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.     

Fatty acid fouling of forward osmosis membrane: Effects of pH, calcium, membrane orientation, initial permeate flux and foulant composition

Octanoic acid (OA) was selected to represent fatty acids in effluent organic matter (EOM). The effects of feed solution (FS) properties, membrane orientation and initial permeate flux on OA fouling in forward osmosis (FO) were investigated. The undissociated OA formed a cake layer quickly and caused the water flux to decline significantly in the initial 0.5 hr at unadjusted pH 3.56; while the fully dissociated OA behaved as an anionic surfactant and promoted the water permeation at an elevated pH of 9.00. Moreover, except at the initial stage, the sudden decline of water flux (meaning the occurrence of severe membrane fouling) occurred in two conditions: 1. 0.5 mmol/L Ca^2 +, active layer facing draw solution (AL-DS) and 1.5 mol/L NaCl (DS); 2. No Ca^2 +, active layer-facing FS (AL-FS) and 4 mol/L NaCl (DS). This demonstrated that cake layer compaction or pore blocking occurred only when enough foulants were absorbed into the membrane surface, and the water permeation was high enough to compact the deposit inside the porous substrate. Furthermore, bovine serum albumin (BSA) was selected as a co-foulant. The water flux of both co-foulants was between the fluxes obtained separately for the two foulants at pH 3.56, and larger than the two values at pH 9.00. This manifested that, at pH 3.56, BSA alleviated the effect of the cake layer caused by OA, and OA enhanced BSA fouling simultaneously; while at pH 9.00, the mutual effects of OA and BSA eased the membrane fouling.     

XDLVO理论解析不同离子条件下海藻酸钠微滤膜污染

应用extended Derjaguin-Laudau-Verwey-Overbeek(XDLVO)理论定量解析海藻酸钠微滤膜污染中界面微距作用力,探讨不同离子条件对膜污染影响的主控机制.结果表明,对于亲水性膜表面,范德华力促进膜污染,极性作用力阻碍膜污染;而对于疏水性膜表面,范德华力减缓膜污染,极性作用力加速膜污染.海藻酸钠与微滤膜接触时双电层作用力对膜污染贡献相对微弱.离子强度及钙离子对海藻酸钠微滤膜污染的影响主要是通过改变极性作用力来实现的.较高的离子强度会降低极性作用力的排斥性或升高极性作用力的吸引性,从而加重海藻酸钠微滤膜污染.虽然钙离子使出水通量急速下降,但钙离子的存在使得物理清洗效率提高.不同离子条件下初始阶段及后期阶段污染趋势K分别与膜-海藻酸钠粘附自由能及海藻酸钠-海藻酸钠粘聚自由能具有良好的线性相关性,表明XDLVO理论适用于描述不同离子条件下海藻酸钠微滤膜污染行为.     

蛋白质及无机离子对纳滤膜去除PFOS的影响

以全氟辛烷磺酸（PFOS）为目标去除物,选取牛血清蛋白（BSA）为典型蛋白质类有机物,考察了BSA及其浓度,以及BSA与无机离子共存时,离子强度、离子种类对聚酰胺纳滤膜去除水中PFOS的影响.研究发现,原液中存在BSA时,PFOS的去除率有显著提高,而且BSA浓度越高,PFOS的去除率越高;当BSA与无机离子共存时,离子强度越大,PFOS去除率越高.这可能是因为BSA不但会吸附一部分PFOS,还会造成膜污染,BSA浓度越大,膜污染越严重,膜的筛分能力越强,且膜面与PFOS之间的静电排斥力越大,从而提高了PFOS的截留率.而无机离子的存在减小了BSA分子之间及与膜面之间的静电排斥力,使BSA污染层更加厚实,进一步增强了膜的筛分能力.此外,Ca²⁺提高PFOS去除率的能力优于Na⁺.     

基于膜特征参数变化的蛋白质超滤过程膜污染研究

为进一步研究多种蛋白质体系超滤过程的膜污染机制,采用切割相对分子质量为50×103的聚醚砜(polyethersulfone,PES)超滤膜,对溶菌酶(lysozyme,LYS)、牛血清蛋白(bovine serum albumin,BSA)、LYS+BSA等3种不同蛋白质溶液的超滤过程进行了研究.运用接触角仪、场发射扫描电镜(field emission scanning electron microscope,FESEM)、原子力显微镜(atomic force microscope,AFM)测定了不同污染阶段膜特征参数的变化.结果表明,超滤膜通量变化明显呈现3个阶段:初期(约0~5min)衰减迅速、中期(约5~60 min)衰减缓慢、后期(约60~120 min)趋于稳定;整个超滤过程中,LYS污染膜的通量衰减幅度最大,LYS+BSA次之,BSA最小.膜特征参数变化表明:LYS对膜的初期污染主要以膜孔窄化为主,中期污染由膜孔堵塞和膜孔窄化共同控制;BSA初期膜污染以膜孔堵塞为主,中期污染以膜孔窄化为主;滤饼层过滤是BSA、LYS后期膜污染的主要机制.LYS+BSA二元混合溶液中的LYS对膜污染的产生起主导作用.     

阳离子强度对鼠李糖脂作用下三氯生在底泥-水相中分配的影响

探讨了阳离子强度(Na~+/Ca~(2+))对鼠李糖脂(RL)胶束形态的影响,并据此阐述了阳离子强度对RL作用下三氯生(TCS)在底泥-水相中分配的影响规律.结果表明,阳离子对TCS的表观溶解度和其在底泥-水中的分配无明显作用,但能通过与RL分子间产生的盐桥作用影响RL的胶束聚集程度及溶液的稳定性,使水相中的RL浓度发生变化,进而导致RL作用下TCS的表观溶解度及其在底泥-水相中分配的差异.随着阳离子强度的增加,RL胶束粒径在Na~+溶液中先减小后增大,而在Ca~(2+)溶液中持续减小;RL溶液的zeta电位在Na+/Ca~(2+)溶液中逐渐减小,其溶液的稳定度下降.相比Na~+,Ca~(2+)与RL分子间的盐桥作用更强.低浓度Na~+(50 mmol·L~(-1))可促进RL胶束的形成,提高其对TCS的增溶能力,促进TCS从底泥迁移至水相,提高了TCS在水相的分配比例(K*d值从64.16 L·kg~(-1)降低到40.81 L·kg~(-1)(30 mmol·L~(-1)Na~+));但高浓度Na~+(50 mmol·L~(-1))会因盐析作用降低TCS的表观溶解度,并抑制其在RL作用下向水相的迁移.而Ca~(2+)在很低浓度下(1 mmol·L~(-1))就能与RL分子产生强的盐桥作用而生成紧密的胶束聚集体,致使RL沉淀,大大降低RL对TCS的增溶作用,反而提高TCS在底泥相的分配比例(K*d值从64.16 L·kg~(-1)提高到4987.76 L·kg~(-1)(30 mmol·L~(-1)Ca~(2+))).     

中亚热带常绿阔叶林湿沉降过程中盐基离子变化特征

基于野外实验和室内实验相结合的方法,于2012年9月至2013年8月对四面山常绿阔叶林大气降水、穿透水、地表枯透水、土壤渗滤液进行了持续一年的森林不同层次盐基离子季节动态变化特征的研究.结果表明,四面山大气降水全年pH平均值为4.90,最大值为5.14,大气降水明显偏酸性;土壤层和林冠层能使降雨的p H值有所升高,其中土壤层对p H值的调升幅度最大,其次为森林冠层;森林冠层只对Na~+有一定的截留作用,降雨能够淋溶森林冠层的Ca~(2+)、Mg~(2+)、K~+;研究结果也表明,枯枝落叶的降解是导致各盐基离子质量浓度在枯透水中增加的主要原因;枯透水下渗的过程淋溶了森林土壤中的Ca~(2+)、Mg~(2+)、Na~+.四面山大气降水经过森林生态系统后Ca~(~(2+))、Mg~(2+)、Na~+、K~+的总截留率分别为33.82%、-7.06%、74.36%、42.87%,森林生态系统对Ca~(2+)、Na~+、K~+表现出了截留作用,其中对Na~+截留率最大.     

沙尘天气对兰州市PM10中主要水溶性离子的影响

利用在线监测仪器MARGA在兰州大学盘旋路校区对兰州市大气PM10中水溶性离子进行监测,监测期间(2011-04-01~2011-06-30)有15 d出现沙尘天气.兰州市PM10中主要水溶性离子物种为Ca2+、SO2-4和NO-3.扬沙天气期间NO-3和NH+4的浓度比非沙尘期间低,说明沙尘天气对当地人为源所排放污染物具有清除作用.沙尘天气期间,作为土壤污染源标识物的Mg2+、Na+和Ca2+离子都有明显增加,Na+和Mg2+相关系数为0.520,Na+和Ca2+相关系数为0.659,Mg2+和Ca2+相关系数为0.671,而非沙尘天气期间三者的相关系数并不高,Na+和Mg2+相关系数为0.065,Na+和Ca2+相关系数为0.131,Mg2+和Ca2+相关系数为0.163,说明沙尘天气期间三者之间具有相同的污染源,主要来自于土壤风沙尘,而非沙尘天气期间三者来源不同.Cl-的浓度在扬沙天气明显高于浮尘和非沙尘天气期间,说明外来的土壤风沙尘是Cl-的主要来源.     

Chemistry of atmospheric precipitation at the Western Arabian Gulf Coast

Rainwater and atmospheric bulk deposition samples were collected at a station on the rooftop of the Research Institute of King Fahd University of Petroleum and Minerals in Dhahran. Continuous sampling was carried out manually throughout the rainy season between December 1987 and February 1988, and for one rainfall event in March 1987. A total number of 13 samples were collected and investigated for pH and dissolved ionic composition using inductivity coupled plasma emission spectrometry (ICP) and ion chromatography (IC). The range and volume-weighted average pH were 5.1–7.2 and 5.48, respectively. Significant negative linear correlations were observed between the precipitation pH and rain depth, and between pH and the summation of dissolved {(Ca²⁺ + Mg²⁺)−(SO₄²⁻ + NO₃⁻ + NO₂⁻)} (in μeqℓ⁻¹). The ionic summation also correlated negatively with rain depth. The ionic abundance in rainwater (in μeqℓ⁻¹) expressed in concentration order showed the general trend SO₄²⁻ > HCO₃⁻¹ = Cl⁻ = NO₃⁻ > NO₂⁻ for anions and Ca²⁺ > Na⁺ > Mg²⁺ > NH₄⁺ > K⁺ > H⁺ > Sr²⁺ for cations. Good mass balance between cations and anions was observed. Total NO₃⁻ contribute equally to precipitation acidity as SO₄²⁻ and Ca²⁺ plus Mg²⁺ in alkaline suspended particulates from natural sources are the major ions which buffer the acidity of precipitation. The NH₄⁺ ion which is also present plays an insignificant role in the acid/base equilibrium of rainwater.     

Japanese Papilio butterflies puddle using Na+ detected by contact chemosensilla in the proboscis

Many butterflies acquire nutrients from non-nectar sources such as puddles. To better understand how male Papilio butterflies identify suitable sites for puddling, we used behavioral and electrophysiological methods to examine the responses of Japanese Papilio butterflies to Na⁺, K⁺, Ca²⁺, and Mg²⁺. Based on behavioral analyses, these butterflies preferred a 10-mM Na⁺ solution to K⁺, Ca²⁺, and Mg²⁺ solutions of the same concentration and among a tested range of 1?mM to 1?M NaCl. We also measured the ion concentrations of solutions sampled from puddling sites in the field. Na⁺ concentrations of the samples were up to 6?mM, slightly lower than that preferred by butterflies in the behavioral experiments. Butterflies that sipped the 10?mM Na⁺ solution from the experimental trays did not continue to puddle on the ground. Additionally, butterflies puddled at sites where the concentrations of K⁺, Ca²⁺, and/or Mg²⁺ were higher than that of Na⁺. This suggests that K⁺, Ca²⁺, and Mg²⁺ do not interfere with the detection of Na⁺ by the Papilio butterfly. Using an electrophysiological method, tip recordings, receptor neurons in contact chemosensilla inside the proboscis evoked regularly firing impulses to 1, 10, and 100?mM NaCl solutions but not to CaCl₂ or MgCl₂. The dose?Cresponse patterns to the NaCl solutions were different among the neurons, which were classified into three types. These results showed that Japanese Papilio butterflies puddle using Na⁺ detected by the contact chemosensilla in the proboscis, which measure its concentration.     

XDLVO理论解析钙离子对腐殖酸反渗透膜污染的影响机制

以XDLVO（extended Derjaguin-Landau-Verwey-Overbeek）理论定量解析腐殖酸反渗透（reverse osmosis,RO）膜污染过程中的界面相互作用,分析3种界面相互作用力在膜污染过程中的贡献,重点探究不同溶液pH条件下Ca2＋对腐殖酸RO膜污染的影响.结果表明,无论Ca2＋是否存在,对膜污染起促进作用的范德华力在pH 3时为主导作用力,而减缓膜污染的极性作用力在pH 7及pH 10时成为主控因素.静电力在所有测试条件下作用微弱,因此对膜污染贡献很小.Ca2＋主要通过改变极性作用力影响腐殖酸RO膜污染行为,且其影响随溶液pH值的降低而凸显,多数情况下Ca2＋会促进腐殖酸RO膜污染.界面自由能与膜污染程度相关性分析表明,XDLVO理论可以合理预测不同溶液条件下腐殖酸RO膜污染行为.     

臭氧-CNT膜改性联用工艺阈通量及膜污染分析

采用碳纳米管(carbon nanotube,CNT)对聚偏氟乙烯(polyvinylidene fluoride,PVDF)中空纤维超滤膜进行改性,结合臭氧预氧化技术,考察了臭氧-CNT膜改性联用工艺的阈通量及膜表面污染情况.结果表明,原膜阈通量为45 L·(m~2·h)~(-1),联用工艺下阈通量为81 L·(m~2·h)~(-1),联用工艺相对原膜阈通量提高了约80%;且联用工艺的污染速率最低,约为0. 001 37k Pa·min-1·L-1·m~2·h.相同臭氧投量与CNT负载量下,对比联用工艺阈通量与临界通量运行情况,得出阈通量下运行过水量高于临界通量运行,表明阈通量下运行能够缓解膜污染,延长膜组件的运行时间.膜污染碳平衡实验结果表明,采用CNT对膜改性后,膜组件的纳污能力与可恢复性得到明显提高,臭氧氧化能够进一步提高CNT改性膜组件的可恢复性,大幅提高其过水性能和使用时间.     

太湖流域污水排放对湖水天然水化学的影响

为揭示太湖流域污水排放对湖水天然水化学(主要离子)的影响,对太湖上游19个污水处理厂的进水、出水及雨水、入湖河水和湖水中主要离子进行了分析,同时收集历史数据对比了太湖1950s年代和目前的天然水化学特征.结果表明,太湖水体天然水化学类型主要受流域碳酸盐岩风化作用控制,而受雨水影响较小;流域排放的污水主要离子特征类似于干旱地区的河水,部分工业污水甚至具有海水水化学特征,说明人为活动对当地淡水水质的重要影响.同时,太湖水化学已从60年前的重碳酸盐钙型水转变为目前的氯化物钠型水.进一步通过修正的完全混合断面污染物浓度模型的计算结果显示,生活污水排放可以解释对太湖多数主要离子的影响,生活和工业污水的排放可以更好地解释Cl#的变化;但太湖Ca2+和Mg2+浓度(硬度)的增长受污水影响较小,而是受流域酸沉降的影响控制.分析显示,60年来受流域不断增长的污水排放影响,太湖水体的优势阴阳离子组分均已发生了显著变化,目前湖水(Ca2++Mg2+)-HCO-3和(Na++K+)-Cl-均分布在1∶1线上侧,而(Ca2++Mg2+)/(Na++K+)比值则下降了约1半,同时湖水的Cl#/Na+比值显示出显著的升高趋势,说明流域人类活动已经成为影响太湖水化学的主要原因.本研究可为湖泊水化学演化研究及强烈人为干预条件下的水环境管理提供新的基础.     

全氟辛酸对酿酒酵母细胞毒性作用

全氟辛酸(PFOA)广泛应用于工业生产中,具有高度的生物毒性及生物蓄积性,然而PFOA对环境微生物的毒性影响仍有待深入开展.通过流式细胞术测定了酵母菌在不同浓度PFOA胁迫下细胞膜通透性、ROS、线粒体跨膜电位的变化,并且测定了MDA含量和Na+K+-ATPase、Ca2+Mg2+-ATPase活性变化.结果显示PFOA可使PI染色细胞比例增高,酿酒酵母细胞膜通透性增大、ROS和MDA含量升高、线粒体跨膜电位降低,且ROS含量、MDA含量与线粒体跨膜电位降幅均与PFOA胁迫浓度和时间呈正相关.Na+K+-ATPase、Ca2+Mg2+-ATPase活性先上升后降低,表明酿酒酵母在PFOA胁迫下,其生理活性受到抑制甚至发生细胞凋亡.证明PFOA对酿酒酵母具有生物毒性,100 mg·L-1PFOA对酿酒酵母具有即时毒性.该结果可为PFOA的影响评价提供更多依据.     

然乌湖流域地表水水化学特征及控制因素

为研究然乌湖流域地表水水化学特征及离子来源,在然乌湖流域采集了地表水样品和雨水样品,综合利用相关性分析、Piper三线图和Gibbs模型等方法,分析了该区地表水主要离子特征及其控制因素,揭示了该区地表水水中的主要物质来源.结果表明,然乌湖流域地表水pH为7.54～8.48,呈弱碱性,并具有较低的溶解性总固体(59.89～96.75 mg·L~(-1)),阳离子主要以Ca~(2+)和Mg~(2+)为主,Ca~(2+)当量浓度占阳离子总量的63.3%～76.2%,均值为67.2%, Mg~(2+)当量浓度占阳离子总量的23.4%～36.2%,均值为31.4%, Ca~(2+)和Mg~(2+)约占阳离子总量的98.5%.阴离子以HCO~-_3为主, HCO~-_3占阴离子总量的74.31%～84.29%,均值为78.21%, SO_4~(2-)占阴离子总量的9.59%～19.37%,二者约占阴离子总量的93.55%.水化学类型为HCO_3-Ca和HCO_3-Ca·Mg型,水文地球化学过程受人类活动影响较弱,主要受岩石风化作用控制,主要离子来源于碳酸盐岩及硅酸盐岩的风化溶解.     

烟台夹河河口海水混合过程的地球化学特征研究

海(咸)水混入是河口河水重要的地质过程,深刻地影响河水地球化学过程。本文系统采集夹河河口水样,分析海淡水混合过程的地球化学特征。结果表明,远离河口段(J10~J14)为淡水性质,主要受水-岩作用及人类活动等影响;近河口段(J1~J8)海水混入严重,F~-、Cl~-、Br~-、SO~(2-)_4、Na~+、K~+、Mg~(2+)、Ca~(2+)、盐度等明显较高,主要受海水混入影响。近河口段存在Na-Ca离子交换过程,约占Na~+总量的0.9%~1.5%,离子交换量随海水混入比例增加而增加,Na~+离子交换量与K~+,Ca~(2+)、Mg~(2+)、Br~-、F~-、SO~(2-)_4离子交换量相关,且河水离子含量与盐度回归系数略低于与盐度、Na~+交换量回归系数,表明河口段河水离子交换影响河水地球化学特征。     

Adsorption of herbicide triclopyr on homoionic clays

ＡｄｓｏｒｐｔｉｏｎｏｆｈｅｒｂｉｃｉｄｅｔｒｉｃｌｏｐｙｒｏｎｈｏｍｏｉｏｎｉｃｃｌａｙｓＬｉｕＷｅｉｐｉｎｇ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＺｈｅｊｉａｎｇＵｎｉｖｅｒｓｉｔｙ，Ｈａｎｇｚｈｏｕ３１００２７，Ｃｈｉｎａ）ＡｌｂａＰｕ...     

超滤膜材料对SiO2-有机物膜污染行为的影响

选用聚偏氟乙烯（PVDF）及乙烯乙烯醇共聚物（EVOH）2种超滤膜，针对SiO₂-牛血清蛋白（BSA）及SiO₂-腐殖酸（HA）2种无机-有机混合污染物，通过单种及混合污染物过滤实验，结合各污染物与膜之间作用力的测定，考察膜材料对SiO₂-有机混合污染物膜污染行为的影响机制.结果表明：与单种有机污染物HA或BSA相比，SiO₂-HA/BSA混合污染物对PVDF及EVOH超滤膜的污染会出现加剧和减缓2种相反的现象.结合作用力结果发现：当膜-SiO₂之间的作用力大于膜-有机污染物之间作用力时，与单种有机污染物相比，SiO₂的存在会加剧膜污染；相反，当膜-SiO₂之间作用力小于膜-有机污染物之间作用力时，SiO₂的存在会有效减缓膜污染.上述结果说明膜材料是控制无机-有机混合污染物膜污染行为的关键因素.     

MWCNTs预涂覆及预吸附处理缓解低压膜腐殖酸污染的机制研究

以腐殖酸(Humic Acid,HA)为研究对象,采用多壁碳纳米管(Multiwalled Carbon Nanotubes,MWCNTs)对聚偏氟乙烯(Polyvinylidene Fluoride,PVDF)平板超滤膜进行预涂覆改性处理,并与等量MWCNTs分散状态时吸附处理HA对膜污染的缓解效果进行了对比,考察了MWCNTs在处理HA过程中缓解膜污染的机制.同时,分析了MWCNTs投量和溶液离子变化对MWCNTs吸附及截留作用缓解膜污染的影响.结果表明,MWCNTs预涂覆与吸附相比,能够更有效地缓解膜污染,其中,分散剂为乙醇的MWCNTs预涂覆层对膜污染的缓解效果最好.增加MWCNTs投量不能无限地提高其对HA的吸附及截留效果;添加Na~+会造成MWCNTs对HA的吸附及截留效果变差;添加Ca~(2+)能够提高MWCNTs对HA的吸附及截留效果.膜表面污染照片及膜电镜观测结果表明,乙醇分散MWCNTs在超滤膜(UF)表面形成的预涂覆层呈均匀的层状结构,HA被拦截在MWCNTs层的多孔结构内,不易进入PVDF膜膜孔,反洗时易脱附,可逆性高;纯水分散MWCNTs在超滤膜表面形成的预涂覆层易于团聚,HA容易透过MWCNTs涂覆层进而堵塞PVDF膜膜孔,可逆性低;MWCNTs预吸附处理后形成MWCNTs和HA的包裹体,不经微滤膜滤除,会在PVDF膜表面产生复合污染.     

溶液特性及共存物对纳滤膜去除水中全氟辛酸的影响

利用聚酰胺复合纳滤(NF)膜去除水中的持久性有机污染物—全氟辛酸(PFOA),分别研究了PFOA浓度、溶液离子强度、pH值、典型大分子有机物—牛血清蛋白(BSA)以及BSA与Na+共存对PFOA截留率的影响.结果表明,在0.8MPa下过滤24h,随着PFOA浓度增大,PFOA截留率提高;溶液离子强度、pH值越高,PFO...