ > proteins > xenobiotic organic matter > humic acid. The fluorescence components fulvic acid I and fulvic acid II were significantly correlated with the DOC and UV254 (R2 = 0.9652 and 0.8817、R2 = 0.8851 and 0.8270). Thus, fulvic acid I and fulvic acid II can effectively characterize the change of water quality in the treatment process of SPW, and can be used as an important indicator for monitoring wastewater quality. Coagulant-O3 or Coagulant-UV/O3 oxidation treatment can either effectively remove organic matters with UV absorption. After 60 min of reaction, the removal rate of SUVA [ratio of UV254 and Dissolved Organic Carbon (DOC) concentration] value reached 55.1% and 69.9% respectively. The treatment effect of UV/O3 irradiation oxidation on DOC was obviously better than that of single O3 oxidation process, with the DOC removal rate being 55.8% and 43.3%, respectively. The Synchronous fluorescence spectroscopy (SFS) integrating two-dimensional correlation and principal component analysis (PCA) were applied to identify the tryptophan fluorescent substance (TRLF), the tyrosine fluorescence (TYLF), the microbial humid acid fluorescent substance (MHLF), the fulvic acid fluorescent substances (FLF) and the humic acid fluorescent substances (HLF). MHLF and FLF were the dominant components of Dissolved Organic Matter (DOM) in SPW, which were transferred into TRLF during the oxidation process. In the UV/O3 process, the degradation order was HLF→FLF→MHLF→TRLF→TYLF. The coagulation-UV/H2O2 oxidation was used to remove the four DOM fractions of hydrophobic acids, non-acid hydrophobics, transphilics and hydrophilics in the SPW, finding that the low molecular weight (MW) hydrophilic substances were the main components of UV/H2O2 effluent. Under the optimized technical condition of coagulant (PFS) dosage at 0.4g/L, initial wastewater pH at 7.0, H2O2 dosage at 250mg/L, and UV power at 15W, the DOC removal rate was 75.1%, while that of the single UV/H2O2 was just 35.9%. The PARAFAC method was used to study the variation characteristics of the fluorescent organic compounds in the coagulation-UV/H2O2 process. The removal rate of the component fulvic acid II was the highest reaching 70.8%, while the component xenobiotic organic matter and fulvic acid I were difficult to be degraded. Significant correlations (R2 > 0.8) between xenobiotic organic matter and the hydrophobic acids as well as non-acid hydrophobics suggested that the fluorescence spectroscopy was the effective tool for study on the DOM removal in coagulation-UV/H2O2 system. After the combined Coagulation-UV/H2O2 treatment of SPW, the light loss rate of Vibrio Fisher decreased from 88.0% to 47.0% and the BOD5/COD ratio increased from 0.1 to 0.52. It indicated that the wastewater toxicity was reduced whiel the biodegradability was increased, which is beneficial for subsequent biochemical treatment. The coupling treatment by Coagulation-UV/H2O2-BAC is an efficient technology for removing DOM from hardly degradable, toxic and harmful SPW. After the treatment thereof, the removal rates of hydrophobic acid component (HPOA), hydrophobic neutral component (HPON), transphilic acid component (TPHA), transphilic neutral component (TPHN) and hydrophilic component (HPI) were 86.6%、92.9%、70.0%、78.7% and 40.1%, respectively. The light loss rate of Vibrio Fisher decreased further from 47.0% after Coagulation-UV/H2O2 to 15.0%, with further decline of wastewater toxicity. The correlation between the organic components and the water quality indexes was analyzed by Canonical Correlation Analysis (CCA). The humic acid and xenobiotic organic matter were positively correlated with the HPI, indicating that humic acid and xenobiotic organic matter were the characteristic pollutant components of the SPW. CCA was used to analyze the transformation characteristics of typical organic components in each process section, finding that the coagulation mainly removed fulvic acid I and fulvic acid II, which indirectly verified that the process mainly removed hydrophobic organic matters with larger MW. UV/H2O2 mainly removed humic acid and xenobiotic organic matter, indicating that the process can effectively degrade the toxicity of wastewater. The HPI component was mainly removed by the BAC process, indicating that the small molecule hydrophilic components were adsorbed and biodegraded by activated carbon.