Membrane fouling in ultrafiltration of natural water after pretreatment to different extents

The combined fouling during ultrafiltration(UF) of surface water pretreated to different extents was investigated to disclose the roles of polysaccharides, proteins, and inorganic particles in UF membrane fouling. Both reversible and irreversible fouling decreased with enhanced pretreatment(biologically active carbon(BAC) treatment and sand filtration). The sand filter effluent fouled the membrane very slowly. The UF membrane removed turbidity to less than 0.1 nephelometric turbidity unit(NTU), reduced polysaccharides by 25.4%–29.9%, but rejected few proteins. Both polysaccharides and inorganic particles were detected on the fouled membranes, but inorganic particles could be effectively removed by backwashing. The increase of turbidity in the sand filter effluent to 3.05 NTU did not significantly increase the fouling rate, but an increase in the turbidity in the BAC effluent to6.11 NTU increased the fouling rate by more than 100%. The results demonstrated that the polysaccharide, not the protein, constituents of biopolymers were responsible for membrane fouling. Membrane fouling was closely associated with a small fraction of polysaccharides in the feed water. Inorganic particles exacerbated membrane fouling only when the concentration of fouling–inducing polysaccharides in the feed water was relatively high. The combined fouling was largely reversible, and polysaccharides were the predominant substances responsible for irreversible fouling.     

Towards a better hydraulic cleaning strategy for ultrafiltration membrane fouling by humic acid: Effect of backwash water composition

As a routine measurement to alleviate membrane fouling, hydraulic cleaning is of great significance for the steady operation of ultrafiltration (UF) systems in water treatment processes. In this work, a comparative study was performed to investigate the effects of the composition of backwash water on the hydraulic cleaning performance of UF membranes fouled by humic acid (HA). Various types of backwash water, including UF permeate, Milli-Q water, NaCl solution, CaCl₂ solution and HA solution, were compared in terms of hydraulically irreversible fouling index, total surface tension and residual HA. The results indicated that Milli-Q water backwash was superior to UF permeate backwash in cleaning HA-fouled membranes, and the backwash water containing Na⁺ or HA outperformed Milli-Q water in alleviating HA fouling. On the contrary, the presence of Ca^2 + in backwash water significantly decreased the backwash efficiency. Moreover, Ca^2 + played an important role in foulant removal, and the residual HA content closely related to the residual Ca^2 + content. Mechanism analysis suggested that the backwash process may involve fouling layer swelling, ion exchange, electric double layer release and competitive complexation. Ion exchange and competitive complexation played significant roles in the efficient hydraulic cleaning associated with Na⁺ and HA, respectively.     

Effects of protein properties on ultrafiltration membrane fouling performance in water treatment

Protein-like substances always induce severe ultrafiltration (UF) membrane fouling. To systematically understand the effect of proteins, regenerated cellulose UF membrane (commonly used for protein separation) performance was investigated in the presence of bovine serum albumin (BSA) under various water conditions. Results showed that although trypsin enhanced the membrane flux via proteolysis, catalysis took a long time. Membrane fouling was alleviated at high solution pH and low water temperature owing to the strong electrostatic repulsion force among BSA molecules. Both Na⁺ and Ca²⁺ could increase membrane flux. However, Ca²⁺ played a bridging role between adjacent BSA molecules, whereas membrane fouling was alleviated via a hydration repulsion force with Na⁺. The order of influence on membrane fouling was as follows: Ca²⁺ concentration > Na⁺ concentration > pH > temperature > trypsin concentration. Furthermore, a polyvinylidene fluoride UF membrane experiment showed that Ca²⁺ could reduce the fouling induced by BSA. Thus, the differences in UF membrane performance will have application potential for alleviating UF membrane fouling induced by proteins during water treatment.     

Characterization of dissolved organic matter and membrane fouling in coagulation-ultrafiltration process treating micro-polluted surface water

Coagulation–ultrafiltration(C–UF) is widely used for surface water treatment. With the removal of pollutants, the characteristics of organic matter change and affect the final treatment efficiency and the development of membrane fouling. In this study, we built a dynamic C–UF set-up to carry out the treatment of micro-polluted surface water, to investigate the characteristics of dissolved organic matter from different units. The influences of poly aluminum chloride and poly dimethyldiallylammonium chloride(PDMDAAC) on removal efficiency and membrane fouling were also investigated. Results showed that the dosage of PDMDAAC evidently increased the UV254 and dissolved organic carbon removal efficiencies,and thereby alleviated membrane fouling in the C–UF process. Most hydrophobic bases(HoB)and hydrophobic neutral fractions could be removed by coagulation. Similarly, UF was good at removing HoB compared to hydrophilic substances(HiS) and hydrophobic acid(HoA)fractions. HiS and HoA fractions with low molecule weight accumulated on the surface of the membrane, causing the increase of transmembrane pressure(TMP). Membrane fouling was mainly caused by a removable cake layer, and mechanical cleaning was an efficient way to decrease the TMP.     

Fenton cleaning strategy for ceramic membrane fouling in wastewater treatment

Membrane fouling is an obstacle impeding the wide applications of ceramic membranes and organics are responsible for most of the membrane fouling issues in wastewater treatment. In this study, Fenton cleaning strategy was firstly proposed to clean ceramic membrane fouling in wastewater treatment. Fe~(2+)efficiently catalyzed fouling cleaning with H_2O_2(1.5%) to recover the filterability of ceramic membrane. The maximum ΔTMP recovery(over 99%) was achieved at an optimal Fe~(2+)dosage of 124 mg/L after 6 hr of immersion cleaning. The total residual membrane fouling resistance decreased gradually from this optimum value as the Fe~(2+)dosage increased above 124 mg/L. The residual hydraulically reversible fouling resistance accounted for most of the membrane fouling and was basically removed(≤3.0 × 10~9 m~(-1)) when Fe~(2+)dosages higher than 124 mg/L were used. The foulants responsible for the formation of a residual hydraulically reversible fouling layer(DOC(dissolved organic carbon), proteins, polysaccharides, EEM(fluorescence excitationemission matrix spectra), SS(suspended solids), and VSS(volatile suspended solids)) were gradually removed as the Fe~(2+)dosage increased. These residual organic foulants were degraded from biopolymers(10–200 kDa) to low molecular weight substances(0.1–1 kDa),and the particle size of these residual foulants decreased significantly as a result. The strong oxidation power of hydrogen peroxide/hydroxy radicals towards organic foulants was enhanced by Fe~(2+). Fe~(2+)played a significant role in the removal of hydraulically reversible fouling and irreversible fouling from the ceramic membrane. However, Fe~(2+)(≥ 124 mg/L) increased the likelihood of forming secondary iron-organics aggregates.     

不同原水中膜污染物质的表征与确定

本文采用有机物的组分分析、相对分子质量分布及三维荧光等分析手段,研究了青草沙水库和滆湖原水的膜过滤通量的表现,探讨了膜污染的机理.试验结果表明,中亲组分有机物造成的微滤膜和超滤膜的通量下降最为严重,而疏水性有机物对通量的影响甚微.滆湖水对微滤膜的通量下降较青草沙水库水严重,而青草沙水库水对超滤膜的通量下降较滆湖水严重.膜污染机理的分析表明,微滤膜污染主要由膜孔堵塞造成,而超滤膜的通量主要受大分子有机物形成的滤饼层的影响.三维荧光分析表明,蛋白质类的有机物是造成膜污染的主要物质.     

污泥龄对膜生物反应器污泥特性及膜污染的影响

研究了污泥龄对胞外聚合物(EPS)总量、紧密粘附胞外聚合物(TB)和松散附着胞外聚合物(LB)含量及其中蛋白质与多糖比例的影响.结果表明,随污泥龄的延长,混合液EPS总量增加,TB和LB中蛋白质与多糖比例发生变化.这种变化改变了细菌表面电荷分布,增大了细菌表面亲水基和疏水基的比例,使细菌的存在状态由不稳定型(R型)向稳定型(S型)转变,降低了混合液Zeta电位,SVI值增大.采用SPSS软件对膜污染的主要因子进行了相关性分析,Zeta电位、上清液悬浮固体浓度、相对疏水性的相关系数分别为-0.818、0.853、0.832.综合考虑膜污染阻力和污泥特性,膜生物反应器的污泥龄应控制在优势菌最小世代时间的120倍以下.     

Effects of different Ca2+ behavior patterns in the electric field on membrane fouling formation and removal of trace organic compounds

The effects of Ca²⁺on membrane fouling and trace organic compounds(TrOCs) removal in an electric field-assisted microfiltration system were investigated in the presence of Na+alone for comparison. In the electric field, negatively charged bovine serum albumin(BSA)migrated towards the anode far away from the membrane surface, resulting in a 42.9% transmembrane pressure(TMP) reduction in the presence of Na+at 1.5 V. In contrast, because of the stronger charge shielding of Ca²⁺     

不同细菌分泌物及其反渗透膜污堵特性比较

反渗透(RO)工艺在城市污水再生处理中的应用越来越多,但膜污堵严重影响了该工艺的稳定运行.溶解性微生物产物(SMP)是造成RO膜污堵的最主要的有机物.本文以再生水厂RO膜面分离的两种细菌Pseudomonas sp. AM1-1和Chromobacterium sp.AM1-2的SMP为研究对象,比较了两者SMP的组成成分及其对RO膜的污堵能力.结果发现,在葡萄糖培养基中培养至稳定期后,两者产生的SMP中多糖与蛋白质比例均约为1∶1,AM1-1的SMP中多糖和蛋白质均呈双峰式分布,分布于大于10~5Da和小于10~3Da两个范围;AM1-2的SMP中,多糖分子量呈双峰式分布,主要分布于大于10~6Da的范围,有少量小于10~3Da,蛋白质分子量小于10~3Da.通过RO错流过滤污堵实验装置考察了两种SMP对RO膜的污堵特性,发现SMP中大分子有机物的分子量与SMP的膜污堵潜力密切相关,有机物分子量越大,SMP的膜污堵潜力越高,而多糖和蛋白质的比例并不是决定SMP膜污堵潜力的关键.因此,减少SMP中的大分子量物质(特别是大分子多糖)在RO膜表面的沉积,是缓解SMP造成的RO膜污堵的关键.     

太湖水体溶解性有机质荧光特征及其来源解析

利用三维荧光光谱(3DEEM)-平行因子分析(PARAFAC)技术,通过野外现场调查和室内模拟实验,分析富营养化湖泊(太湖)水体溶解性有机质(DOM)组成结构、分布规律及其来源,进一步研究藻类和水生植物残骸腐烂分解以及沉积物释放对水体DOM荧光组成特征的影响.结果表明:1太湖水体各个湖区DOM主要以类色氨酸物质(T1、T2峰)为主,竺山湾还存在类腐殖质和类富里酸物质,其荧光指数(f450/500)为1.53±0.06,接近陆源f450/500值(1.4),DOC浓度全湖最高((7.13±2.45)mg·L-1),兼具陆源与生物来源的双重特性.2太湖藻类DOM组成丰富,出现了7种荧光组分,主要为类腐殖质、类富里酸和类蛋白物质(包括类色氨酸和类酪氨酸),藻类腐烂分解后,紫外区类色氨酸T2峰和类酪氨酸B2峰消失,其他类蛋白物质和部分易降解的类富里酸物质向水体中释放,其中A峰和C峰所代表的类富里酸物质降解率较高,分别降解了70.3%和41.0%.3水生植物DOM以类腐殖酸物质为主,其残骸腐烂分解后DOM由陆源类腐殖质向类腐殖酸物质转化.4沉积物DOM出现了5类荧光峰,兼具外源污染的类富里酸荧光C峰和A峰,同时含有生物来源的B1、B2、T2类蛋白荧光峰,随其降解时间的增长,T2荧光峰消失,B1、B2荧光物质降解率分别高达86.5%和82.5%,而C峰和A峰分别上升25.1%和1.5%,沉积物降解过程中大量类蛋白物质向上覆水体中释放,同时部分类蛋白物质向着更稳定的类富里酸物质转化.因此,外源输入和内源负荷(藻类和水生植物残骸腐烂分解以及沉积物释放等)对湖泊水体DOM组成结构以及富营养化过程具有重要影响.     

Comparison of UV-based advanced oxidation processes for the removal of different fractions of NOM from drinking water

This study examined the effectiveness for degradation of hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) fractions of natural organic matter (NOM) during UV/H₂O₂, UV/TiO₂ and UV/K₂S₂O₈ (UV/PS) advanced oxidation processes (AOPs). The changing characteristics of NOM were evaluated by dissolved organic carbon (DOC), the specific UV absorbance (SUVA), trihalomethanes formation potential (THMFP), organic halogen adsorbable on activated carbon formation potential (AOXFP) and parallel factor analysis of excitation–emission matrices (PARAFAC-EEMs). In the three UV-based AOPs, HPI fraction with low molecular weight and aromaticity was more likely to degradate than HPO and TPI, and the removal efficiency of SUVA for HPO was much higher than TPI and HPI fraction. In terms of the specific THMFP of HPO, TPI and HPI, a reduction was achieved in the UV/H₂O₂ process, and the higest removal rate even reached to 83%. UV/TiO₂ and UV/PS processes can only decrease the specific THMFP of HPI. The specific AOXFP of HPO, TPI and HPI fractions were all able to be degraded by the three UV-based AOPs, and HPO content is more susceptible to decompose than TPI and HPI content. UV/H₂O₂ was found to be the most effective treatment for the removal of THMFP and AOXFP under given conditions. C1 (microbial or marine derived humic-like substances), C2 (terrestrially derived humic-like substances) and C3 (tryptophan-like proteins) fluorescent components of HPO fraction were fairly labile across the UV-based AOPs treatment. C3 of each fraction of NOM was the most resistant to degrade upon the UV-based AOPs. Results from this study may provide the prediction about the consequence of UV-based AOPs for the degradation of different fractions of NOM with varied characteristics.     

Roles of membrane and organic fouling layers on the removal of endocrine disrupting chemicals in microfiltration

To understand the adsorption behavior of endocrine disrupting chemicals(EDCs) is important for enhancing the treatment performance and preventing potential secondary pollution caused by EDCs desorption in a microfiltration system. The dynamic adsorption of four representative EDCs, namely estriol(E3), 17β-estradiol(E2), 17α-ethynylestradiol(EE2), and 4-nonylphenol(4-NP) in a microfiltration system was investigated using the Thomas' model.The product of the equilibrium constant and the total adsorption capacity of the membrane,Ka, for E3, E2, EE2, and 4-NP were 4.91, 9.78, 15.6, and 826, respectively, strongly correlating with the compound octanol–water partition coefficient(KOW). Adsorption appeared to be enhanced when organic fouling formed on the surface of membrane, indicating the role of an additional adsorption column for EDCs acted by a fouling layer in microfiltration. Results of a comparison between the Ka values for clean membrane and fouled membrane illustrated that the significant contribution made by fouling layers may be attributed to the foulant layer's hydrophobicity(in the case of calcium humate layer) and thickness(in the case of calcium alginate layer). This study provided a novel perspective to quantitatively analyze the dynamic adsorption behavior of trace pollutants in membrane process.     

光谱特征法辨识不同污染景观河道中溶解性有机物的组分与来源

利用三维荧光光谱(EEMs)结合平行因子分析方法(PARAFAC)及紫外-可见光谱技术(UV-vis),对苏州古城区内不同污染状况的景观河道中溶解性有机物(DOM)的光谱特征和来源进行解析.结果表明,苏州古城区内景观河道水体总体上表现为氮、磷营养盐污染.水体中的DOM解析出4种荧光组分,分别为自源类色氨酸C1(AEx/...     

Simulated photo-degradation of dissolved organic matter in lakes revealed by three-dimensional excitation-emission matrix with regional integration and parallel factor analysis

Simulated photo-degradation of fluorescent dissolved organic matter(FDOM) in Lake Baihua(BH) and Lake Hongfeng(HF) was investigated with three-dimensional excitationemission matrix(3 DEEM) fluorescence combined with the fluorescence regional integration(FRI),parallel factor(PARAFAC) analysis,and multi-order kinetic models.In the FRI analysis,fulvic-like and humic-like materials were the main constituents for both BH-FDOM and HF-FDOM.Four individual components were identified by use of PARAFAC analysis as humic-like components(C1),fulvic-like components(C2),protein-like components(C3) and unidentified components(C4).The maximum 3 DEEM fluorescence intensity of PARAFAC components C1-C3 decreased by about 60%,70% and 90%,respectively after photo-degradation.The multi-order kinetic model was acceptable to represent the photo-degradation of FDOM with correlation coefficient(R_(adj)~2)(0.963-0.998).The photo-degradation rate constants(k_n) showed differences of three orders of magnitude,from 1.09 x 10~(-6) to 4.02 x 10~(-4) min-1,and half-life of multi-order model(T_(1/2)~n)ranged from 5.26 to 64.01 min.The decreased values of fluorescence index(FI) and biogenic index(BI),the fact that of percent fluorescence response parameter of Region I(P_(Ⅰ,n)) showed the greatest change ratio,followed by percent fluorescence response parameter of Region II(P_(Ⅱ,n),while the largest decrease ratio was found for C3 components,and the lowest T_(1/2)~n was observed for C3,indicated preferential degradation of protein-like materials/components derived from biological sources during photodegradation.This research on the degradation of FDOM by 3 DEEM/FRI-PARAFAC would be beneficial to understanding the photo-degradation of FD OM in natural environments and accurately predicting the environmental behaviors of contaminants in the presence of FDOM.     

呼伦湖水体溶解性有机物荧光特征及来源分析

呼伦湖是我国北方生态安全屏障的重要组成部分,为探究呼伦湖水体中有机物的组成及来源,利用三维荧光光谱（EEMs）结合平行因子（PARAFAC）分析技术进行溶解性有机物（DOM）荧光特征及来源研究。结果表明：呼伦湖DOM中含有3种荧光组分,分别为类色氨酸（C1）、类腐殖酸（C2）和类富里酸（C3）;平水期、丰水期和枯水期的C2和C3荧光强度占比约70%,表明呼伦湖水体DOM以腐殖质类物质为主,其中不同水期生态补水工程入湖口的C2和C3荧光强度均高于其他区域;平水期、丰水期和枯水期的荧光指数、生物指数和腐殖化指数平均值分别为1.50~1.54、0.85~1.00和4.12~4.68,表明呼伦湖DOM由陆源和自生源混合组成,具有明显的自生源特征;水质监测数据表明,2021年呼伦湖平水期、丰水期和枯水期水质均为GB 3838—2002《地表水环境质量标准》劣Ⅴ类,其中平水期和丰水期的BOD₅平均值高于枯水期,而平水期总有机碳平均浓度高于丰水期和枯水期;不同水期C2和C3的荧光强度均呈显著正相关,表明DOM中组分C2和C3的产生及来源具有一致性。

     

平寨水库荧光溶解性有机质的来源、特征及其动态转化

利用三维激发发射矩阵光谱(3-D EEM)和平行因子分析,研究了三岔河流域平寨水库溶解有机质的来源、组成和转化情况。在平寨水库的入库水、表层水(0～5 m)、深层水(10～60 m)和出库水中,检测到了几种荧光溶解有机质组分,分别为陆源类腐殖质、自源类腐殖质和浮游植物源的类蛋白质(或类色氨酸或类酪氨酸)。陆源类腐殖质的荧光强度在入库水中略高于出库水,表明陆源类腐殖质在水库系统中相对稳定,大坝截流对其影响不大。自源类腐殖质的荧光强度在库区明显高于入库水和出库水,表明自源类腐殖质既由自源有机物分解产生,又在光化学、微生物和大坝物理拦截过程的影响下发生分解;其他荧光组分中也检测到相似的结果。水温、pH、溶解氧和有色溶解有机质表现出相似的季节变化,光化学和微生物以及大坝拦截是引起水库入库水、库区表层水、库区深层水和出库水中荧光溶解有机质时空动态变化的主要原因。     

盐度冲击下MBR污泥SMP和EPS的三维荧光光谱解析

利用三维荧光(EEM)技术研究了不同盐度冲击下膜-生物反应器(MBR)污泥微生物溶解性产物(SMP)和胞外聚合物(EPS)的变化规律,分析不同盐度冲击下MBR污泥SMP和EPS的EEM图谱.结果表明,当冲击盐度大于2.5g/L时,SMP的EEM图谱中色氨酸荧光峰B(270nm,350nm)、类胡敏酸荧光峰C(375,475nm)、类富里酸荧光峰D(260,460nm)以及EPS的EEM图谱中色氨酸荧光峰B的荧光强度随冲击盐度的提升而增加,EPS的EEM图谱中类胡敏酸C峰的荧光强度则随冲击盐度的提升而下降.用平行因子分析(PARAFAC)方法确定EEM图谱中存在的4个组分,分别为类蛋白质组分C1(230/280,350nm),类胡敏酸组分C2(290/310,380nm)、C3(290/360,460nm)和C4(270/340,440nm);当冲击盐度大于2.5g/L时,SMP中C1、C3和C4组分的荧光强度与冲击盐度呈正相关,而EPS中C3和C4组分的荧光强度分别与冲击盐度呈正相关和负相关,其相关系数均≥0.90;SMP中类蛋白质荧光组分和类胡敏酸组分的荧光强度之和分别与测定的蛋白质含量和胡敏酸含量呈明显的正相关性,相关系数均＞0.93,可作为荧光组分强度定量计算的依据,而EPS中此相关性并不明显.     

氟中毒地区饮水水质标准的确定方法

在对饮水致病的水化学机理进行简要讨论后,提出使用以所有水溶组分活度为变量的多元逐步判别分析法作为饮水水质标准的确定方法。经对一个地区的实例研究发现,总氟含量用于判别水质时存在无效判别区间问题,这一发现提示我们有必要重新考虑现行水质标准中总氟浓度只有一个标准值的适宜性问题。     

干湿季节下再生水补给河流的溶解性有机物组成特征及其与致病菌基因的相互关系

水体中溶解性有机物(DOM)对各种类型污染物的迁移转化具有重要影响.为了考察干湿季节下再生水补给水体的DOM分子多样性变化及其主要成分对致病菌分布及迁移的影响,本研究以北京两个典型的再生水补给水体(清河和沙河水库)为对象,分别在旱季和雨季采集水样,采用三维荧光光谱(3D-EEM)、平行因子分析(PARAFAC)、光谱指...     

思林水库荧光溶解性有机质的特征、来源及其转化动力学

利用三维荧光光谱(EEM)结合平行因子分析(PARAFAC),研究了思林水库冬季(1月)、春季(4月)、夏季(6月)和秋季(10月)上游入库水体、库区表层水(0 m)、库区深层水(20 m)、出库水体的荧光溶解性有机质(FDOM)不同组分的特征、来源及其转化动力学.结果表明,思林水库的溶解性有机质由3种荧光组分组成,分别是:陆源类腐殖质(C类,C1)、浮游植物源的微生物类腐殖质(M类,C2)和浮游植物源的类蛋白或类色氨酸或类酪氨酸(C3).其中陆源类腐殖质的荧光强度随着入库水、库区表层水、库区深层水和出库水逐渐减少,这表明由于光化学作用、微生物作用、大坝拦截效应等环境因素的影响,类腐殖质随着水体由入库向出库的流动而逐渐降解.相反,微生物类腐殖质(M类)的荧光强度结果表明,在入库-出库过程中,微生物类腐殖质处于产生及部分或完全降解的波动中,这表明微生物类腐殖质是浮游植物的原生产物,并且对于光化学作用、微生物作用和大坝拦截效应有很强的不稳定性.类蛋白或类色氨酸或类酪氨酸主要新产生于夏季和秋季的表层水体中,在冬季和春季表层和深层水体中也有产生;并在出库过程中逐渐减少.这表明类蛋白或类色氨酸或类酪氨酸是浮游植物的原生产物;并且它们受到光化学作用、微生物作用和大坝拦截效应的共同影响,在表层和深层水中生成和降解.因此,这些结果意味着通过平行因子分析确定的荧光溶解性有机质组分的方法,对于更好地理解溶解性有机质在水库水体的转化动力学机制至关重要.