Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)吸附性能及其作用机理研究

采用水浴共沉淀法在碱性条件下制备两种Zn系层状双金属氢氧化物(Zn-LDHs),并对天然麦饭石进行覆膜改性得到Zn-LDHs覆膜改性麦饭石.运用能谱分析仪(EDS)配合场发射扫描电子显微镜(FE-SEM)检测改性前后麦饭石,及吸附试验后ZnFe-LDHs覆膜改性麦饭石的形貌和元素变化;采用X射线衍射仪(XRD)对天然麦饭石和ZnFe-LDHs覆膜改性麦饭石的结构进行表征;通过等温吸附试验、解吸附试验、吸附动力学试验、吸附热力学试验、不同pH值条件下的吸附试验和竞争离子吸附试验,探究Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)的吸附效果及其作用机理.结果表明,Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)的吸附性能显著提升,其中ZnFe-LDHs覆膜改性麦饭石饱和吸附容量(2500 mg·kg~(-1))较天然麦饭石(714.29 mg·kg~(-1))提高了3.5倍;吸附时间、pH值和温度条件均对吸附容量产生影响;Zn-LDHs覆膜改性麦饭石吸附过程更符合Langmuir等温模型、准二级动力学模型、Elovich模型,为均匀的单分子层化学吸附,而天然麦饭石吸附过程符合Freundlich等温模型和准一级动力学模型,吸附类型为非均匀多分子层物理吸附;Zn-LDHs覆膜改性麦饭石热力学参数ΔG~θ0,ΔH~θ0,ΔS~θ0,说明Zn-LDHs覆膜改性麦饭石对Cd(Ⅱ)的吸附是自发放热过程,天然麦饭石吸附则为自发的吸热过程.研究结果可为ZnFe-LDHs覆膜改性麦饭石有效应用于生态工程除Cd(Ⅱ)提供理论依据和技术参考.     

重庆市不同材质路面径流污染特征分析

通过采集和监测2010年雨季重庆市同一区域的2条不同材质公路的3次降雨径流过程水样,研究了沥青路面和水泥路面径流的污染特征和差异.结果表明,2种材质路面径流中化学需氧量(COD)、总氮(TN)和总磷(TP)的次降雨平均浓度(EMC)均超过国家地表水环境质量V类水质标准(GB 3838—2002);沥青路面径流中总悬浮物(TSS)、COD和TP的浓度明显高于水泥路面,分别为水泥路面的2.05、1.35和1.27倍;沥青路面污染物的初始浓度普遍高于水泥路面,TSS和TP浓度最大值的出现时间滞后于水泥路面.在2010年6月19日、7月4日和7月9日的3场降雨事件中,沥青路面30%径流量与此时径流污染物浓度之比的平均值(FF₃₀)分别为水泥路面的1.26、1.07和1.32倍.沥青路面坑槽较多和成分复杂是导致其表现出不同于水泥路面的径流污染特征的重要原因.     

进水氨氮浓度对生物除磷颗粒系统的影响

在SBR反应器中接种成熟的生物除磷颗粒,通过分阶段提高进水中氨氮浓度,研究了进水氨氮浓度对生物除磷颗粒系统的影响,确定系统对进水氨氮负荷的承受能力.结果表明,进水氨氮浓度低于45 mg·L~(-1)时,生物除磷颗粒系统具有良好的性能,TP去除率在96%以上,COD去除率在89%以上,出水TP浓度和COD浓度分别在0. 4 mg·L~(-1)和25 mg·L~(-1)以下,颗粒粒径在950μm以上,SVI在45 m L·g~(-1)以下;进水氨氮浓度为60 mg·L~(-1)时,TP去除率在95%以上,出水TP浓度在0. 5mg·L~(-1)以下,颗粒粒径为760μm,SVI为56 m L·g~(-1),系统中生物除磷颗粒出现部分解体,PAOs代谢和生长开始受到抑制.进水氨氮浓度达到70 mg·L~(-1)时,TP去除率为70%,出水TP浓度在3 mg·L~(-1)左右,颗粒粒径为570μm,SVI为75 m L·g~(-1),PN/PS值达到7. 50左右,系统中生物除磷颗粒严重解体,PAOs代谢和生长被严重抑制.随着进水氨氮浓度上升,导致生物除磷颗粒中微生物分泌蛋白质增加和多糖减少,PN/PS值增大,出现生物除磷颗粒解体,颗粒粒径减小和SVI上升,生物除磷颗粒的结构和功能被破坏.     

透水路面-生物滞留池组合道路的城市面源污染控制效果评估

不同低影响开发(LID)技术组合对于控制城市面源污染具有重要应用价值,但是其对城市面源污染形成过程(污染物累积-冲刷-输送)的影响及污染负荷削减效果的评估鲜见报道.本研究以深圳市国际低碳城为例,分析了6场降雨事件下透水路面-生物滞留池组合对城市面源晴天污染物累积量、降雨径流冲刷量、不同LID设施的削减量、溢流的负荷量的影响.结果表明,研究区地表颗粒物平均累积量为(15.80±3.79)g·m~(-2),粒径250μm的颗粒物质量占比约为65.14%;6场不同强度降雨对地表颗粒物的平均冲刷率为17.15%,粒径105μm的颗粒物冲刷率为62.71%~74.94%;降雨冲刷地表径流污染物SS、TN、TP的平均污染负荷分别为2.02、0.025、0.001 3 g·m~(-2);透水路面下渗、过滤作用对污染物SS、TN、TP的去除率分别为70.26%、46.29%、19.27%;生物滞留池对径流二次净化去除率分别为85.25%、20.22%、70.27%;入河径流污染物SS、TN、TP的平均污染负荷分别为0.08、0.011、0.000 3 g·m~(-2),是地表冲刷污染负荷的4.05%、43.47%、24.39%.透水路面-生物滞留池组合应用对道路径流中污染物的净化效果显著.通过定量化表征透水路面-生物滞留池组合应用道路的城市面源污染形成过程,以期为城市面源污染形成过程的污染负荷估算及LID工程绩效评估提供科学依据,为LID在国内的推广应用和海绵城市设计提供参考.     

碱和磁复合改性小麦秸秆生物炭对水体中镉的吸附特性及机制

通过对小麦秸秆生物炭(BC)进行碱和磁复合改性得到改性小麦秸秆生物炭(FKC),在SEM-EDS、 BET、 FT-IR、 XRD和VSM等表征的基础上,研究了FKC对水中Cd~(2+)的吸附特性及温度、pH值和投加量等对吸附特性的影响,探讨了碱和磁复合改性提高小麦秸秆生物炭吸附Cd~(2+)性能的机制.结果表明,与BC相比,KFC结构疏松多孔,表面积增加了19.11倍,O—H、■等芳香族和含氧官能团数量增多,并且出现新的官能团Fe—O. FKC具有磁性,其磁化强度为8.43 emu·g~(-1),能够回收重复使用. FKC对Cd~(2+)的吸附更符合准二级动力学和Langmuir等温吸附模型,表明其主要以化学吸附为主,FKC的理论最大平衡吸附量为23.44mg·g~(-1),是BC的1.47倍. FKC对Cd~(2+)的吸附是自发的吸热过程.在pH为2～8范围内,随pH的升高FKC的吸附能力逐渐提高.生物炭的投加量为10 g·L~(-1)较好.经3次"吸附-解吸-再吸附"循环后,FKC对Cd~(2+)的吸附量仍达到17.71mg·g~(-1),表明其有良好的重复利用性.该研究结果可为碱和磁复合改性小麦秸杆生物炭应用于Cd污染废水处理提供理论指导.     

不同锆负载量锆改性膨润土对水中磷酸盐吸附作用的对比

通过实验对比考察了不同锆负载量的锆改性膨润土对水中磷酸盐的吸附作用.结果表明,锆改性膨润土对水中磷酸盐的吸附动力学过程符合准二级动力学模型,整个过程可以分为快速吸附阶段、缓慢吸附阶段和平衡吸附阶段,其中缓慢吸附阶段的吸附速率受膜扩散和颗粒内扩散所控制.锆改性膨润土对水中磷酸盐的吸附等温实验数据可以采用Langmuir、Freundlich、Sips和Dubinin-Radushkevich等温吸附模型进行拟合.实验条件下,磷酸盐吸附性能随pH增加而降低.溶液共存的Na~+、K~+和Ca~(2+)促进了锆改性膨润土对磷酸盐的吸附,并且Ca~(2+)的促进作用远远大于Na~+和K+,而溶液共存的HCO-3和SO2-4一定程度上抑制了锆改性膨润土对磷酸盐的吸附.锆改性膨润土吸附水中磷酸盐的主要机制为配位体交换并形成内层磷酸盐配合物.锆改性膨润土对水中磷酸盐的吸附能力随着锆负载量的增加而增加,而锆改性膨润土中单位质量ZrO_2对水中磷酸盐的吸附量则随着锆负载量的增加而降低.当ZrO_2负载量由3.61%增加到13.15%时锆改性膨润土的最大单层单位吸附量(以P计)显著地由3.83 mg·g~(-1)增加到9.03 mg·g~(-1),而继续增加ZrO_2负载量至19.63%时锆改性膨润土的最大单层单位吸附量则缓慢地提高到9.66 mg·g~(-1)(以P计).当ZrO_2负载量由3.61%逐渐增加到19.63%时,锆改性膨润土中单位质量ZrO_2的磷酸盐最大吸附量[m(P)/m(ZrO_2)]由106 mg·g~(-1)逐渐下降到49.2 mg·g~(-1).综合考虑吸附剂的经济成本和吸附容量,ZrO_2负载量为13.15%锆改性膨润土更为适合作为吸附剂去除水中磷酸盐.     

三峡库区典型紫色土小流域径流及氮磷流失特征

为了解三峡库区典型紫色土小流域径流污染特征,对新政小流域典型土地利用类型下降雨-径流时间过程和小流域集水区出口径流中氮磷浓度进行动态监测,监测分析库区小流域氮磷在降雨径流中的流失规律.结果表明,小流域径流氮磷损失量分别为13. 69 kg·(hm~2·a)-1和1. 50 kg·(hm~2·a)-1.农肥所含氮磷及降雨冲刷是小流域径流污染的主要原因.小流域的总氮(TN)和总磷(TP)平均浓度达10. 05 mg·L~(-1)和1. 10 mg·L~(-1),远超过富营养化发生标准,须引起关注.本研究观测的两场降雨中,8月15日降雨中硝态氮(NN)和颗粒态磷(PP)分别为69. 47 kg和6. 83 kg,分别占TN和TP的53. 91%和53. 78%; 8月26日降雨中NN、氨氮(AN)和PP分别为6. 68、5. 61和1. 36 kg,分别占TN和TP的37. 74%、31. 69%和57. 63%,表明氮素流失主要通过可溶态的方式,而磷素迁移则以颗粒态为主.小流域强降雨对于氮磷流失的影响显著.这与紫色土土层薄、耕作频繁、土壤相对疏松等性质有关.     

锆改性硅藻土吸附水中磷的研究

采用锆对硅藻土进行改性所得锆改性硅藻土,其氧化锆质量分数占12.39%,经XRD鉴定为无定形.SEM结果显示,改性后硅藻土表面出现粗糙多孔的絮状物.相比硅藻土,锆改性硅藻土的比表面积由14.00 m~2·g~(-1)扩大到75.22 m~2·g~(-1).XPS谱图显示,氧化锆与硅藻土之间以化学键方式,而非物理沉积方式结合.锆改性硅藻土对磷的等温吸附线更符合Langmuir模型,拟合得到最大吸附量为10.56 mg·g~(-1).锆改性硅藻土的吸附量按照氧化锆的质量分数计算为81.67 mg·g~(-1)ZrO_2,高于文献报道的纯氧化锆吸附剂.锆改性硅藻土对磷的吸附随pH的上升而下降,结合吸附前后材料的Zr3d高分辨XPS图谱,确定锆改性硅藻土对磷的吸附为配体交换过程.氯离子、硫酸根离子和硝酸根离子共存不会抑制磷的吸附,而碳酸氢根离子具有一定的抑制作用.对磷浓度为2 mg·L~(-1)的富营养化湖水,锆改性硅藻土投加量大于1.25 g·L~(-1)时,反应后磷浓度即可满足《地表水环境质量标准》规定的湖库Ⅲ类标准.     

紫外辐照改性生物炭对VOCs的动态吸附

采用365 nm紫外光辐照改性椰壳生物炭,以提升对挥发性有机污染物(VOCs)的吸附性能.选取苯和甲苯两种典型的VOCs为吸附质,考察了改性前后生物炭的吸附穿透曲线.结果表明,紫外辐照改性后的生物炭其吸附性能显著增加,对苯和甲苯的饱和吸附量分别由7.27 mg·g~(-1)和7.98 mg·g~(-1)提升至122.80 mg·g~(-1)和236.36 mg·g~(-1),吸附穿透时间也由1 min和2 min大大延长至390 min和620 min.生物炭表面理化特征分析表明,紫外辐照增大了生物炭表面含氧官能团的含量和外比表面积,这可能是改性生物炭吸附性能提升的关键因素.Yoon-Nelson、Thomas和BDST模型均能很好地模拟改性生物炭对不同浓度苯和甲苯的吸附过程,其相关系数大于0.992.热重分析结果表明,紫外辐射对生物炭的热稳定性影响甚微.改性生物炭吸附饱和后,可经热再生后重复利用,对甲苯的吸附重复利用5次后仍有较高的吸附能力.     

改性海绵铁深度除磷及其再生磷回收方法

为了从污染水体中去除磷并有效回收磷资源,本文研究了海绵铁改性前后吸附除磷特性,并构建海绵铁除磷渗滤床,考察了其连续流除磷特性及再生活化方法,并探究再生废液中磷回收生成鸟粪石的工艺条件.结果表明:硫酸改性后的海绵铁对磷的最大理论吸附容量从改性前4.17 mg·g~(-1)提升至18.18 mg·g~(-1).吸附饱和的改性海绵铁,采用1 mol·L~(-1)氢氧化钠解吸和6%硫酸再活化后,能够达到98%的活化率.海绵铁除磷渗滤床在长达约200 d的连续流运行实验中表现出良好的除磷能力,在进水TP=10 mg·L~(-1),HRT=1 h条件下,磷综合去除率达30%～89%,累积单位容积磷吸附量达到6.95 kg·m~(-3).海绵铁碱再生后的废液可以用于回收鸟粪石,其最佳生成条件为:pH=10,n(Mg~(2+))∶n(PO_4~(3-))∶n(NH~+_4)=1.3∶1∶1.1.在最优条件下,磷回收率可以达到97.8%.本研究提供的方法对于污染水体中磷营养元素的去除及回收利用具有理论与实践意义.     

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.     

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.