亲水荷电超滤膜的制备及对腐殖酸的分离性能

为改善聚醚砜(PES)超滤膜的抗污染性能和提高对腐殖酸(HA)的截留率,以介孔二氧化硅(MS)为添加剂,采用相转化法制备了亲水性PES/MS复合超滤膜,并对膜表面进行荷电改性.研究了MS对膜的断面结构、表面化学性质和过滤性能的影响,考察了荷电改性PES/MS超滤膜对水中HA的分离性能以及溶液pH值、离子强度和钙离子浓度等因素对荷电膜超滤过程的影响.SEM表征结果显示,MS颗粒在PES/MS复合膜的表面分散均匀,膜孔的连通性改善.亲水荷电改性后,膜表面接触角由68°降至57°,zeta电位由-6.31mV降至-11.45mV,膜对HA的去除率由72%提高到95%,通量衰减率由29.8%减小到4.9%.结果表明,对PES超滤膜进行亲水荷电改性可有效提高对HA的截留率,同时减轻膜污染;另外,溶液的pH值、离子强度和钙离子浓度对荷电超滤膜的过滤性能有较大影响,调节合适的溶液环境可在提高截留率的同时,减轻膜污染.     

亲水聚合物改性微滤膜在膜生物反应器中的膜污染研究

采用经过聚合多巴胺和氨基聚乙二醇(mPEG-NH_2)表面改性的PVDF微滤膜,通过浸没在膜生物反应器(MBR)中验证改性微滤膜的抗污染性能.同时,采用多种分析手段对改性膜进行表征,包括膜表面微观形貌、润湿性、粗糙度和表面官能团等.实验同时考察了改性膜在MBR中运行的水通量衰减、污染膜的阻力分布,以及对膜面污染物的胞外多聚物组分的影响.结果发现,所采用的膜改性方法明显改善了膜表面的亲水性.短期过滤实验结果表明,多巴胺涂覆膜的稳定通量比原膜高47%,PEG改性膜则在水通量方面有进一步提高;在长期恒通量过滤阶段,多巴胺涂覆膜和PEG接枝膜的比膜通量分别比原膜高37%和88%.实验还发现,改性膜表面滤饼层中蛋白质和多糖含量均低于原膜.     

PVDF超滤膜进行聚乙二醇甲基丙烯酸甲酯 (PEGMA)紫外光照射接枝的膜面表征与抗污染分析

本文采用紫外光照射接枝的方法将聚乙二醇甲基丙烯酸甲酯(PEGMA)亲水单体接枝在疏水性聚偏氟乙烯(PVDF)超滤膜表面,改善PVDF膜的亲水性能.实验中以N,N-亚甲基双丙烯酰胺(MBAA)为交联剂作为对比,发现添加MBAA可以减少PEG接枝层的溶胀性.本实验研究不同改性条件对膜性能的影响,利用表面接触角(CA)、红外光谱分析(ATR-IR)、扫描电镜(SEM)等手段表征膜表面特征,同时研究了改性膜对乳化油和牛血清蛋白溶液分离效率和抗污染能力.实验结果表明,经改性后膜亲水性明显提高,对污染物的截留效果和抗污染能力均有所提高.     

聚离子液体刷接枝改性PVDF膜及其对药物硫酸氢氯吡咯雷分离性能研究

以聚偏氟乙烯(PVDF)超滤膜为底膜,通过浸渍法使多巴胺(DOPA)在膜表面形成聚多巴胺(PDOPA)层,然后由化学反应固定溴代卤化物,并通过原子转移自由基聚合(ATRP)反应在膜表面接枝聚离子液体刷(PBIVm-Br),以制备聚离子液体刷改性PVDF膜,即PVDF-g-PBIVm-Br膜.结果表明,改性PVDF膜的接触角下降至60°以下且显示出良好的荷正电性.改性膜的药物通量和截留率均大于未改性PVDF膜,分离10 mg·L~(-1)的硫酸氢氯吡咯雷时,改性膜(M4)的药物通量可达27.62 L·m~(-2)·h~(-1),截留率为89.03%,通量恢复率为95.32%.经过60 h分离实验后,膜M4对硫酸氢氯吡咯雷溶液的分离通量维持在18.05 L·m~(-2)·h~(-1),截留率从89.03%上升到92.19%.以上结果表明,聚离子液体刷改性膜在荷正电有机污染物的分离方面具有一定的应用前景.     

城市污水二级出水超滤膜污染与膜特性的研究

以城市污水二级出水为过滤介质,考察了PVA、PVP、PMMA等与PVDF的二元及三元共混超滤膜的过滤污染行为.结果表明,共混优化了PVDF超滤膜的结构参数,添加剂PVP、PVA可有效改善膜的亲水化程度,提高膜渗透通量.超滤膜的亲水性和结构特性对膜抗污染性能影响较大;堵孔阻力是二级出水过滤膜污染不可逆的主要原因.亲水性较强的超滤膜,二级出水过滤初期易因浓差极化而导致滤饼层污染,造成一定的通量衰减,但易清洗恢复,不可逆污染指数(rir)为0,抗污染性能好.致密的超滤膜表面有利于防止二级出水中的中低分子量污染物进入膜内部,而断面通透大孔和疏松海绵层结构的超滤膜,能减少二级出水中的污染物在膜中沉积形成堵孔阻力.膜表面多孔,内部大孔发育不充分,易形成堵孔污染,通量衰减大且不易清洗恢复,膜污染不可逆.     

基于HBPs接枝的PVDF膜亲水改性及抗污染性能

在聚偏氟乙烯（PVDF）微滤膜表面接枝超支化聚合物聚乙烯亚胺（HPEI）,并通过环氧丙醇与氨基的开环反应在PVDF膜表面形成高密度的多羟基结构,实现PVDF膜的亲水改性.实验对膜的表面亲水性、抗粘附性能和抗污染性能进行表征,并采用原子力显微镜（AFM）测量膜与污染物探针之间的粘附力以进一步探究改性膜的抗污染机理.实验结果显示,改性后,PVDF膜的接触角从85°减小至42°,润湿时间从20s缩短至10s,表面亲水性显著提高;在静态吸附实验中,改性膜表面粘附的蛋白质和多糖数量明显减少;在动态污染实验中,改性膜的水通量恢复率（FRR）较高,不可逆通量下降率（IFR）较低,说明其较强的抗污染性能.AFM界面粘附力的测试结果表明污染物探针与改性膜面的粘附力较弱,进一步证实改性膜表面丰富的亲水基团以及超支化结构的位阻效应可以有效改善PVDF膜的抗污染性能.     

多巴胺非共价改性碳纳米管超滤膜的制备及抗污染性能

利用多巴胺(DA)的自聚合特性对多壁碳纳米管(MWCNT)进行非共价改性,制备了多巴胺改性碳纳米管超滤膜(PDA/MWCNT),并对其抗污染性能进行了系统研究.采用X射线光电子能谱、傅里叶红外光谱、接触角测量仪和扫描电镜对PDA/MWCNT膜进行亲水性和化学组成的表征.选取大肠杆菌菌液为目标污染物,研究了不同改性条件对PDA/MWCNT膜抗污染性能及抗蛋白黏附能力的影响.结果表明,DA成功引入到MWCNT表面.DA与MWCNT交联时间为5h、DA浓度1g/L、MWCNT负载量2.17mg/cm²时,MWCNT膜的接触角由改性前112.79°降至8.4°.改性后PDA/MWCNT膜表面的氧元素含量为改性前的2.9倍,膜的亲水性得到显著改善.膜通量较改性前提高1倍,膜的抗污染性能、抗菌性及抗蛋白黏附能力得到显著提高,错流冲洗后的膜通量恢复率从56.62%增加到88.74%.     

远程氩等离子体对聚醚砜膜表面性能的改性

采用双悬浮探针和电子自旋共振法定量对远程氩等离子体进行诊断,确定了电子、离子浓度和自由基浓度的分布,以预测表面改性的最佳区;利用远程氩等离子体对聚醚砜（PES）超滤膜进行表面改性,通过接触角测量、扫描电子显微镜和X射线光电子能谱分析改性前后膜表面结构和性能的变化,最后利用牛血清蛋白分离实验分析改性前后膜的分离性能和抗污染性能变化.结果表明,氩等离子体中电子、离子浓度沿轴向距离逐渐降低,在30cm后接近于0,而40cm处自由基浓度仍维持在90%以上,为可能的最佳表面改性区;在该区对PES超滤膜改性后,引入含氧基团和含氮基团,膜表面（O+N）/C原子比从0.18增大到0.46,增强膜表面极性;在最佳处理条件下,膜表面接触角从67°减小到18°,使膜表面亲水性能增强,抑制了电子、离子对膜的刻蚀作用;通过牛血清蛋白实验测定改性后膜污染率由70.3%减小到64.7%,抗污染性能提高.     

纳米二氧化硅改性聚酰胺复合膜及其抗污染性能

采用经3-氨基丙基三甲氧基硅烷（APTMS）修饰的纳米二氧化硅（SiNPs）,对正渗透聚酰胺复合膜（TFC）进行抗污染改性.在静电吸附作用下,APTMS-SiNPs可通过表面涂覆的方式接枝在带负电的TFC表面,以提高膜的亲水性和抗污染效能.改性后,大量纳米材料成功接枝在膜表面,膜表面的接触角降低了54%,而膜电位和表面粗糙度无明显变化.采用海藻酸钠作为代表污染物,对原膜和改性膜的动态污染行为进行探究,通过监测污染阶段的通量变化和膜表面滤饼层含量,发现改性膜在膜污染后期表现出优良的抗污染性能,最终通量衰减降低了28%,膜表面滤饼层含量减少了35%.改性膜的抗污染性能主要归因于APTMS-SiNPs带来的膜表面亲水性的大幅提高.     

制备高通量、抗污染PDA/PEI纳米颗粒膜用于农村含油生活污水处理

水处理分离膜具有纳米尺度筛分孔道,虽适合分散式处理农村生活污水中油水乳化液,但膜污染严重,导致膜通量较低.因此,设计抗污染、高通量水处理分离膜可实现农村含油生活污水高效处理.本文采用真空辅助自组装技术,在高分子膜表面及内部负载聚多巴胺（PDA）/聚乙烯亚胺（PEI）纳米颗粒,制备了PDA-NP膜.由于纳米颗粒含有丰富的亲水基团,改性后膜纯水通量及农村含油生活污水通量恢复率分别高达（741.23±17） L/（m²·h）及99.4%,实现了高通量、抗污染目标;另外,对农村含油生活污水TOC的去除率达45.12%,具有较强的实际意义.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.