脱硫类水滑石衍生复合氧化物不同方法的制备与表征

采用尿素水解法和共沉淀法制备了MgAl类水滑石,高温焙烧获得衍生复合氧化物.采用X射线衍射(XRD)、热重分析(TG-DTG)、扫描电镜(SEM)、N2-吸附/脱附和CO2程序升温脱附(CO2-TPD)等手段对所制备的复合氧化物结构特征进行表征,并研究其对SO2脱除性能的差异.结果表明,共沉淀法制备的MgAlO复合氧化物比尿素法具有更大的比表面积(148.1m2·g-1)和更多碱性位,这些特点可能促使该方法制备的复合氧化物具有更高的SO2储存容量和反应速率.采用尿素法和共沉淀法制备的MgAl水滑石复合氧化物在700℃温度下SO2吸附容量分别可达0.55g·g-1和0.79 g·g-1.     

铁镧复合氧化物纳米吸附剂的制备、表征及As（Ⅲ）吸附性能研究

本研究采用共沉淀法制备了一种新型铁镧复合氧化物吸附剂(Fe-La),并对其表面特性及As(Ⅲ)吸附行为进行了系统研究.扫描电镜(SEM)和透射电镜(TEM)结果表明,铁镧复合氧化物具有纳米结构,初级粒子粒径范围为20~200 nm.X-射线衍射仪(XRD)表征结果表明,铁镧复合氧化物具有类似氢氧化镧的晶型结构.N2吸附BET法结果表明,铁镧复合氧化物的比表面积为99.3 m2·g-1.盐加入法测得吸附剂的等电点为7.8.As(Ⅲ)吸附实验结果分析表明,铁镧复合氧化物对As(Ⅲ)具有良好的吸附效果,最大吸附量(pH 7.0)为58.2 mg·g-1,Langmuir吸附等温线可较好地拟合铁镧复合氧化物对溶液中As(Ⅲ)的吸附(R2=0.95);吸附速率较快,240 min内可完成吸附容量的80%,Elovich模型能较好地描述吸附过程(R2=0.97);溶液pH对铁镧复合氧化物吸附As(Ⅲ)的影响较为明显;共存阴离子对吸附影响的大小顺序为SO2-4相似文献   

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.     

新型纳米结构铈锰复合氧化物的磷吸附行为与机制研究

采用共沉淀法制备了一种新型铈锰复合氧化物吸附剂,对其进行了表征,并对磷吸附行为与机制进行了研究.表征结果分析表明,此氧化物由纳米级颗粒组成;铈锰复合氧化物中的铈氧化物有类似水合氧化铈的无定形结构;BET比表面积为157 m2·g-1,等电点为6.5.吸附实验结果表明,Langmuir吸附等温线模型可以更好地拟合铈锰复合氧化物对磷的吸附,最大吸附量为28.6 mg·g-1(p H=7.0);铈锰复合氧化物对磷具有较高的吸附速率,更符合准二级动力学模型;溶液p H对铈锰复合氧化物吸附磷的影响较为明显,随p H升高,吸附量降低;离子强度则影响不大;共存阴离子对吸附影响的大小顺序为Si O2-3CO2-3Cl-≥SO2-4.通过对铈锰复合氧化物吸附磷前后Zeta电位和红外谱图(FTIR)分析,可以推断磷在铈锰复合氧化物表面发生了特性吸附,磷酸根主要通过取代复合氧化物表面的金属羟基而被吸附去除.     

硫氰酸根在粒状镁铝复合氧化物上的吸附性能

以镁铝水滑石(Mg/Al-LDH)为前驱物制备了粒状镁铝复合氧化物(G-Mg3.3AlO4.8),采用BET、XRD、SEM和FT-IR方法对其结构进行了表征,考察了这种新材料对硫氰酸根(SCN-)的吸附性能.G-Mg3.3AlO4.8的比表面积和平均孔径分别为269.4 m2.g-1和13.25 nm,成型造粒保留了层状结构且无新相生成.Freundlich等温式和准二级动力学方程能很好地描述SCN-在G-Mg3.3AlO4.8上的静态吸附过程,25℃初始浓度为500 mg.L-1时静态吸附量可达165.8 mg.g-1;Yoon-Nelson模型能很好地预测SCN-在G-Mg3.3AlO4.8上的穿透曲线,初始浓度100 mg.L-1、流速5 mL.min-1、床层高度10 cm和pH=6时穿透点吸附量可达50.73 mg.g-1,重复使用4次对SCN-的脱除率均保持在98%以上,是一种可重复利用的高效吸附剂.     

还原共沉淀法制备Fe-Ti复合氧化物及其吸附水中As(Ⅴ)的研究

采用还原-共沉淀法制备了无定型纳米复合Fe-Ti氧化物(FFT)吸附剂,并研究其对水中低浓度As(Ⅴ)的去除性能.XRD表征结果表明,制备的纳米FFT物相为无定型,BET比表面积达325.3 m2·g-1,计算得到的BJH吸附平均孔径为2.46 nm(4V/A),颗粒分布均匀.同时,考察了纳米FFT吸附As(Ⅴ)的动力学、热力学、吸附等温线,以及温度、水中共存离子对其去除As(Ⅴ)的影响.结果发现,纳米FFT对As(Ⅴ)的吸附符合拟二级动力学模型,计算出的孔道扩散系数DP在10-11~10-13cm2·s-1之间,显示孔扩散是速率限速步骤.Langmuir、Freundlich和DubininRadushkevich(D-R)吸附等温式均可较好地拟合吸附行为,低浓度下Langmuir吸附模型计算出的Qm达到26.46 mg·g-1.最后,研究了地下水中常见的共存离子对吸附的影响,发现Ca2+、Mg2+能够促进吸附,H2PO-4和HCO-3则明显抑制吸附过程.     

凹凸棒石吸附氧化催化剂对甲醛的脱除研究

以酸改性凹凸棒石为载体,采用浸渍法以不同金属氧化物做活性组分进行了脱除甲醛的活性组分筛选,通过正交实验优化制备氧化锰凹凸棒吸附氧化催化剂工艺条件.结果表明,负载9%(质量分数)的锰氧化物,300℃焙烧4h制备的粒度为40～60目的凹凸棒吸附氧化催化剂在初始浓度为9.5552mg·m-3的甲醛空气中,24h时对甲醛的吸附量可达到0.188mg·g-1,甲醛脱除率达到98.35%.傅立叶变换红外光谱(FTIR)及X射线衍射(XRD)测试表明,凹凸棒吸附氧化催化剂对空气中的甲醛在室温下起到了吸附与催化氧化的作用.     

MgAlFe复合氧化物氧化吸附SO_2的性质

MgAlFe水滑石在 6 0 0℃以上焙烧后脱去表面水和层间水形成MgAlFe复合氧化物 通过对MgAlFe复合氧化物BET、XRD表征和测定它的吸附硫容 ,发现它对SO2 有优良的氧化吸附性能 吸附SO2 后MgO和尖晶石相消失 ,形成硫酸盐晶相 用氢气对饱和吸附SO2 后的MgAlFe复合氧化物进行还原再生 ,发现它经过 10次吸附还原循环后 ,MgO和尖晶石的晶相依然存在 ,是一种可循环利用脱除SO2 的环境催化材料     

铁锰氧化物/生物炭复合材料对水中硝酸根的吸附特性

热解经过氯化铁和高锰酸钾浸渍的小麦秸秆,制备铁锰金属氧化物/生物炭复合材料,用以去除水中硝酸根.通过X射线光电子能谱和扫描电镜分析,发现复合材料表面形成了Fe(Ⅲ)/Mn(Ⅳ)二元金属氧化物颗粒.制备优化结果表明,复合材料比表面积可达153.116 m2·g-1,零电荷点可达9.76.同时,还调查了固液比、溶液初始pH值和共存阴离子等因素的影响.研究发现,复合材料在溶液pH值1.00~9.05时对NO-3的去除率维持在75.40%~78.70%,且以配位交换为主要吸附机制.共存阴离子对吸附NO-3竞争吸附的影响顺序为:Cl-SO2-4PO3-4.等温吸附实验数据符合Langmuir方程,且最大吸附量为37.361 3 mg·g-1.吸附动力学分析发现,吸附过程遵循二级动力学方程,且以化学吸附为主.热动力学分析表明,吸附过程为自发吸热过程.上述结果说明铁锰氧化物/生物炭复合材料对于去除水中NO-3具有潜在价值.     

热解条件对生物炭性质和氮、磷吸附性能的影响

以橡木为原料,在不同的热解终温、升温速率和恒温时间下制备生物炭.对生物炭产率、p H、元素组分、工业组分、比表面积、红外光谱等理化特征进行分析,并考察生物炭对水溶液体系中NO-3-N、NH+4-N、PO3-4-P的吸附性能.结果表明:生物炭的产率受热解终温影响最大(极差:54.57%),恒温时间次之(极差:1.16%),升温速率最小(极差:0.42%).随热解终温、升温速率和恒温时间的增加,所得生物炭的p H和C含量增加,而H和O含量降低.热解终温对生物炭表面官能团影响较大,升温速率和恒温时间基本无影响.生物炭对氮、磷的吸附性能主要受热解终温影响.NO-3-N的吸附量最大可达2.80 mg·g-1(600℃),且随热解终温的升高呈指数增加.比表面积、表面碱性官能团和表面金属氧化物与NO-3-N吸附有关.随热解终温的增加,NH+4-N吸附量降低,最大吸附量为3.12 mg·g-1(300℃).阳离子交换量(CEC)是影响NH+4-N吸附的主要因素.PO3-4-P吸附量随热解终温的增加呈先增后减的趋势(在500℃达到最大,为9.75 mg·g-1),且吸附过程主要受生物炭表面碱性官能团和表面金属氧化物的影响.     

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.     

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.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

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.     

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.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.     

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.