臭氧对混凝剂形态及功能的影响

应用Ferron逐时络合比色法,从铝形态分布及其转化的角度,研究了臭氧对聚合氯化铝混凝性能影响并探究其原因。结果表明,预臭氧对聚合氯化铝(PAC)的混凝效果有显著影响。在一定质量浓度范围内(0~3.60mg/L),臭氧浓度越高,水样浊度越高(其UV254(即254nm波长下水样的紫外吸光度值,表征含芳香环结构和共轭双键结构的有机物含量)和溶解性有机碳(DOC)的去除效果较显著)。臭氧对混凝剂水解形态有显著影响。预臭氧后,混凝絮体形成和浊度的去除与铝混凝剂中中等聚合态铝(Alb)的含量有关,Alb的含量越高,浊度去除效果越好。因此,臭氧剂量的增加抑制Alb生成可能是导致浊度升高的一个重要原因。     

臭氧强化BAF工艺处理微污染窖水

采用臭氧-BAF组合工艺处理西北地区微污染窖水,使用比紫外吸收值(SUVA)、有机物分子量分布和三维荧光光谱等指标分析了臭氧预氧化对微污染窖水有机物特性的影响,研究了组合工艺对不同污染物的去除效果。结果表明:原水经臭氧预氧化后类腐殖质、类色氨酸物质含量分别下降65%、18%;水中小分子有机物含量增加,进水可生化性提高;经臭氧预氧化后BAF反应器出水类色氨酸物质含量低于未经臭氧预氧化的BAF反应器出水,臭氧预氧化起到了强化后续生物处理的作用。反应器出水CODMn、NH_3-N浓度分别为2.97 mg·L~(-1)、0.12 mg·L~(-1),满足生活饮用水卫生标准的要求;TOC、UV254和TN去除率分别为55%、53%和45%,水中污染物质得到有效去除。     

新型复合预氧化技术控制副产物的试验研究

臭氧被广泛应用于饮用水预氧化工艺中,但是成本较高,而且会生成臭氧化副产物,如可同化有机碳(AOC)、溴酸盐和甲醛.因此,提出臭氧/高锰酸钾复合预氧化技术,并对照预臭氧化技术,进行了消毒副产物前质及臭氧化副产物控制的小试试验研究.结果表明,与预臭氧化(1.5 mg/L臭氧)相比,复合预氧化(0.6 mg/L臭氧 0.4 mg/L高锰酸钾)能促进混凝沉淀对消毒副产物前质的去除,总去除率与单独预臭氧化的去除率相当.而且又能降低AOC生成量,并促进混凝沉淀对AOC的去除,合计AOC去除率达43%左右.此外,对溴酸盐和甲醛生成量也有明显去除效果,比单独预臭氧化降低了78.4%和21.2%.     

O_3-BAC工艺臭氧优化和有机物分子质量分布研究

为了确定3种工艺:混凝-沉淀-砂滤-后臭氧-生物活性炭滤池(工艺Ⅰ)、预臭氧-混凝-沉淀-砂滤-生物活性炭滤池(工艺Ⅱ)和预臭氧-混凝-沉淀-砂滤-后臭氧-生物活性炭滤池(工艺Ⅲ)中臭氧的最优投加量和投加方式,采用动态实验进行了不同工况下有机物的去除效果研究,并从臭氧利用率的角度对3种工艺进行比较。同时,为了明晰工艺Ⅲ中各个单元对有机物的去除机制,研究了各处理阶段的有机物分子质量分布情况。结果表明,工艺Ⅲ在最佳工况下出水水质最优,但单位臭氧利用率较低,单位臭氧去除CODMn、TOC分别为0.92 mg/L和0.55 mg/L。该工艺中预臭氧可显著降低有机物分子质量水平,混凝沉淀砂滤主要去除分子质量3 k Da的有机物,后臭氧则将大分子有机物进一步氧化为分子质量3k Da的有机物,后者通过生物活性炭滤池得到有效地去除。因此,通过臭氧和生物活性炭的联用,能够有效去除有机物,是一种适宜的饮用水深度处理工艺。     

O3／GAC-常规处理珠江水系不同原水

以东江、西江和北江3种原水为研究对象,采用臭氧预处理-常规处理-臭氧活性炭系列处理,研究原水中有机物的去除及臭氧化副产物的产生和转化。结果表明,东江、西江和北江水中CODMn、UV254、甲醛和溴酸盐沿各处理单元过程变化规律基本一致;CODMn总去除率分别为60％、51％和39％,uV。总去除率分别为74％、96％和97％,最终出水甲醛浓度分别为0．004mg／L、0mg／L和0mg／L,B-O3-分别为3．1μg／L、8．7μg/L和35．5μg／L;CODMn的去除主要在预臭氧和活性炭过滤2个处理单元,预臭氧对UV254总去除率贡献最大,甲醛和溴酸盐浓度在主臭氧处理单元达到其峰值（西江甲醛除外）;氨氮和有机物浓度较低、pH值较高的北江原水,出水溴酸盐浓度最高。     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H₂O₂在催化臭氧化中的作用。结果表明,有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时,自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时,O₃和Fe²⁺/O₃对乙酸有着相似的降解效率。以上结果表明,自由基引发反应并不是臭氧化降解效率提高的充分条件。另外,当臭氧化过程有H₂O₂产生时,必须考虑类Fenton反应对臭氧化效率的影响。     

造纸中段废水的混凝-臭氧氧化深度处理研究

就混凝-臭氧氧化组合工艺对造纸中段废水生物处理出水的净化效果进行了研究.结果表明,Ca(OH)2对废水色度、TOC、COD和254 nm的紫外吸收值(UV254)的去除效果均优于聚合氯化铝/聚丙烯酰胺(PAC/PAM);Ca(OH)2-O3组合工艺的处理效果也优于PAC/PAM-O3工艺.当Ca(OH)2投加量为1 g/L、臭氧投加量为50 mg/L时,废水色度降低至10倍以下,COD小于150 mg/L.经Ca(OH)2混凝处理后,相对分子量在0.5～1.0 ku和10.0 ku以上的有机物显著减少;进一步臭氧氧化处理后,除0.5 ～1.0 ku范围的有机物大幅度增加外,其余分子量有机物显著减少.由于对色度贡献很大的大分子量物质的去除,废水的色度显著下降直至无色.     

O3/GAC-常规处理珠江水系不同原水简

以东江、西江和北江3种原水为研究对象,采用臭氧预处理-常规处理-臭氧活性炭系列处理,研究原水中有机物的去除及臭氧化副产物的产生和转化。结果表明,东江、西江和北江水中COD_Mn、UV₂₅₄、甲醛和溴酸盐沿各处理单元过程变化规律基本一致;COD_Mn总去除率分别为60%、51%和39%,UV₂₅₄总去除率分别为74%、96%和97%,最终出水甲醛浓度分别为0.004 mg/L、0 mg/L和0 mg/L,BrO₃^-分别为3.1 μg/L、8.7 μg/L和35.5 μg/L;COD_Mn的去除主要在预臭氧和活性炭过滤2个处理单元,预臭氧对UV₂₅₄总去除率贡献最大,甲醛和溴酸盐浓度在主臭氧处理单元达到其峰值（西江甲醛除外）;氨氮和有机物浓度较低、pH值较高的北江原水,出水溴酸盐浓度最高。     

引黄水臭氧预氧化强化混凝处理及安全性研究

分析了山西省太原段的引黄水水质,探讨了臭氧预氧化强化混凝处理引黄水的适用性、处理效果及安全性。结果表明,引黄水原水中的COD含量较高,而Br-未检出,提示可以采用臭氧预氧化强化混凝处理;总体来说,臭氧低投加量(0.52～0.98mg/L)时的助凝效果更为显著,在不同的聚合氯化铝(PAC)投加量下的除浊效果都优于常规混凝处理;单独投加臭氧时,随着臭氧投加量的增加,水体紫外吸光度(UV254)逐渐降低,当臭氧投加量为2.52mg/L时,UV254去除率为44%;虽然常规混凝处理即可控制出水的浊度和UV254,但由于混凝剂投加量大,综合效益较低,而臭氧预氧化在一定程度上能起到助凝作用,也能对水体UV254起到良好的控制作用;从甲醛、BrO3-产生量控制的角度来看,太原段引黄水水质适用臭氧预氧化强化混凝处理,安全性较好。     

臭氧氧化对二级出水有机物(EfOM)特性机制的影响

开展了臭氧氧化对二级出水有机物(effluent organic matter,Ef OM)的去除效能研究,并进一步采用超滤分离、三维荧光光谱等方法,系统研究了不同臭氧投加量下,Ef OM的分子量分布、亲疏水特性以及荧光特性的变化规律。结果表明,臭氧化去除Ef OM的效果有限,但能够有效分解二级出水中具有强烈紫外吸收的有机物。此外,臭氧能优先氧化分解二级出水中大分子有机物,有效提高二级出水的可生化性。臭氧氧化过程中,分子质量(molecular weight,MW)100 k Da的有机物组分被完全氧化分解,10 k DaMW100 k Da和1 k DaMW10 k D的有机物组分含量总体呈下降趋势,而MW1k Da的有机物组分随臭氧投加时间的延长含量不断上升。臭氧化后,Ef OM中疏水组分减少,亲水组分升高;酸性组分减少。随着臭氧投量的增加,蛋白质与腐殖酸类物质的荧光吸收强度迅速下降。     

垂直潜流人工湿地有机物积累及去向初步分析

为防治湿地堵塞、改善湿地处理效果,初步探讨了湿地中有机物的积累规律,并估算湿地中有机物不同去除途径的贡献率。结果表明,垂直潜流人工湿地中基质间积累的有机物主要是不可溶有机物,且粒径主要集中在5.00μm以上,分析是不同粒径有机物凝聚积累的缘故;垂向沿程基质间有机物的积累量受进水水力负荷影响明显;进入垂直潜流人工湿地中的有机物绝大部分都被生物(植物和微生物)吸收和利用而得以去除,该途径贡献率可达99.9%以上。     

水力停留时间对曝气生物滤池处理效能及运行特性的影响

通过实验室模型试验研究了曝气生物滤池处理模拟生活污水的效能,分析了水力停留时间(HRT)变化对曝气生物滤池处理效果及运行特性的影响规律。研究发现,当HRT大于0.6h时,曝气生物滤池具有良好的有机物和浊度的去除效果,而当HRT为0．4h时,处理效果则显著下降;反应器的硝化反硝化脱氮能力受HRT的影响比较明显,缩短HRT将使氨氮和总氮去除率迅速下降,当HRT为1.25h时,氨氮和总氮去除率分别达到70%和40％以上;缩短HRT会在一定程度上促进亚硝酸盐积累现象的发生。而反应器的过滤周期则与HRT呈明显的线性关系。     

Performance evaluation of the UV/H2O2 process on selected nitrogenous organic compounds: reductions of organic contents vs. corresponding C-, N-DBPs formations

The presence of various organic contaminants in water sources is of concern due to their direct threats to human health and potential to react with disinfectants to form carcinogenic byproducts including trihalomethanes, haloacetic acids and nitrosamines in finished water. This study applied both medium-pressure and low-pressure ultraviolet light coupled with hydrogen peroxide (UV/H₂O₂) to evaluate its efficacy for degradation of selected nitrogenous organic compounds and corresponding disinfection byproduct (DBP) formation. Six organic compounds were chosen as target precursors based on their nitrogen contents and molecular structures. The results showed that higher oxidation capacity resulted in better reduction of organic matters and DBP formation potentials (DBPFPs). However, insufficient contact time and oxidant doses could lead to a rise of DBPFPs in the early stages of UV/H₂O₂ reactions. A greater percentage removal was achieved for organic carbon than organic nitrogen after UV/H₂O₂ treatment, especially for compounds with complicated structure such as diltiazem. During the UV/H₂O₂ treatment, the intermediate products include tertiary amine, dimethyl amine (DMA) or DMA-like structures, which are N-nitrosodimethylamine (NDMA) precursors after chlorination or chloramination. Furthermore, it was observed that using dissolved organic nitrogen and DMA to predict NDMAFP could lead to biased conclusions because of the complex nature of nitrogenous matters in aqueous environments.     

用于污水再生利用的生物活性炭床的有机物降解特性

以微生物增殖动力学的基本方程-莫诺方程为出发点,通过氮同位素分析比较了具有同源性微生物的生物陶粒滤床和生物活性炭床的有机物生物降解规律,建立了生物活性炭床的有机物生物降解动力学方程,提出在污水再生利用过程中生物活性炭床符合高基质有机物降解动力学模型,即有机物降解呈一级反应动力学方程。以此方程为基础,分析计算了生物活性炭床沿炭床深度的吸附性能,结果表明,在生物活性炭床中,随生物功能的减弱,生物活性炭床对有机物的吸附能力逐渐加强。     

生物反应器填埋的沉降加速效应

通过实验室填埋柱模拟实验,研究了生物反应器填埋操作方式对填埋层沉降的影响。结果表明：与传统卫生填埋方式相比,回灌经厌氧生物处理后渗滤液的生物反应器填埋方式能够加速填埋层的沉降,140 d内沉降提高比例达10%以上。我国填埋垃圾高含水率、高易腐有机物含量的特性,使得其填埋层的次沉降系数高于文献值。填埋垃圾有机物降解量及其引起的垃圾水分排出量与填埋层沉降有显著相关性,表明有机物降解是引起填埋层沉降的重要因素,也是造成生物反应器填埋与传统卫生填埋方式初期沉降差异的主要原因。     

Effect of preozonation on the characteristic transformation of fulvic acid and its subsequent trichloromethane formation potential: presence or absence of bicarbonate

The effects of bicarbonate on the characteristic transformation of fulvic acid (FA) and its subsequent trichloromethane formation potential (TCMFP) were investigated in the process of preozonation. Dissolved organic carbon (DOC) removal rate and the residual aqueous ozone concentration during preozonation were measured with different bicarbonate concentration. The presence of bicarbonate inhibited DOC removal and decreased TCMFP yields in the initial oxidation period. In order to explain these phenomena, the molecular weight (MW) distribution (<5, 5-10, 10-30, and >30 kDa) and corresponding TCMFP were investigated for FA and its subsequent oxidation products. Furthermore, transformation of molecular structure, based on MW distribution, was also characterized with Fourier transform infrared (FTIR) spectrum. Bicarbonate showed different inhibiting effects on TCMFP of organic species with different MW, and more significant TCMFP decrement was observed for the high MW fraction (>30 kDa) than for the low MW fractions. Preozonation led to obvious reduction on DOC and UV254 in most of MW fractions wherever bicarbonate was present or not, demonstrating that ozone contributed to both organics mineralization and structure variation, synchronously. As being indicated from the results of FTIR and gas chromatography-mass spectrometry, the functional groups such as alcohols, epoxides and phenols, the formation of which was promoted with hydroxyl radicals (.OH) and would be remarkably inhibited by bicarbonate, were responsible for the increment of TCM precursor's concentration during ozonation. Results of these studies confirmed low dosage bicarbonate affecting the ozonation pathways, influencing the intermediate species formation and impacting its subsequent TCMFP yields through inhibiting the .OH radicals reactions mainly occurred in high MW fractions.     

不同工艺对含高浓度腐殖酸地下水处理的可行性

针对内蒙古农村地区高腐殖酸地下水的处理问题,分别对（pH调节）-PAC强化混凝、高锰酸钾预氧化／混凝、活性炭吸附／混凝、Fenton氧化等技术处理的可行性进行了研究,同时利用三维荧光和高效体积排阻色谱分析处理前后水中有机物的组成变化特征。有机分析结果显示,水中的有机物为腐殖酸类物质,分子量分别为1600和3500,腐殖酸类物质为水中色度的主要贡献者。原水PAC强化混凝、高锰酸钾预氧化／PAC混凝对有机物的去除效果不佳,处理前后水样DOC浓度无明显变化,而pH调节．PAC强化混凝、微米活性炭吸附和Fenton氧化均能有效去除有机物。将原水pH调节至6．5,经300mg／LPAC混凝后出水DOC降至5．99mg／L。活性炭投加量为0．6g／L时,DOC降至7．6mg／L,然后采用60mg／LPAC混凝出去高度分散而不易沉降的小颗粒活性炭。此外,当反应初始pH值为3,过氧化氢投加量为0．5％（v／v）,亚铁和双氧水摩尔比为0．05时,出水DOC降至5．6mg／L,氧化后有小分子有机物生成。     

The enhancement of the biodegradability of phenolic solution using preozonation based on high ozone utilization

In this research, the effects of preozonation on the biodegradability of 4-cresol, 4-nitrophenol and 2-chlorophenol solutions were investigated using a new gas-inducing reactor with high ozone utilization rate. The extent of preozonation may be monitored by determining the characteristic ozonation behaviors of preozonized phenolic solutions, such as residual phenolic concentration, ADMI value and ozone gas outlet concentration. Experimental results showed that as the initial phenolic compounds decomposed completely, the ozone gas outlet concentration rapidly increases. In addition, at pH 7, a peak ADMI value appears during the preozonation of 4-cresol and 2-chlorophenol, while for 4-nitrophenol the ADMI value decreases monotonically. Based on the characteristic ozonation behaviors and the ozone utilization rate, three characteristic times were chosen in order to have better control on the extent of preozonation. The effect of preozonation on the biodegradability of preozonized phenolic solution was studied based on these characteristic times. The intermediate products during the preozonation were also identified. The variation of BOD5 is strongly dependent on the accumulation of intermediate products. It is suggested that the best characteristic time is as the rapid increase of ozone gas outlet concentration in this study. The biodegradability (BOD5/COD) of preozonized 4-cresol, 2-chlorophenol and 4-nitrophenol solutions increase to 0.18, 0.26 and 0.33, respectively, for the best characteristic time.     

Change of genotoxicity for raw and finished water: role of purification processes

In China, the safety of drinking water becomes a significant issue due to serious aquatic environmental pollution. The genotoxic levels of raw and finished water from seven typical waterworks located in the five basins in China were then evaluated using umu test. Effect of conventional treatment processes (coagulation, filtration and disinfection) on the genotoxicity and the fate of dissolved organic matter (DOM) was discussed. The results showed that most of the selected finished water presented genotoxicity at or lower than 300 mL water sample exposure dose. The genotoxic effects of finished water were significantly higher than those of raw water. It also exhibited that there existed higher correlation between genotoxic effect and Br(-) than the other water quality parameters. The brominated trihalomethanes played a more important role in finished water genotoxicity than brominated haloacetic acids. The treatment processes could increase the genotoxic effects of finished water, especially for the chlorination treatment. The fluorescence spectra and high performance size-exclusion chromatogram analysis of DOM characters indicated that the proportion of low molecular weight acids, nitrogen containing aromatics, proteinaceous and microbially derived organic matters (200-300 Da) increased during purification processes, which indicated probably the release or formation of drinking water genotoxins.