温度对合成钛酸盐纳米材料的影响及其对水中Cd (Ⅱ)的去除效果

为有效去除水中Cd（Ⅱ）,以TiO₂纳米粉和NaOH为原料,调节水热反应温度分别为100、120、150和190℃,制备出了不同形貌的TNs（钛酸盐纳米材料）,分别记为TNs-100、TNs-120、TNs-150和TNs-190,并对其形貌、结构、比表面积、化学组成等物理化学性能进行了表征;通过对水中Cd（Ⅱ）的静态吸附试验,考察了TNs对Cd（Ⅱ）的吸附性能.结果表明:随着合成温度的升高,TNs的形貌逐渐从纳米片演变成纳米管,管长逐渐变长,最后变成纳米棒.TNs-100的晶型结构主要是锐钛矿型;随着温度升高,结晶度逐渐增强;TNs-190出现了部分金红石相.TNs-150对Cd（Ⅱ）的吸附能力最强,最大平衡吸附量为254.66 mg/g,最佳吸附pH为5.0.再生的TNs-150对Cd（Ⅱ）循环吸附6次的去除率和解吸率均可达93%以上.TNs-150对Cd（Ⅱ）的吸附过程符合准二阶动力学方程和Langmuir吸附等温模型,吸附机制主要是TNs层间Na+和H+与溶液中Cd（Ⅱ）的离子交换.研究显示,TNs的饱和吸附量均高于同类吸附剂,能有效去除水中Cd（Ⅱ）.      

温和水热法合成钛酸盐纳米管及其对水中重金属离子的吸附研究

采用温和水热法一步快速合成了钛酸盐纳米管(TNTs),并应用于对水中重金属离子Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ)的吸附.通过选择纳米级锐钛矿替代P25型二氧化钛作为反应原材料,成功将水热反应时间从72 h缩短至6 h.TEM,XRD和FT-IR等表征证实了新合成材料的为管状钛酸盐结构.TNTs对3种重金属离子的吸附动力学均符合准二级动力学方程,吸附等温线均符合Langmuir模型,且对Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ)的理论最大吸附量分别高达525.58、214.41和69.65 mg·g~(-1).p H=5时,吸附动力学实验表明对于初始浓度分别为200、100和50 mg·L~(-1)的Pb(Ⅱ)、Cd(Ⅱ)和Cr(Ⅲ),在TNTs上的平衡吸附量分别为513.04、212.46和66.35 mg·g~(-1),吸附性能优于传统吸附材料.合成的TNTs结构为三联的[Ti O6]八面体骨架和层间H+/Na+,其吸附机理为金属阳离子与TNTs层间Na+的离子交换.同时,共存离子对吸附的影响实验表明TNTs对重金属离子的吸附存在选择性,即使在较高的共存离子浓度下(10 mmol·L~(-1))TNTs对目标重金属离子的吸附性能依然优异.该研究提供了一种应用钛酸纳米材料高效去除水体重金属离子的方法.     

碳纳米管-羟磷灰石对铅的吸附特性研究

采用多壁碳纳米管-羟磷灰石(MWCNT-HAP)复合材料,通过间歇试验研究了MWCNT-HAP对Pb(Ⅱ)的吸附特性.主要探讨了固液比、p H、离子强度、反应时间、Pb(Ⅱ)的初始质量浓度及温度等因素对吸附的影响.结果表明,固液比、p H与温度对于去除Pb(Ⅱ)的影响较大,离子强度影响较小.当温度为20℃,固液比为0.08 g·L-1,p H0为5.5,Pb(Ⅱ)的初始质量浓度为100 mg·L-1时,吸附量为716.13 mg·g-1.动力学试验结果表明,MWCNT-HAP吸附Pb(Ⅱ)为快速反应过程,在30 min时,吸附量可达最大吸附量的90%,60 min即可达平衡.伪二级动力学模型可较好地拟合动力学试验数据,可采用该模型描述MWCNT-HAP对Pb(Ⅱ)吸附的动力学过程.热力学试验结果表明,在不同温度下的自由能变均为负值,表明MWCNT-HAP对Pb(Ⅱ)的吸附为自发反应,升温有利于反应进行.Langmuir模型拟合不同温度下的等温试验结果得到可决定系数(R2为0.999 8~1.000 0),可采用该模型模拟MWCNT-HAP对Pb(Ⅱ)的等温吸附过程.MWCNT-HAP去除Pb(Ⅱ)的主要机制为MWCNT-HAP表面含氧官能团与Pb2+间的络合反应、HAP的分解-沉淀、Pb2+与Ca2+离子交换等.     

茶叶基水合氧化铁吸附水体中Pb(Ⅱ)的性能

采用原位沉积技术将水合氧化铁(HFO)负载于废弃茶叶渣表面制备了复合材料茶叶基水合氧化铁(HFO-TW),研究了HFO-TW对水溶液中Pb(Ⅱ)的吸附特性,探讨了溶液pH值、时间、共存碱土离子、温度、Pb(Ⅱ)初始浓度等因素对Pb(Ⅱ)的吸附效果的影响.结果表明酸性范围内,Pb(Ⅱ)的吸附量随溶液pH升高而增大;Pb(Ⅱ)的吸附速度较快,100 min内便可达吸附平衡,且动力学曲线较好地符合伪一级和伪二级动力学模型,拟合系数可达98.8%;在竞争离子Ca(Ⅱ)/Mg(Ⅱ)的浓度高于Pb(Ⅱ)50倍时,HFO-TW对Pb(Ⅱ)仍具有较强的吸附能力,Pb(Ⅱ)的吸附量仅分别下降12.1 mg·g-1和8.1 mg·g-1;Pb(Ⅱ)的吸附过程较好地符合Langmuir等温模型,理论最大吸附容量为89.43 mg·g-1,远高于未经改性的茶叶渣和其他生物吸附剂.所有结果均证实HFO-TW在净化实际铅污染水体中有着较为广阔的应用潜力.     

钛酸盐纳米管对水中氨氮的吸附特性

以P25和Na OH为原料,采用水热法制备钛酸盐纳米管(TNTs),利用X射线衍射(XRD)、透射电镜(TEM)对材料的组成和形貌进行表征,通过其对水中氨氮的静态吸附实验,考察TNTs对水中氨氮的吸附特性及规律.结果表明碱浓度为10mol·L-1时,可以获得管长约120 nm,管径约为8 nm的钛酸盐纳米管,其对氨氮的平衡吸附量达到10. 67 mg·g-1. p H值介于3～8时,TNTs能有效地吸附水中的氨氮.吸附过程在1 h基本达到平衡,符合准二级动力学方程.颗粒内扩散方程拟合结果发现,TNTs对氨氮的吸附过程由表面吸附和颗粒内扩散共同控制. Temkin方程能较好地描述TNTs对氨氮的吸附行为.热力学实验表明钛酸盐纳米管对氨氮的吸附是自发进行的吸热过程.共存阴阳离子对氨氮的吸附具有抑制作用,分别表现为SO_4~(2-) Cl~- H_2PO_4~-、K~+ Na~+ Ca~(2+).再生的钛酸盐纳米管对氨氮循环吸附5次仍有88. 64%的吸附效果.红外光谱(FT-IR)研究表明钛酸盐纳米管对氨氮的吸附机制是TNTs层间的Na~+与溶液中的NH_4~+之间发生离子交换.钛酸盐纳米管的优良循环使用性能和大吸附容量使得其能有效地去除水中氨氮.     

酸和热处理对海泡石结构及吸附Pb2+、 Cd2+性能的影响

通过X射线衍射、傅里叶变换红外光谱及比表面积分析等研究了酸和热处理对天然海泡石结构的影响,并考察不同处理后的海泡石样品吸附重金属Pb2+、Cd2+性能.结果表明,海泡石比表面积均随盐酸浓度、处理时间的增加而略有增大,而结构无明显变化,0.5 mol·L-1 HCl处理时,天然海泡石中的CaCO3未能被完全去除,6.0 mol·L-1 HCl处理72 h时,海泡石比表面积达到最大301.47 m2·g-1.盐酸热处理并不能提高海泡石的比表面积,也不会使海泡石结构产生明显变化.不同类型酸处理对海泡石比表面积提高顺序依次为:HCl>HNO3>H2SO4;海泡石经焙烧后比表面积迅速下降,由100℃的21.44 m2·g-1下降到900℃的0.17 m2·g-1.重金属吸附实验表明,盐酸处理浓度和时间对海泡石吸附Pb2+、Cd2+离子性能无明显影响;不同酸处理对海泡石吸附Pb2+、Cd2+离子性能存在一定影响,H2SO4处理后海泡石对Pb2+、Cd2+离子吸附量明显高于HCl和HNO3处理.海泡石焙烧处理后对Pb2+离子吸附量无明显影响,但对Cd2+离子吸附量在焙烧700℃以上时增加明显.     

柱状污泥基活性炭制备方法及其除污染效能研究

以城市污水厂剩余污泥为原料,用氯化锌活化法研究一种柱状污泥基活性炭(CSAC)的制备方法及其工艺条件优化,并选择粉末污泥基活性炭(PSAC)和一种商品煤质碳(MAC)作为对照,考察了CSAC对重金属离子Cu(Ⅱ)和Pb(Ⅱ)及有机污染物硝基苯的吸附去除效能.结果表明,CSAC的比表面积及微孔容积分别是306.9 m2·g-1和0.109 cm3·g-1,仅为MAC的36.7%和23.6%,但其对Cu(Ⅱ)和Pb(Ⅱ)的平衡吸附量却远远高于MAC,说明CSAC表面存在的高含量酸性官能团在吸附去除重金属过程中起到了重要的作用.由于制备原料相同及制备工艺相似,CSAC与PSAC的理化性质基本相同,两种炭的表面酸性官能团含量较高,对Cu(Ⅱ)和Pb(Ⅱ)均具有较好的吸附去除效果,优于MAC,只是CSAC的比表面积和微孔容积略低于PSAC;在对硝基苯的吸附实验中,CSAC及PSAC的吸附效率均远远低于MAC,说明在对有机物硝基苯的吸附中,活性炭的比表面积等物理性质起到了较大的作用.同时,所制备的CSAC的稳定度大于95%,易于分离回收,不会造成二次污染,适合废水中重金属离子的吸附去除.     

酿酒酵母吸附Zn2+、Pb(2+)、Ag+、Cu2+的动力学特性研究

利用静态摇瓶实验方法,研究了工业废弃酿酒酵母无缓冲溶液体系吸附Zn2 、Pb2 、Ag 、Cu2 的动力学特性.结果表明,酵母吸附Zn2 、Pb2 、Ag 、Cu2 的动力学过程可以用准二级动力学方程进行描述.金属离子初始浓度在0.08～3.0 mmol·L-1范围内,Langmuir方程可以较好地描述Zn、Pb、Ag的等温吸附行为,Zn、Pb、Ag的理论饱和吸附量分别为0.522 mmol·g-1(34.11 mg·g-1)、0.577 mmol·g-1(119.50mg·g-1)和0.329 mmol·g-1(35.50 mg·g-1).以mol为基础的金属离子吸附量顺序是:Pb＞Zn＞Ag;以mg为基础的金属离子吸附量顺序是:Pb＞Ag＞Zn.Freundlich方程对整个浓度范围内的平衡数据拟合效果较差,但是它可以较好地描述低浓度Zn2 (初始浓度0.08～0.5mmol·L-1)、低浓度Pb2 (0.08～1.0 mmol·L-1)以及高浓度Ag (1.5～3.0 mmol·L-1)的等温吸附行为.酵母吸附Zn2 、Pb2 、Ag 、Cu2 过程中,溶液pH值有不同程度的增加,增加幅度大小顺序是Zn＞Pb＞Ag＞Cu,这间接反映出Zn2 、Pb2 、Ag 、Cu2 与水溶液中H 的竞争力逐步减弱.吸附过程中酵母释放大量的K ,其次是Mg2 ,而Ca2 、Na 的释放量较低,数量级一般可分别达到几百μmol·g-1 、几十μmol·g-1、几到几十μmol·g-1、十几μmol·g-1.     

花椰菜基生物炭对水中Pb (II)的吸附性能

以农业废弃物花椰菜的根和叶为原材料,采用限氧裂解法在500℃条件下制备花椰菜根基生物炭(BCR)和叶基生物炭(BCL),探究了吸附时间、温度、Pb(Ⅱ)初始浓度、pH及不同共存离子对2种生物炭吸附性能的影响,并通过扫描电镜(SEM)、能谱分析(EDS)、红外光谱(FTIR)及比表面积测定(BET)等手段对生物炭的结构和性质进行了表征,初步探讨了吸附机理.结果表明,2种生物炭对Pb(Ⅱ)的吸附符合准二级动力学和颗粒内扩散模型,BCR和BCL对Pb(Ⅱ)的吸附分别在3 h和6 h达到吸附平衡;2种生物炭对不同浓度下Pb(Ⅱ)的吸附符合Langmuir和Freundlich等温吸附模型;在25℃条件下,BCR和BCL对Pb(Ⅱ)的最大吸附量分别达到454.55和434.78 mg·g~(-1),BCR和BCL具有良好的吸附效果,可作为优良的生物质基吸附材料.     

毛木耳和白木耳子实体对Cd(Ⅱ)、Cu(Ⅱ)、Pb(Ⅱ)和Zn(Ⅱ)的吸附特性研究

通过批量实验研究了毛木耳(Auricularia polytricha)子实体和白木耳(Tremella fuciformis)子实体对水溶液中不同浓度的Cd(Ⅱ)、Cu(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)的吸附能力和吸附动力学特性.此外,研究了多种离子共存对吸附效果的影响,以及吸附剂在多重金属混合溶液中对各重金属离子的吸附量大小顺序.结果表明,毛木耳子实体对单金属溶液中Cd(Ⅱ)、Cu(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)的最大吸附量分别为18.91、18.69、20.33和12.42mg·g-1,最大去除率在实验设置条件下均在85%以上;白木耳子实体对单金属溶液中Cd(Ⅱ)、Cu(Ⅱ)、Pb(Ⅱ)、Zn(Ⅱ)的最大吸附量分别为19.98、20.15、19.16和16.41mg·g-1,最大去除率在实验条件下均在75%以上.在初始浓度分别为10、50和100mg·L-1的溶液中,随初始浓度的增加,菌体对重金属的吸附量增加,但去除率下降.准二阶模型比准一阶模型能更好地描述吸附动力学过程.2种吸附剂对多金属溶液中重金属离子吸附量的大小均呈现Pb(Ⅱ)Cu(Ⅱ)Zn(Ⅱ)Cd(Ⅱ)的吸附规律,电负性大的金属离子被优先吸附.溶液中其它重金属离子的存在使白木耳子实体对Pb(Ⅱ)的吸附量上升,而使毛木耳子实体对4种离子和白木耳子实体对其它3种离子的吸附量下降.研究发现,毛木耳和白木耳子实体都是潜在的生物吸附剂.     

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.     

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.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.