不同分子质量区间腐殖酸的氯化反应特性研究

以自配的腐殖酸水样为研究对象,投加次氯酸钠对其进行消毒,考察了消毒过程中三卤甲烷、卤乙酸的生成量及DOC、UV254、A410、A465/A656的变化情况。结果表明,分子质量为50—100ku的腐殖酸为生成三卤甲烷和卤乙酸的最主要前体物;消毒反应后,各分子质量区间腐殖酸的DOC、UV254和A410都有不同程度的下降,且对小分子质量腐殖酸的DOC、UV254和A410的去除率高于对大分子质量腐殖酸的;A465／A656的变化表明消毒过程中腐殖酸的分子质量呈下降趋势。     

水中腐殖酸氯化生成卤代苯醌类消毒副产物的特性

采用腐殖酸配水,研究了氯化消毒过程中二氯对苯醌（DCBQ）、二溴对苯醌（DBBQ）、2,3-二溴-5,6-二甲基对苯醌（DBDMBQ）、四溴对苯醌（TBBQ）等卤代苯醌（HBQs）类消毒副产物的生成特性和影响因素。结果表明,腐殖酸氯化生成DCBQ和DBBQ的产率高于DBDMBQ和TBBQ。随着反应时间的增加,4种HBQs的生成量均呈现先快速升高之后保持稳定并稍有下降的趋势;随着温度的升高,HBQs的生成量呈增加趋势;弱酸性条件有利于HBQs的生成;在有效氯投加量为3～30mg/L范围内,DCBQ与DBBQ的生成量随加氯量的增加而增加,TBBQ与DBDMBQ的生成量随加氯量的增加先增加后减少;随着DOC浓度的增加,HBQs的生成量逐渐增加,其中分子质量<1 ku组分的单位质量有机物HBQs生成势最高。     

天然有机物氯消毒副产物的生成及影响因素研究

根据台湾自来水厂现场操作现状,以水体中典型天然有机物腐殖酸为研究对象,研究有机物性质、加氯量、溴离子、反应时间、温度等因素对氯消毒副产物生成的影响。结果表明,腐殖酸经臭氧氧化(投量为6 mg/mg C)后,富里酸和类腐殖酸的荧光强度均呈现下降趋势,A_(200-400)值下降、SR值增加,表征芳香族不饱和结构的减少及有机物分子质量的下降。对于含二溴或含二氯以上的三卤甲烷(THMs)的生成量,溴离子与反应时间的交互作用影响非常明显。CHBr_3和THMs的生成量与FIX和BIX指标均呈极显著相关性(p0.01),与A_(200-400)值呈显著相关性(p0.05),这意味着以光谱特征位置的讯号强度可进行自来水厂出水THMs或CHBr_3浓度的监控。     

臭氧活性炭工艺对三卤甲烷前体物的去除性能研究

通过两组试验对水厂臭氧活性炭深度处理工艺去除三卤甲烷前体物的性能进行了研究。结果表明:…臭氧活性炭工艺能有效去除TOC和UV254;对三卤甲烷前体物去除效果显著,去除率达40%以上;臭氧氧化对三卤甲烷前体物去除能力较小,活性炭滤池过滤去除效果显著。经臭氧活性炭工艺处理的水加氯消毒后三氯甲烷生成量较处理前可减少50%以上。臭氧活性炭工艺能有效降低消毒生成三卤甲烷的风险。     

改进现有的投氯消毒工艺

1　加强原水的调质手段在 ｐＨ 3～ 11范围内 ,三卤甲烷生成量与 ｐＨ成正比 ,卤乙酸生成量与 ｐＨ成反比。一般认为最适宜的ｐＨ范围为 6 .5～ 7.5 ,在此范围 ,既有利于提高消毒效果 ,又能减少由于氯消毒产生的消毒副产物。2　投氯点的变更原水中三卤甲烷前体物含量高时不能采用一级泵前、沉淀池或过滤前加氯 ,而应采用生物预处理 ,以免恶化水质 ,增加三卤甲烷和卤乙酸等消毒副产物。若需要灭藻或清洁滤池 ,可在进水处采用间歇大剂量投氯 ,以替代经常性预氯化 ,同时后氯化时间在 30ｍｉｎ以上 ,以提高消毒效果。3　控制投氯量加氯过多 ,能…     

磺胺甲口恶唑氯化消毒副产物生成势及影响因素研究

研究了东太湖水源水中典型抗生素磺胺甲口恶唑(SMX)氯化消毒副产物(DBPs)生成势及影响因素。结果表明:SMX经氯化反应后可生成三卤甲烷、卤乙腈、卤乙酸、卤乙醛、卤代丙酮等多种DBPs,且加氯量、反应时间、反应温度、pH值等因素均会影响其DBPs生成势。当溶液中存在溴离子时,SMX氯化生成的三卤甲烷、卤乙酸的组分及生成量有较大变化,且随着溴离子浓度的增大,一些氯代消毒副产物(Cl-DBPs)会转化为具有更高毒性的溴代消毒副产物(Br-DBPs)。     

氯化消毒条件及污水水质对生成THMs、HAAs的影响

系统地研究了消毒务件和水质在城市污水氯化消毒过程中对生成三卤甲烷和卤乙酸的影响。结果表明，投氯量对三卤甲烷和卤乙酸生成量的影响最大，投氯量为40mg／L时的生成量分别约是投氯量为5mg／L时的30倍和70倍。三卤甲烷浓度随反应时间和温度无明显变化，而卤乙酸浓度在反应2h后达到峰值并在之后逐渐降低，且随温度的升高呈下降趋势。pH对两类副产物生成的影响几乎相反，近中性条件下的三卤甲烷生成量最多而卤乙酸生成量最少。水中氨氮浓度的增加会导致三卤甲烷生成量略有下降，而卤乙酸浓度却大幅上升。溴离子浓度升高将导致三卤甲烷和卤乙酸生成量显著增加，其中三氯甲烷浓度下降，三溴甲烷浓度显著上升，混合取代的三卤甲烷浓度先增加后减少。与此类似，二氯乙酸和三氯乙酸浓度随溴离子浓度的增加而减少，含溴卤乙酸浓度则有不同程度的增加。反应温度、反应时间、pH和氨氮对污水消毒副产物生成的影响与已报道的饮用水消毒中的作用规律存在显著差异，甚至截然相反，这为有针对性地选取消毒工艺参数提供了依据。     

五种消毒剂消毒饮水后形成三卤甲烷的研究

五种消毒剂消毒三种水源后都产生了三卤甲烷。消毒剂不同产生的三卤甲烷其组成也不相同。提高有机物浓度，消毒剂剂量，水温和延长反应时间，都可以增加三卤甲烷的生成量。ＰＨ＝９时，三卤甲烷的生成量最高。     

三卤甲烷生成势测定方法的优化

三卤甲烷是饮用水中加氯消毒的主要副产物,长期饮用含三卤甲烷的水会对人体的健康产生影响。三卤甲烷生成势是指某一水质在一定的加氯量和反应时间下,能生成三卤甲烷的最大量。针对原有三卤甲烷生成势测定方法步骤复杂,培养周期长,加氯量公式不够通用的问题,建立了简便的测定方法。该方法缩短培养周期为72小时,取消4小时培养的步骤,提出了较为合理的加氯量及补氯时间,完善了测定方法,经过多次实验尝试结果满意。     

东湖水厂自来水中三卤甲烷及对策研究

论述了武汉东湖水厂制水过程中三卤甲烷的产生原因,提出了增加生物预处理、取消预加氯、强化净化措施,减少三卤甲烷生成量的对策。     

Characteristic transformation of humic acid during photoelectrocatalysis process and its subsequent disinfection byproduct formation potential

In this study, degradation of humic acid (HA) via photoelectrocatalysis (PEC) process and corresponding disinfection byproduct formation potential (DBPFP) were investigated. Particularly, structure variation and subsequent DBPFP of HA during PEC treatment were correlated. The PEC process was found to be effective in reducing dissolved organic carbon concentration by 75.0% and UV absorbance at 254 nm by 92.0%. Furthermore, 90.3% of haloacetic acids formation potential and 89.8% of trihalomethanes formation potential were reduced within 180 min. Based on molecular weight and resin fraction results, it was demonstrated that HA with large aromatic, hydrophobic and long aliphatic chain organics were transformed into small and hydrophilic organics during PEC process. Combined with the fourier transform infrared spectra and ¹³C nuclear magnetic resonance spectra analysis of HA fractions, it was concluded that phenolic hydroxyl and conjugated double bonds tended to be attacked by hydroxyl radicals during PEC process; these groups were reactive with chlorine to produce disinfection byproducts (DBP), especially trihalomethane and trichloroacetic acid. By contrast, amino, carboxyl and alcoholic hydroxyl groups were relatively difficult to be oxidized during PEC process; these groups had the potential to form dichloroacetic acid during chlorination. Results of these studies confirmed that PEC process was a safe and effective technique to decrease DBP formation significantly in water treatment plant.     

Correlation of humic substance trihalomethane formation potential and adsorption behavior to molecular weight distribution in raw and chemically treated waters

The molecular weight distributions (MWDs) of several commercially prepared humic and fulvic acids and organic matter present in natural waters were analyzed by gel chromatography. The responses of these substances to treatment by alum coagulation, lime softening, and activated carbon adsorption were also analyzed, as were their trihalomethane formation potentials before and after each treatment. The treatability characteristics and trihalomethane formation properties of the different organic substances were then related to their respective MWDs. Differences in the MWDs were found to effect differences in the behavior of lumped parameter measures of organic matter (such as TOC) with respect to the several treatment operations. The treatments in turn were observed to alter the MWDs of the organic substances as well as their phenomenological behavior in subsequent process operations.     

Characterization of aquatic humic substances

Aquatic natural organic matter (NOM) is composed of a large variety of compounds. In this study, NOM from Uzquiza Reservoir in Burgos (Spain) was fractionated using a resin adsorption procedure, and three humic substances – natural fulvic and humic acids (NFA and NHA, respectively) extracted from the mentioned reservoir and a commercially supplied humic acid (CHA) – were characterized by molecular weight (MW) distribution, elemental composition, organic acidity and ultraviolet and infrared spectroscopy. The results indicate that Uzquiza Reservoir NOM is mainly composed of fulvic acids (45%) and low MW hydrophilic acids (27%). MWs obtained are in the following order: CHA (4500 Da)>NHA (2500 Da)>NFA (1000 Da). Both humic acids (CHA and NHA) have the highest specific UV absorbance values (SUVA, an aromaticity indicator) whereas NFA shows a higher total and carboxylic acidity, which is in accordance with its higher solubility in water. Infrared spectra confirm these results.     

O3/BAC对氯化消毒副产物的控制作用

采用臭氧化—生物活性炭(O3／BAC)深度处理工艺去除水中消毒副产物前质的试验结果表明，该工艺能够有效去除水中消毒副产物前质，可控制氯化消毒副产物的生成，其中主臭氧化对三卤甲烷前质和卤乙酸前质均具有很好的去除效果，生物活性炭对卤乙酸前质表现出较好的去除效果，但对三卤甲烷前质的去除效果有限；藻类、有机物等在滤层的累积使得砂滤池在同一工作周期中的不同阶段对水中三卤甲烷前质的去除效果有所不同，因而需要合理设置砂滤池的反冲洗周期。臭氧化—生物活性炭工艺充分发挥了臭氧化和生物活性炭两种技术的优点，并相互促进和补充，能够充分保障饮用水的安全性。     

饮用水中溴化物的混凝去除及影响因素研究

在饮用水的消毒过程中，溴化物可与消毒剂反应生成具有“三致”效应的消毒副产物。为此，选择AlCl3作混凝剂，研究了混凝去除溴化物的效果及影响因素。结果表明，向模拟水样（溴化物初始浓度为0．2mg／L）中投加3-15mg／L的AlCl3，当无腐殖酸存在时对溴化物的去除率为93．3％-99．2％，当有腐殖酸存在时对溴化物的去除率为78．4％～98．4％；对于湘江原水。投加15mg／L的AlCl3时对溴化物的去除率为87．0％。在低混凝剂投量或高pH值条件下，腐殖酸的存在明显降低了对溴化物的去除率；在高混凝剂投量或低pH值条件下，腐殖酸对去除溴化物的影响较小。因此，可采用强化混凝去除饮用水中的溴化物。     

Comparison of NOM character in selected Australian and Norwegian drinking waters

Observations from many countries around the world during the past 10-20 years indicate increasing natural organic matter (NOM) concentration levels in water sources, due to issues such as global warming, changes in soil acidification, increased drought severity and more intensive rain events. In addition to the trend towards increasing NOM concentration, the character of NOM can vary with source and time (season). The great seasonal variability and the trend towards elevated NOM concentration levels impose challenges to the water industry and the water treatment facilities in terms of operational optimisation and proper process control. The aim of this investigation was to compare selected raw and conventionally treated drinking water sources from different hemispheres with regard to NOM character which may lead to better understanding of the impact of source water on water treatment. Results from the analyses of selected Norwegian and Australian water samples showed that Norwegian NOM exhibited greater humic nature, indicating a stronger bias of allochthonous versus autochthonous organic origin. Similarly, Norwegian source waters had higher average molecular weights than Australian waters. Following coagulation treatment, the organic character of the recalcitrant NOM in both countries was similar. Differences in organic character of these source waters after treatment were found to be related to treatment practice rather than origin of the source water. The characterisation techniques employed also enabled identification of the coagulation processes which were not necessarily optimised for dissolved organic carbon (DOC) removal. The reactivity with chlorine as well as trihalomethane formation potential (THMFP) of the treated waters showed differences in behaviour between Norwegian and Australian sources that appeared to be related to residual higher molecular weight organic material. By evaluation of changes in specific molecular weight regions and disinfection parameters before and after treatment, correlations were found that relate treatment strategy to chlorine demand and DBP formation.     

Use of three-dimensional excitation and emission matrix fluorescence spectroscopy for predicting the disinfection by-product formation potential of reclaimed water

This study was undertaken to demonstrate the feasibility of using three-dimensional excitation-emission matrix (3DEEM) fluorescence spectroscopy for the determination of chlorination disinfection by-product (DBP) precursors and the disinfection by-product formation potential (DBPFP) of reclaimed water samples. Two major DBP precursors were examined in this study, including humic acid (HA) and fulvic acid (FA). The 3DEEM fluorescence results obtained from various reclaimed water samples indicated that the reclaimed water samples were rich in fulvic acid-like substances that were associated with two main peaks (Ex/Em = 235-245/420-440 nm, and Ex/Em = 330-340/410-430 nm) in the fluorescence spectrum. The results also illustrated that the wavelength location of peak fluorescence intensity of a reclaimed water sample was independent of the influent water quality and the wastewater treatment process used in the reclamation plant. As a result, the peak fluorescence intensity and the wavelength location of the peak were used to identify the species of DBP precursors and their concentrations in the reclaimed water sample. Four regression models were then developed to relate the peak fluorescence intensity of the water sample to its DBPFP, including the formation potential of trihalomethane (THMFP) and the formation potential of haloacetic acid (HAAFP). The regression models were verified using the measured DBPFP results of a series of reclaimed water samples. It was found that the regression modeling results matched the measured DBPFP values well, with prediction errors below 10%. Therefore, the use of 3DEEM fluorescence spectroscopy together with the developed regression models in this study can provide a reliable and rapid tool for monitoring the quality of reclaimed water. Using this method, water quality could be monitored online, without utilizing the lengthy conventional DBPFP measurement.     

Influence of humic substances on the ultraviolet disinfection of surface waters

The efficiency of ultraviolet (UV) disinfection and the regrowth potential of total coliforms were investigated in humic waters. Experiments were conducted according to an experimental design in which a UV radiation dose range of 68–681 mW s/cm² was applied to waters containing various concentrations (0–10 mg/L) of fulvic acid. Experimental results strongly suggested that the harmful effect of UV radiation on bacteria was diminished in humic waters due to absorption of UV light. Increasing concentrations of fulvic acid appeared to enhance its influence with elevated doses of UV radiation. Measured inactivation responses were on the order of 1–6 log₁₀ units for the UV dose range used. Comparison of k (inactivation coefficient) values for nonhumic water to highly humic water indicated that k decreased proportionally as the fulvic acid concentration of water was increased. The results of dark‐incubation tests indicated significant regrowth of bacteria in fulvic acid‐containing waters.     

Characterization of humic substances present in landfill leachates with different landfill ages and its implications

Humic and fulvic acids extracted from landfill leachates were characterized using elemental analysis and various spectroscopic methods. Molecular size distribution of the humic substances (HS) was also determined using batch ultrafiltration technique and permeation coefficient model. The element analysis and spectral features obtained from UV/visible, IR, and 1H and 13C NMR showed that the aromatic character in the leachate HS was relatively lower than that of commercial humic acid (Aldrich Co.), and higher in the HS of older landfill leachate. Fluorescence spectra indicated that humic acids had a relatively higher content of condensed aromatic compounds than the fulvic acids obtained from the same sources, and the spectrum of commercial humic acid showed that aromatic compounds may be present in a much more condensed and complex form. Molecular size distribution data revealed that the leachate humic acids contained a higher percentage of smaller molecules of < 10,000 D, compared with that of the commercial humic acid (45 approximately 49% vs. 33%), and molecular size of the leachate HS had a tendency to increase as landfill age increased. These results indicate that the HS from landfill leachates were in an early stage of humification, and the degree of humification increased as the landfilling age increased, which implies important information on various related researches, such as interactions of HA with pollutants in terrestrial environments, and optimization of leachate treatment processes with respect to landfill age.