铁盐和铝盐混凝剂对消毒副产物的控制作用及机制研究

以三氯化铁和硫酸铝为研究对象,探讨了两种混凝剂对三氯甲烷生成量的控制作用及控制机制．结果表明,与硫酸铝相比,三氯化铁可以更好地控制三氯甲烷的生成量,对有机物的去除方面,也具有良好的效果．E4／E6变化表明,三氯化铁和硫酸铝对水中有机物的去除机制不同,硫酸铝主要去除水中大分子的有机物,三氯化铁更倾向于去除水中小分子有机物,而这些小分子有机物通常是消毒副产物的前体物,从而使三氯化铁对消毒副产物的控制作用较硫酸铝明显．     

光催化氧化（UV+TiO2）法处理印染废水生化出水及其各类有机物去除

采用UV+TiO2光催化氧化法处理印染废水生化出水,考察了反应时间、TiO2投加量以及初始pH对反应的影响,结果表明,TiO2投加量800 mg·L-1,反应时间8 h,反应pH为原水pH(6.5～8.0),在此操作条件下,ADMI7.6、DOC和COD的去除率分别为86%、20%及46%;选取两组反应条件,对其进出水采用XAD-8/XAD-4树脂联用技术,分析疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物的去除情况,结果表明,UV+TiO2光催化氧化处理工艺都能够长期有效去除印染废水生化出水中的弱疏水物质、疏水物质和非酸疏水物质引起的色度.     

活性炭吸附对生化出水中不同种类有机物的去除效果

研究活性炭吸附对城市污水生化出水中疏水酸、非酸疏水物质、弱疏水物质及亲水物质的去除效果,在静态吸附实验中,当活性炭投加量为0.3g·l-1时,达到吸附平衡后,对DOC和UV254的去除率可分别达到54%和76%,同时能够完全消除生化出水的生物毒性,活性炭吸附对疏水酸和亲水物质均有良好的去除效果,其DOC去除率分别达到50%和80%,对非酸疏水物质和弱疏水物质去除率相对稍低,DOC去除率分别为29%和28%,活性炭吸附对有机物的亲疏水性没有明显偏好.     

还原铁法处理印染废水生化出水及原理

采用还原铁粉处理印染废水生化出水,以ADMI7.6作为主要测试指标,考察铁粉投加量、反应时间以及进水pH对出水水质的影响,并研究在此过程中铁粉还原作用和混凝絮凝作用对整体效果的贡献比.结果表明,条件1:铁粉投加量=1.0 g.L-1,反应时间150 min,进水pH 2;条件2:铁粉投加量1.0 g.L-1,反应时间150 min,进水pH 3.条件1时,ADMI7.6去除率达到80%,但铁泥量大,酸碱消耗大,在此反应条件下,铁粉还原去除40%,混凝絮凝去除60%;条件2时,ADMI7.6去除率达到50%左右,产铁泥量小,经济合理;在此反应条件下,铁粉还原去除55%—63%左右,混凝絮凝去除37%—45%左右.经XAD8/XAD4树脂联用,分析疏水酸、非酸疏水物质、弱疏水物质及亲水物质4类有机物的去除情况表明,条件1时,能够高效去除非酸疏水物质,去除率为95%,对于疏水酸以及弱疏水物质也有一定的去除效果;条件2时,对4类有机物去除均有一定作用,但对于非酸疏水物质以及疏水酸的去除效果要略差于条件1.     

印染废水生化出水高锰酸钾强化混凝深度处理溶解性有机物的去除特性

采用高锰酸钾预氧化,强化某印染废水生化出水铁盐混凝深度处理溶解性有机物(DOM),考察了高锰酸钾强化混凝对印染废水生化出水中DOM的去除特性并为优化混凝深度处理工艺提供理论参考.在最优投加条件下,高锰酸钾强化混凝处理提高了DOM色度的去除效果,以美国染料生产协会色度值(ADMI7.6)表征时为84%,出水ADMI7.6值较单独混凝处理降低了43%.但以溶解性有机碳(DOC)表征时去除率基本保持不变,为55%.通过XAD-8/XAD-4吸附树脂分离技术和分子量分布分析发现,高锰酸钾强化混凝处理通过有效去除疏水性和弱疏水性DOM色度降低了出水的色度.同时,出水中亲水性和小分子DOM(MW<1 kDa)较单独混凝处理分别增加了34%和15%,导致了DOM去除率以DOC表征时无显著改善.采用三维荧光光谱技术定性分析表明,引起色度的可见类富里酸和类腐殖酸物质被进一步去除使出水色度降低,此时出水中增多的小分子亲水性DOM主要为类蛋白质和富里酸物质.因此,高锰酸钾强化混凝处理过程仍需与其它能去除亲水性、小分子量DOM(MW<1 kDa)的处理工艺结合,以提高总体去除效率.     

印染废水生化出水中有机污染物特性及在硫酸镁混凝过程中的去除行为

以某印染废水二级生化出水为研究对象,考察了生化出水中有机污染物中各组分含量、分子量分布特点等特性,以及各类有机物在硫酸镁混凝处理过程中的去除行为.实验结果表明,该印染废水的生化出水溶解性有机物的主要成分是疏水性物质,以溶解性有机碳（DOC）表征时占总DOC的78%,其中非酸疏水物质约占46%,而以UV254表征时约占总55%,以美国染料生产协会色度值（ADMI7.6）表征时为97%,其中以非酸疏水物质的贡献最大,达到66%,并且非酸疏水物质中不饱和双键或芳香环有机物的含量较高.生化出水中的DOC主要集中在小于1000 D的有机物上,占37%.在硫酸镁的最佳混凝条件下,可以有效地去除由大分子量的非酸疏水物质引起的色度,而对小分子量的有机物也有一定的去除效果.     

卤代醛/酮消毒副产物的生成潜能及其前驱物的结构特征

卤代醛和卤代酮类消毒副产物因具有"致畸、致癌、致突变"作用而倍受关注.对卤代醛/酮类消毒副产物控制及其前体物识别对饮用水安全保障具有重要意义.以大分子酸、疏水性酸、芳香族类亲水酸、亲水酸、糖类和氨基酸6类共14种常见有机物为对象,研究了不同有机物在氯化消毒过程中的卤代醛/酮生成潜力.结果表明,富里酸、柠檬酸、苹果酸、L-苏氨酸和L-天冬酰胺具有较高的卤代醛/酮生成势.有机物生成卤代醛/酮的过程包括2个阶段:前体物首先经氧化、脱羧等过程生成乙醛和丙酮,乙醛和丙酮被逐步氯代而生成氯代醛和氯代酮.实际水体的消毒实验表明,卤代醛/酮的生成势与水样中有机物的浓度无必然联系,但与水样中醇羟基及羰基官能团的含量呈正相关(R~2=0.69—0.98).     

饮用水中消毒副产物的消减措施

为了去除水中的病毒和细菌等有毒物质,在饮用水中添加氯是最常用的一种消毒方法.但是由于加入的氯会与水中的天然有机物(NOM)反应,产生包括三卤甲烷(THMs)和卤乙酸(HAAs)在内的各种氯化消毒副产物.这些消毒副产物的去除对饮用水的安全是一个值得关注的问题.     

焦化废水二级生化出水中有机污染物的氧化特性

考察了O3氧化法与UV/O3氧化法对焦化废水二级生化出水中溶解性有机物的去除效果,以及二级出水中有机污染物的氧化特性.结果表明,O3氧化法对于二级出水的UV254值具有较高的去除效率,30min内即可达75.7%,但对COD和DOC的去除效果很差,150min的去除率仅为37.1%和33.7%.而UV/O3氧化法对二级生化出水UV254,COD和DOC均具有良好的去除效果,150min时的去除率分别为95.3%,90.2%和77.8%.经过O3氧化法处理后,疏水性物质的浓度明显下降,而弱疏水有机物与亲水性有机物浓度有所上升;UV/O3氧化法处理对疏水性有机物和弱疏水有机物均具有良好的去除效果,而亲水性有机物浓度仅得到部分降低.     

海水循环养殖系统水处理工艺综述

论述了海水循环养殖系统(RAS)需要控制的水质参数及相关单元水处理工艺.RAS需要对盐度、pH、温度、溶解氧等水质参数进行监测控制,并常采用物理、生物、化学处理的组合工艺,使固体物质、氨氮、亚硝酸盐、硝酸盐、有机物以及致病微生物等的浓度维持在安全范围内.固体物质根据粒径和可沉降性的不同,可采用沉降、过滤、泡沫分离或生物过滤法去除;氨氮、亚硝酸盐以及硝酸盐主要通过生物的硝化和反硝化作用去除;有机物主要通过生物降解去除;化学药剂消毒以及紫外辐照是RAS常用的消毒方法,消毒剂残余及消毒副产物对水质和动物健康的影响是选择合适消毒方法需要考虑的两个关键因素.最后,列举了几种海水RAS常用的组合处理工艺,并提出了针对性的改进建议.     

Removal of organic matter and disinfection by-products precursors in a hybrid process combining ozonation with ceramic membrane ultrafiltration

The performance of an integrated process including coagulation, ozonation, ceramic ultrafiltration (UF) and biologic activated carbon (BAC) filtration was investigated for the removal of organic matter and disinfection by-products (DBPs) precursors from micro-polluted surface water. A pilot scale plant with the capacity of 120 m³ per day was set up and operated for the treatment of drinking water. Ceramic membranes were used with the filtration area of 50 m² and a pore size of 60 nm. Dissolved organic matter was divided into five fractions including hydrophobic acid (HoA), base (HoB) and neutral (HoN), weakly hydrophobic acid (WHoA) and hydrophilic matter (HiM) by DAX-8 and XAD-4 resins. The experiment results showed that the removal of organic matter was significantly improved with ozonation in advance. In sum, the integrated process removed 73% of dissolved organic carbon (DOC), 87% of UV₂₅₄, 77% of trihalomethane (THMs) precursors, 76% of haloacetic acid (HAAs) precursors, 83%of trichloracetic aldehyde (CH) precursor, 77% of dichloroacetonitrile (DCAN) precursor, 51% of trichloroacetonitrile (TCAN) precursor, 96% of 1,1,1-trichloroacetone (TCP) precursor and 63% of trichloronitromethane (TCNM) precursor. Hydrophobic organic matter was converted into hydrophilic organic matter during ozonation/UF, while the organic matter with molecular weight of 1000–3000 Da was remarkably decreased and converted into lower molecular weight organic matter ranged from 200–500 Da. DOC had a close linear relationship with the formation potential of DBPs.     

京密引水中天然有机物的形态

用改进的Ｌｅｅｎｈｅｅｒ分离方法，并引入最新的ＸＡＤ－８，ＸＡＤ－４树脂串联技术，将京密引水中有机物定量分离为悬浮和溶解态两大类。后者又进一步分离为憎水有机物、腐殖酸类，ＸＡＤ－４酸和亲水中性有机物等形成。溶解态有机物含量约为３ｍｇＣ／ｌ，其中一半左右为腐殖酸类。ＸＡＤ－４酸占溶解态有机１５－２０％，非极性憎水有机物所占比例很低。     

焦化废水中溶解性有机物组分的特征分析

焦化废水是典型的具有复杂有机质的工业废水,其复杂的有机构成制约了水处理的水质达标,且可能对排入水体构成危害.为了探明其溶解性有机物的组成,采用XAD-8大孔树脂将焦化废水中的溶解性有机物分为亲水性组分(HIS)、疏水酸性组分(HOA)、疏水碱性组分(HOB)和疏水中性组分(HON),分析了各组分的溶解性有机物(DOC)、紫外-可见光谱、色度,并采用GC/MS对各组分中有机物进行定性分析.结果表明,焦化废水中的有机物主要为HIS和HOA组分,其DOC含量分别占总DOC的44.3%和32.4%;焦化废水在200—250 nm和300—400 nm范围内有特征吸收峰,且吸收光强度顺序为HIS>HOA>HON>HOB;焦化废水的色度主要由HOA和HON构成,其在525 nm和436 nm处的吸光度分别占焦化废水吸光度的42.9%(HON)、42.1%(HON)和21.4%(HOA)、15.8%(HOA);焦化废水中亲水性物质主要是苯胺、苯酚、喹啉、异喹啉,疏水酸性物质中主要是各种甲基取代的酚类物质,疏水碱性物质主要是各种胺类和含氮杂环化合物,疏水中性物质主要是吲哚及其衍生物.     

Fluorescence spectroscopic studies of the effect of granular activated carbon adsorption on structural properties of dissolved organic matter fractions

This work investigated the effect of granular activated carbon adsorption (GACA) on fluorescence characteristics of dissolved organic matter (DOM) in secondary effluent, by means of excitation–emission matrix (EEM) spectra, the fluorescence regional integration (FRI) method, synchronous spectra, the fluorescence index defined as the ratio of fluorescence emission intensity at wavelength 450 nm to that at 500 nm at excitation (λ_ex)=370 nm, and the wavelength that corresponds to the position of the normalized emission band at its half intensity (λ_0.5). DOM in the secondary effluent from the North Wastewater Treatment Plant (Shenyang, China) was fractionated using XAD resins into 5 fractions: hydrophobic acid (HPO–A), hydrophobic neutral (HPO–N), transphilic acid (TPI–A), transphilic neutral (TPI–N) and hydrophilic fraction (HPI). Results showed that fluorescent materials in HPO–N and TPI–N were less readily removed than those in the other fractions by GACA. The relative content of fluorescent materials in HPO–A, TPI–A and HPI decreased whereas that in HPO–N and TPI–N increased as a consequence of GACA. Polycyclic aromatics in all DOM fractions were preferentially absorbed by GACA, in comparison with bulk DOM expressed as DOC. On the other hand, the adsorption of aromatic amino acids and humic acid-like fluorophores exhibiting fluorescence peaks in synchronous spectra by GACA seemed to be dependent on the acid/neutral properties of DOM fractions. All five fractions had decreased fluorescence indices as a result of GACA. GACA led to a decreased λ_0.5 value for HPO–A, increased λ_0.5 values for HPO–N, TPI–A and HPI, and a consistent λ_0.5 value for TPI–N.     

Characterization of dissolved organic matter from saline soils by fluorescence spectroscopy

In this paper hydrophilic (HI) and hydrophobic (HO) fractions of dissolved organic matter (DOM) extracted from soils at different degrees of salinisation were characterised by means of fluorescence spectroscopy in the emission, excitation and synchronous-scan modes. Results provided evidence of the different chemical nature of DOM fractions and allowed to distinguish hydrophilic and hydrophobic fractions extracted from the same soil substrate. The strong decrease in fluorescence intensity observed with the increasing salinity of the soils can be utilised to obtain information on the salinity level of different soil substrates by comparison of spectral fluorescence intensities.     

Feasibility of bubble surface modification for natural organic matter removal from river water using dissolved air flotation

A novel, functionalized bubble surface can be obtained in dissolved air flotation (DAF) by dosing chemicals in the saturator. In this study, different cationic chemicals were used as bubble surface modifiers, and their effects on natural organic matter (NOM) removal from river water were investigated. NOM in the samples was fractionated based on molecular weight and hydrophobicity. The disinfection byproduct formation potentials of each fraction and their removal efficiencies were also evaluated. The results showed that chitosan was the most promising bubble modifier compared with a surfactant and a synthetic polymer. Tiny bubbles in the DAF pump system facilitated the adsorption of chitosan onto microbubble surfaces. The hydrophobic NOM fraction was preferentially removed by chitosan-modified bubbles. Decreasing the recycle water pH from 7.0 to 5.5 improved the removal of hydrophilic NOM with low molecular weight. Likewise, hydrophilic organic compounds gave high dihaloacetic acid yields in raw water. An enhanced reduction of haloacetic acid precursors was obtained with recycle water at pH values of 5.5 and 4.0. The experimental results indicate that NOM fractions may interact with bubbles through different mechanisms. Positive bubble modification provides an alternative approach for DAF to enhance NOM removal.

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氯化消毒饮用水中强致突变物MX[3-氯-4-(二氯甲基)-5-羟基-2(5H)-呋喃酮]的形成

利用一系列XAD吸附树脂及大孔阴、阳离子交换树脂,将太湖水中溶解态有机物分离为溶解态富里酸类、腐殖酸类、憎水弱酸类、憎水碱类、憎水中性物类、亲水酸类、亲水碱类七种组分,分别对不同组分的有机物进行氯化处理后,用GC/MS选择离子峰面积法测定了产物中的MX[3-氯-4-（二氯甲基）-5-羟基-2（5H）-呋喃酮]。结果表明,太湖水体中的溶解态腐殖酸类可能是生成MX的重要前驱物。     

Effects of humic acid on residual Al control in drinking water treatment plants with orthophosphate addition

This study aimed to investigate the effects of humic acid (HA) on residual Al control in drinking water facilities that used orthophosphate addition. The results showed that adding orthophosphate was an effective method for residual Al control for the raw water without HA. When orthophosphate was added at 1.0 min before the addition of poly aluminum chloride (PACl), the concentrations of soluble aluminum (Sol-Al) and total aluminum (Tot-Al) residue were 0.08 and 0.086 mg·L^-1, respectively; both were reduced by 46% compared with the control experiment. The presence of HA would notably increase the residual Al concentration. For the raw water with 5 mg·L^-1 of HA, the concentrations of Sol-Al and Tot-Al increased from 0.136 and 0.174 mg·L^-1 to 0.172 and 0.272 mg·L^-1, respectively. For water with a HA concentration above 5 mg·L^-1, orthophosphate was ineffective in the control of residual Al, though there were still parts of orthophosphate were removed in coagulation. The amounts of Al removal were positively correlated with the solids freshly formed in coagulation. Similar to the raw water without HA, the best Al control was obtained with orthophosphate salt added at 1.0 min before PACl. HA concentrations in the raw water, solution pH, and the orthophosphate dosage suitable for residual Al control by orthophosphate precipitation were also investigated.     

Chemical identification and genotoxicity analysis of petrochemical industrial wastewater

The actual harmful effects of industrial wastewater can not be reflected by the conventional water quality index. Therefore, the change in dissolved organic matter and the genetic toxicity of petrochemical wastewater were observed in the current study by examining the wastewater treatment plant of a large petrochemical enterprise in Northwest China. Using XAD-8, MSC, and DA-7 resins, the wastewater was separated into six fractions, namely, hydrophobic acid (HOA), hydrophobic neutral (HOB), hydrophobic alkaline, hydrophilic acid, hydrophilic alkaline, and hydrophilic neutral. Umu-test was used to detect the genetic toxicity of the wastewater samples, and fluorescence spectra were also obtained to examine genetic toxic substances. The results show that wastewater treatment facilities can effectively reduce the concentration of organic matter in petrochemical wastewater (p<0.05). However, the mixing of aniline wastewater can increase the amount of organic carbon (p<0.05) and can overload facilities. This finding shows that the mixed collection and joint treatment of different types of petrochemical wastewater can affect the water quality of the effluent. Particularly, hydrophobic substances can be difficult to remove and account for a relatively large proportion of the effluent. The mixture of aniline wastewater can increase the genetic toxicity of the effluent (p<0.05), and biologic treatment can not effectively decrease the toxicity. Most of the genetic toxicology may exist in the HOA and HOB fractions. Fluorescence spectroscopy also confirms this result, and tryptophan-like substances may play an important role in genetic toxicity.