用于地下水回灌的再生水预处理工艺研究

将再生水回灌到地下含水层前,需对再生水进行预处理,以防止污染地下水.本研究比较了5种不同的再生水深度处理技术(超滤、臭氧、磁性离子交换树脂(MIEX)及超滤和臭氧、MIEX和臭氧两套组合工艺)对城镇二级出水的净化效果,并通过分析5种工艺对含水层净化效果的影响,评价其作为回灌预处理的可行性.针对再生水中的有机污染物溶解性有机碳(dissolved organic carbon,DOC)及比吸光度(specific ultraviolet absorbance,SUVA),MIEX(投加量为5 mL.L-1)能够去除20%的DOC和10%的SUVA;UF对DOC的去除率低于10%,对SUVA无显著去除效果,单独UF和MIEX预处理对后续含水层对再生水DOC的去除无促进作用;与此不同,臭氧[投加量(O3/DOC)为0.6 mg.mg-1]及其组合工艺对二级出水SUVA的去除率达60%～79%,能显著提高再生水的可生化性,强化土壤对回灌水中有机物的去除效果,使最终出水的DOC降低至1～2mg.L-1.针对再生水中的N素,MIEX(5 mL.L-1)能去除再生水中25%的NO3--N,臭氧能去除再生水中72%的NH4+-N.土壤处理能有效地去除NH4+-N,使出水浓度均在0.5 mg.L-1以下,但对NO3--N无显著去除效果.综合对比分析,在再生水回灌的预处理工艺中,需重点考察预处理对再生水中有机物和NO3--N的去除效果.臭氧和MIEX的组合工艺,能显著提高二级出水的可生化性,并去除部分溶解性有机物及NO3--N,与后续土壤处理具有较好的互补性,较适合用作地下回灌前处理工艺.     

Toxicity-based assessment of the treatment performance of wastewater treatment and reclamation processes

The reclamation and reuse of wastewater is one of the possible ways to relieve the serious fresh water resource crisis in China. Efficient reclamation treatment technologies ensure the safe reuse of reclaimed water. In order to screen out and evaluate technologies appropriate for reclamation treatment, a great deal of efforts have been brought to bear. In the present study, a toxicity-based method including a Photobacterium phosphoreum test for acute toxicity and SOS/umu test for genotoxicity, accompanied by the traditional physicochemical parameters DOC (dissolved organic carbon) and UV₂₅₄ (absorbance at 254 nm), was used to measure the treatment performance of different reclamation processes, including the anaerobic-anoxic-oxic biological process (A²O) and subsequent physical/chemical reclamation processes (ultrafiltration, ozonation, chlorination). It was found that for the secondary effluent after the A²O process, both the toxicity and physicochemical indices had greatly decreased compared with those of the influent. However, chemical reclamation processes such as ozonation and chlorination could possibly raise toxicity levels again. Fortunately, the toxicity elevation could be avoided by optimizing the ozone dosage and using activated carbon after ozonation. It was noted that by increasing the ozone dosage to 10 mg/L and employing activated carbon with more than 10 min hydraulic retention time, toxicity elevation was controlled. Furthermore, it was shown that pre-ozonation before activated carbon and chlorination played an important role in removing organic compounds and reducing the toxicity formation potential. The toxicity test could serve as a valuable tool to evaluate the performance of reclamation processes.     

Formation potentials of typical disinfection byproducts and changes of genotoxicity for chlorinated tertiary e uent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

Formation potentials of typical DBPs and changes of genotoxicity for chlorinated tertiary effluent pretreated by ozone

The effects of ozonation on the formation potential of typical disinfection byproducts (DBPs) and the changes of genotoxicity during post chlorination of tertiary effluent from a sewage treatment plant were investigated. Ozonation enhanced the yields of all detected chlorine DBPs except CHCl3. At a chlorine dose of 5 mg/L, the three brominated THMs and five HAAs increased, while chloroform decreased with the increase of ozone dose from 0 to 10 mg/L (ozone dose in consumption base). At a chlorine dose of 10 mg/L, the two mixed bromochloro species THMs and two dominant HAAs (DCAA and TCAA) firstly increased and then decreased with the increase of ozone dose, with the turning point approximately occurring at an ozone dose of 5 mg/L. The genotoxicity detected using umu test, on the other hand, was removed from 7 μg 4-NQO/L to a negligible level by ozonation under an ozone dose of 5 mg/L. Chlorination could further remove the genotoxicity to some extent. It was found that SUVA (UV absorbance divided by DOC concentration) might be used as an indicative parameter for monitoring the removal of genotoxicity during the oxidation.     

臭氧氧化二级出水有机物可生化性研究

通过臭氧氧化北京3个典型城市污水处理厂二级出水,考察臭氧对二级出水有机物可生化性的提高作用.采用批量试验方法,通过调整臭氧投加时间控制臭氧投加浓度为2、4、6、8、10 mg/L.结果表明,UV254与比紫外消光度SUVA(UV254/DOC)随臭氧投加量而降低,臭氧投加量为6 mg/L时,UV254与SUVA分别降低54.4%与56.6%以上;BOD5/COD、BDOC与BDOC/DOC分别提高30%、360%与360%以上,表明适当的臭氧投加量可提高二级出水难降解有机物的可生化性;三维荧光指纹光谱分析臭氧氧化前后二级出水中有机物的变化规律,表明该污水处理厂二级出水的荧光有机物主要为芳香族蛋白类物质和腐殖质类物质,臭氧可显著去除该类有机物.     

城市污水深度处理中有机物的去除

以城市污水地下水回灌为回用目的 ,研究不同的污水深度处理工艺及对二级生物处理出水中有机物的去除 .研究结果表明 ,原水若未经深度处理 ,直接由土壤含水层处理的出水不能满足推荐的回灌水水质要求 .对原水分别采用混凝沉淀、过滤、臭氧氧化、粉末活性炭和粒状活性炭吸附等处理单元及组合工艺进行深度处理效果的对比 ,最终选用由混凝沉淀 ,砂滤 ,粒状活性炭过滤与土壤含水层处理相结合的工艺流程 .城市污水处理厂的二级出水经该工艺处理后 ,出水中的 DOC可降至 3mg/L以下 ,且活性炭柱的产水床体积可达 350 0 BV.     

再生水中色度物质的识别及其臭氧去除特性

针对我国再生水普遍存在的色度问题,以天津市某污水厂二级出水为研究对象,采用三维荧光光谱和GC/MS技术对其进行组成分析,结果表明:再生水中主要带色物质为富里酸与腐殖酸类物质,同时还存在偶氮二甲酸二乙酯、N,N-二甲基乙醇胺、苄醚、1,4-二甲基吡啶氯化物等导致再生水色度的带色有机物。在再生水的臭氧降解实验中,臭氧可有效降解再生水中的富里酸与腐植酸类物质,去除率分别达到96.5%、97.3%。臭氧对再生水的色度与CDOM(有色溶解有机物)的降解也表现出了良好的效果,2 min内去除率可分别达到93.1%、86.2%。并且在色度物质的臭氧降解过程中,臭氧的直接反应占据主导地位,而并非与·OH的间接反应。该结果对再生水臭氧氧化工艺的设计应用有现实的指导意义。     

不同深度处理工艺再生水中余氯衰减规律及溶解性有机物变化特性比较

考察了余氯在不同深度处理工艺再生水中的衰减规律,并利用紫外-可见吸收差光谱和三维荧光光谱对余氯衰减过程的有机物变化进行了初步解析.结果表明,再生水中的余氯衰减迅速,加氯前0.5 h内的氯消耗占8 h内氯消耗的50%以上.混凝出水水样的余氯衰减速率大于超滤出水和臭氧出水.加氯后,混凝出水和超滤出水的紫外-可见吸收差光谱在230 nm和280 nm附近出现特征峰,表明余氯衰减过程中,水中具有不饱和键和生色团的物质被破坏.臭氧出水在波长230 nm附近出现特征峰.加氯使再生水的荧光强度减弱,混凝出水中腐殖质类物质荧光强度的降低程度大于超滤出水和臭氧出水,表明该类物质可能是影响余氯衰减速率的主要物质.     

Degradation behavior of 17αup-ethinylestradiol by ozonation in the synthetic secondary effluent

Endocrine disrupting chemicals (EDCs) in the secondary effluent discharged from wastewater treatment plants (WWTPs) are of great concern in the process of water reuse. Ozonation has been reported as a powerful oxidation technology to eliminate micropollutants in water treatment. Due to the complexity of the wastewater matrix, orthogonal experiments and single factor experiments were conducted to study the influence of operational parameters on the degradation of 17αup-ethinylestradiol (EE2) in the synthetic secondary effluent. The results of the orthogonal experiments indicated that the initial ozone and natural organic matter (NOM) concentration significantly affected EE2 degradation efficiency, which was further validated by the single factor confirmation experiments. EE2 was shown to be effectively degraded by ozonation in the conditions of low pH (6), NOM (10 mg/L), carbonate (50 mg/L), but high suspended solid (20 mg/L) and initial ozone concentration (9 mg/L). The study firstly revealed that the lower pH resulted in higher degradation of EE2 in the synthetic secondary effluent, which differed from EDCs ozonation behavior in pure water. EE2 degradation by ozone molecule instead of hydroxyl radical was proposed to play a key role in the degradation of EDCs by ozonation in the secondary effluent. The ratio between O₃ and TOC was identified as an appropriate index to assess the degradation of EE2 by ozonation in the synthetic secondary effluent.     

厌氧-缺氧-好氧处理出水中溶解性有机物组分的特征分析

本研究利用XAD-8大孔树脂对某城市污水处理厂的厌氧-缺氧-好氧(A2O)工艺出水中的溶解性有机物进行了组分分离,分析了各组分的溶解性有机碳(Dissolved organic carbon,DOC)、紫外-可见光谱和遗传毒性.结果表明,污水中亲水性物质和疏水酸性物质的DOC含量分别占总DOC含量的65%和24%.亲水性物质组分中的芳香族化合物含量显著高于其它组分,但是单位质量的亲水性物质、疏水酸性物质和疏水碱性物质中的芳香族化合物含量相近.污水具有一定的遗传毒性,主要遗传毒性物质为亲水性物质和疏水酸性物质,而疏水碱性物质和疏水中性物质则未检出遗传毒性.     

AAO工艺联合臭氧削减污水中微量有机污染物及遗传毒性

近年来,微量有机污染物(OMPs)的环境赋存及风险越来越受到学者的重视,而城市污水厂出水作为向水环境释放OMPs的重要污染源,应被加以监测和管控.以小试厌氧/缺氧/好氧工艺联合臭氧(AAO-O_3)为研究对象,考察了污水中14种OMPs在组合工艺中的迁移转化规律及遗传毒性的削减.结果表明,活性污泥系统对于大多数OMPs的去除效果不佳,去除率低于50%,而后续臭氧可以弥补其不足.AAO-O_3组合工艺可以保证多数OMPs去除率在90%以上.芳香性结构的取代基中含有酚羟基(—OH)、胺基(—NH2)、甲氧基(—OCH3)的OMPs易于在臭氧过程中降解.遗传毒性结果表明,污水和二级出水都存在一定致突变风险,二级出水经过臭氧处理之后,遗传毒性去除率达到98%,污水厂出水对水环境风险大大降低.     

FeOOH催化臭氧氧化滤后水中NOM的小分子副产物的生成

以滤后水中富集、分离出的6种不同特性的天然有机物(NOM)组分为对象,考察了羟基氧化铁（FeOOH）催化臭氧氧化NOM各组分后小分子醛、酮及酮酸副产物的生成情况.发现FeOOH催化氧化比臭氧氧化提高了对NOM 各组分DOC和SUVA的去除率.FeOOH催化氧化并不能有效地降低NOM各组分小分子副产物的产量.催化氧化和臭氧氧化后,憎水中性物质(HON)的醛、酮、酮酸的总产量都最高,NOM碱性组分的小分子副产物产量都相对最低.NOM各组分催化氧化后甲醛和丙酮酸的产量最大,这和单独臭氧氧化的结论一致.特别是HON的甲醛产率占其醛、酮总产量的71.6%,单位DOC丙酮酸的产量达78.6 μg/mg.用NOM组分的小分子副产物折算DOC占各组分氧化后DOC的质量分数来间接显示氧化后剩余DOC的可生物降解性,发现催化氧化比单独臭氧氧化进一步提高了滤后水中NOM各组分的可生化性.     

Effect of different molecular weight organic components on the increase of microbial growth potential of secondary effluent by ozonation

Ozonation has been widely applied in advanced wastewater treatment. In this study, the effect of ozonation on assimilable organic carbon （AOC） levels in secondary effluents was investigated, and AOC variation of different molecular weight （MW） organic components was analyzed. Although the removal efflciencies were 47%-76% and 94%-100% for UV2s4 and color at ozone dosage of 10 mg/L, dissolved organic carbon （DOC） in secondary effluents was hardly removed by ozonation. The AOC levels increased by 70%-780% at an ozone dosage range of 1-10 mg/L. AOC increased significantly in the instantaneous ozone demand phase, and the increase in AOC was correlated to the decrease in UV254 during ozonation. The results of MW distribution showed that, ozonation led to the transformation of larger molecules into smaller ones, but the increase in low MW （〈1 kDa） fraction did not contribute much to AOC production. The change of high MW （〉100 kDa and 10-100 kDa） fractions itself during ozonation was the main reason for the increase of AOC levels. Furthermore, the oxidation of organic matters with high MWs （〉 100 kDa and 10-100 kDa） resulted in more AOC production than those with low MWs （1-10 kDa and 〈1 kDa）. The results indicated that removing large molecules in secondary effluents could limit the increase of AOC during ozonation.     

城市污水中的生物毒性及其臭氧削减效果研究

分别利用酵母双杂交和umu试验对5个城市9个污水处理厂进出水中生物遗传毒性和视黄酸受体(BAR)结合活性进行了调查.并考察了臭氧氧化对这两种生物效应的去除效果.结果表明,城市污水中存在不同程度的生物遗传毒性和视黄酸受体(RAR)结合活性,通过生物处理可以大幅削减污水中的RAR结合活性和生物遗传毒性,但污水厂出水中仍然普遍具有遗传毒性,部分残留RAR结合活性.5～10mg·L-1的臭氧可以有效削减二级出水中残留的BAR结合活性和遗传毒性,是一种有效的提高水质安全性的污水深度处理技术.     

Removal of fluorescence and ultraviolet absorbance of dissolved organic matter in reclaimed water by solar light

Storing reclaimed water in lakes is a widely used method of accommodating changes in the consumption of reclaimed water during wastewater reclamation and reuse. Solar light serves as an important function in degrading pollutants during storage, and its effect on dissolved organic matter(DOM) was investigated in this study. Solar light significantly decreased the UV_(254) absorbance and fluorescence(FLU) intensity of reclaimed water.However, its effect on the dissolved organic carbon(DOC) value of reclaimed water was very limited. The decrease in the UV_(254) absorbance intensity and FLU excitation–emission matrix regional integration volume(FLU volume) of reclaimed water during solar light irradiation was fit with pseudo-first order reaction kinetics. The decrease of UV_(254) absorbance was much slower than that of the FLU volume. Ultraviolet light in solar light had a key role in decreasing the UV_(254) absorbance and FLU intensity during solar light irradiation. The light fluence-based removal kinetic constants of the UV_(254) and FLU intensity were independent of light intensity. The peaks of the UV_(254) absorbance and FLU intensity with an apparent molecular weight(AMW) of 100 Da to 2000 Da decreased after solar irradiation, whereas the DOC value of the major peaks did not significantly change.     

铝盐混凝剂的混凝效果与残留铝含量和组分之间的关系研究

研究了氯化铝、硫酸铝、聚合氯化铝(poly-aluminum chloride, PAC)3种铝盐混凝剂在腐殖酸-高岭土模拟水样中的应用,以比较3种混凝剂在该水样中的混凝效果与残留铝含量和组分之间的关系.结果表明, 3种铝盐混凝剂在试验选取的投加量下对浊度和UV254的去除率最高可达90%左右,PAC能在较高的投加量下达到较好的混凝效果;较高投加量下PAC混凝沉淀出水中残留总铝含量为0.9 mg/L左右,余铝率为-3.0%左右,均明显低于传统的铝盐混凝剂;3种混凝剂混凝处理腐殖酸-高岭土模拟水样时,残留铝均大部分以溶解性总铝的形式存在,且溶解性有机铝在总溶解性铝中所占比例较大;PAC在腐殖酸-高岭土混凝沉淀出水中残留总铝的含量下降最快,且能够有效降低出水中毒性较大的溶解性铝的含量,其混凝沉淀出水中残留总溶解性铝含量为0.6 mg/L左右.     

催化臭氧氧化与NaClO处理钛白粉废水中试对比

以山东某钛白粉厂二级压滤出水为研究对象,通过自主设计的中试设备考察了催化臭氧氧化工艺与NaClO工艺对钛白粉废水处理情况,确定催化臭氧氧化的最佳工艺实验条件为:在室温条件下,催化臭氧氧化反应时间为60 min,臭氧投加浓度为125 mg/L。对原有NaClO工艺进行优化,优化后的最佳工艺为:NaClO投加量为1.2%,反应时间为30 min。当平均进水ρ（COD）与ρ（NH₃-N）分别为109.7,12.8 mg/L,则催化臭氧工艺平均出水ρ（COD）与ρ（NH₃-N）分别为43.5,3.8 mg/L,平均去除率分别为60%和70.4%,NaClO工艺平均出水ρ（COD）与ρ（NH₃-N）分别为49.8,4.7 mg/L,平均去除率分别为54.5%和63.1%。在30 d内,催化臭氧氧化出水达标率为100%,NaClO出水达标率为26.7%,催化臭氧氧化处理费用为1.12元/t,NaClO处理费用为12元/t,催化臭氧氧化工艺相较于NaClO氧化工艺更适用于处理钛白粉废水。     

自然光和UV辐照下二级出水DOM及毒性的变化

为了探明自然光和紫外光（UV）对二级处理出水中溶解性有机物（DOM）及其毒性效应的削减特性，研究了在自然光和UV两种不同光源的辐照条件下，二级处理出水中DOM的光谱特性、遗传毒性和植物毒性变化，阐明了毒性效应变化的成因.结果表明：相比于自然光照，UV辐照可以明显降低二级处理出水的UV₂₅₄，并达到21%矿化.自然光和UV均可降低二级处理出水中有色溶解性有机物（CDOM），但去除的组分有所差异.同时，自然光照与UV辐照均可降低二级处理出水的遗传毒性，其削减率分别达到92%和61%.遗传毒性的变化与CDOM荧光强度变化有显著相关性.UV辐照可降低二级处理出水的植物毒性，削减率达到81%，而自然光照对二级处理出水植物毒性的削减率仅为19%，削减效果较差.利用UPLC-MS检测二级出水中的除草剂，发现植物毒性削减的差异主要是由于自然光照下二级处理出水中的阿特拉津降解缓慢，表观降解速率常数为0.0033h^-1；但是UV辐照下二级处理出水中的阿特拉津可快速降解，其表观速率常数为0.2225h^-1.这为污水厂排放水毒性效应控制及生态安全保障提供了一定的依据.     

臭氧氧化饮用水过程中可同化有机碳生成的影响因素

研究臭氧化过程中,臭氧投加量、p H值和离子强度对可同化有机碳(assimilable organic carbon,AOC)生成量的影响.结果表明,臭氧投加量在1~5 mg·L~(-1)范围,AOC的生成量随着投加量的增加而增加,但过高的臭氧投加量(9 mg·L~(-1))反而导致AOC生成量下降.p H越高(6~9),AOC的生成量也越高.AOC的生成量随着离子强度的升高而下降.臭氧氧化强疏组分AOC的生成量最高,其次为弱疏,而极亲和中亲最低.研究发现,AOC的生成量与小分子有机物的SUVA有密切的关系,较低的SUVA产生较多的AOC.     

河岸渗滤对不同工艺再生水补给景观水的处理功效

分别采用"二级出水+O3+GFH"和"二级出水+DNBF"两种不同工艺再生水补给人工湖,河岸渗滤(简称BF)作为净化再生水补给人工湖后的维护工艺,分析BF对人工湖中污染物的去除机制。结果表明:以"二级出水+O3+GFH"工艺出水作为人工湖补水,BF对NH4+-N、NO2--N、DOC的去除效率分别为85.1%、52.0%、22.5%。以"二级出水+DNBF"工艺出水作为人工湖补水,BF对NH4+-N、NO2--N、DOC的去除效率分别为64.4%、62.0%、26.4%。人工湖NH4+-N越高,水体中充分富氧,BF砂坝内硝化作用越强,BF对NH4+-N的去除率越高,可有效抑制蓝藻的暴发。