单层硅烷负载磁铁矿纳米颗粒的制备及除磷性能

研究了N-氨乙基-γ-氨丙基三甲氧基硅烷在水溶液中以单层形式负载于磁铁矿纳米颗粒表面的方法,并研究了单分子层硅烷负载磁铁矿纳米颗粒吸附剂(monolayer of silane on magnetite nanoparticles,MSMNPs)的除磷性能。结果表明,在低浓度下(平衡浓度小于300mg·L-1)硅烷在磁铁矿纳米颗粒表面产生单层吸附,而反应温度90℃以上或离子强度0.1mol·L-1 NaCl以上可以使单层硅烷在磁铁矿纳米颗粒表面的覆盖度达到~100%。FTIR和XPS图谱显示负载的硅烷以化学键的形式与磁铁矿纳米颗粒表面相结合。单层硅烷负载不引起磁性强度的明显变化。MSMNPs对磷的吸附等温线更符合Langmuir模型,拟合得到的最大吸附量为7.59mg·g-1。由于磷吸附位位于MSMNPs的最外面,磷的吸附及脱附均很快,30min内达到90%以上,1h内达到平衡。因此,MSMNPs是一种易分离因而可反复使用,并且可快速吸附与脱附污染物的新型吸附剂。     

水合氧化铝负载的磁性核/壳结构Fe3O4@SiO2纳米颗粒对水中磷的去除及再利用

在磁铁矿纳米颗粒表面包被硅壳后再包被水合氧化铝,制备了具备核壳结构的磁性纳米颗粒除磷吸附剂(磁性氧化铝),通过XRD、TEM、VSM、BET比表面积测定进行了表征.XRD和TEM结果显示了核壳结构的存在,其饱和磁化强度达56.00 emu·g~(-1),比表面积达47.27 m~2·g~(-1).Langmuir模型计算的磷最大吸附量为12.90 mg·g~(-1),且在25℃和50℃下均保持稳定,反应快速,40min磷去除率达96%以上.磁性纳米吸附剂对磷的吸附与pH关系密切,在p H为5~9时磷去除率达90%以上.采用实际污水实验,最佳投量为1.25 kg·t~(-1).吸附-脱附-再生实验结果表明,磷吸附率随循环次数增加稍有下降,吸附的磷可以通过1 mol·L~(-1)的NaOH脱附,脱附率为90%左右,且吸附剂可以进行再生,具有反复利用和回收磷资源的潜力.     

铁锰复合氧化物/壳聚糖珠:一种环境友好型除磷吸附剂

采用两步法制备了一种环境友好型除磷基吸附剂——铁锰复合氧化物/壳聚糖珠(FMCB),对其进行了表征,并对其磷吸附行为进行了系统研究.表征结果表明,该吸附剂为多孔纤维结构,比表面积为248 m~2·g~(-1),孔容为0.37 m~3·g~(-1).吸附实验结果表明,FMCB对磷的吸附容量远高于纯的壳聚糖颗粒,且Langmuir模型能更好地拟合FMCB对磷的吸附,最大吸附量为13.3 mg·g~(-1)(pH 7.0);准二级动力学模型能更好地拟合FMCB对磷吸附的动力学实验数据;溶液pH对磷的吸附影响较大,随着pH的增大,磷的吸附量逐渐降低;共存的Ca~(2+)和Mg~(2+)对磷吸附略有促进,而共存阴离子对磷吸附具有抑制作用,影响大小顺序为:SiO_3~(2-)CO_3~(2-)SO_4~(2-)≥Cl~-.吸附磷后的FMCB可用NaOH溶液进行脱附再生,并可重复使用.在进水磷初始浓度为3 mg·L~(-1)条件下,吸附达到穿透时(出水磷浓度达0.5 mg·L~(-1)),可处理约800个柱体积的模拟含磷废水.     

部分还原氧化石墨烯-Fe3O4对水中Cd (Ⅱ)的吸附性能及机理

当前,治理可溶性重金属污染是环境保护的迫切任务.以氧化石墨烯(GO)和铁盐为前驱体,一步合成了部分还原氧化石墨烯-Fe_3O_4复合材料(rGO-Fe_3O_4),探索其作为Cd(II)高效吸附剂的潜力.同时,采用多种手段表征吸附剂结构和特性,重点研究了吸附剂对Cd(Ⅱ)的吸附特性和动力学.结果表明,在吸附剂中,纳米Fe_3O_4颗粒均匀地锚在石墨烯片层之间,避免了片层团聚,赋予其优良的吸附性能.在中性溶液中,使用rGO-Fe_3O_4(500 mg·L~(-1))吸附200.09 mg·L~(-1)Cd(II),5 min即可达到吸附平衡,吸附率和吸附量分别为90.88%和363.99 mg·g~(-1).另外,磁分离回收吸附剂仅需10 s,且循环吸附性良好.进一步研究显示,复合材料对Cd(II)的吸附为吸热、自发的化学吸附,过程受化学吸附和液膜扩散控制.     

铁锰复合氧化物包覆海砂的吸附除磷研究

利用铁锰复合氧化物包覆海砂制备了一种用于污水除磷的新型颗粒状吸附剂,并对其表面特性与磷吸附行为进行了研究.扫描电镜(SEM)分析结果表明,包覆后海砂颗粒表面凹凸不平且多孔,BET比表面积由0.06增至2.52 m2·g-1.磷吸附实验结果表明,包覆后海砂对磷的吸附能力显著提高,最大吸附容量为1.01~1.23 mg·g-1,优于多数文献报道的负载改性砂颗粒吸附剂;吸附动力学更符合准二级动力学方程,推测磷在包覆海砂表面发生了化学吸附;溶液p H对磷吸附有一定影响,离子强度则影响不大;共存阴离子对磷吸附影响的大小顺序为Si O2-3CO2-3F-SO2-4Cl-.     

载镧磁性水热生物炭的制备及其除磷性能

将小麦秸秆在水热条件下(220℃)炭化2 h得到水热生物炭(HTC),以HTC为载体,通过一步共沉淀法制备了一种吸附容量高、易于磁分离回收的载镧磁性水热生物炭复合材料(La-MHTC).通过等温线和动力学等吸附实验方法,研究了该材料对磷酸根的吸附特性,考察了载镧量、初始pH和共存离子等因素对磷酸根吸附过程的影响.结果表明La~(3+)∶Fe~(3+)为2∶1时,材料(2-La-MHTC)具有良好的吸附磷酸根的能力;在吸附剂投加量为0. 1 g·L~(-1),pH为7时,对磷酸盐吸附量达到100. 25mg·g~(-1);吸附符合Langmuir等温模型,吸附动力学过程遵循准二级动力学,并且吸附不受其它离子的影响(在Cl~-、NO_3~-和SO_4~(2-)等共存离子体系磷酸盐去除率达到98%),在较广的pH(3～10)范围都具有良好的吸磷能力.吸附的磷酸根可用NaOH溶液解吸,5次吸附-脱附循环实验中磷酸盐去除率均能达到90%以上,脱附效率为65%左右,说明该吸附剂具有良好的脱附和重复利用能力.应用其处理实际含磷污水,可将磷酸盐浓度从0. 87 mg·L~(-1)降低到0. 05 mg·L~(-1).吸附机制主要为静电吸附作用和La(OH)_3与磷酸盐通过配体交换形成内层络合物.     

开放系统下方解石对磷的去除

通过批量平衡法,研究开放系统条件下方解石对磷的去除特性.结果表明:1方解石在开放系统中的预平衡过程,在24h左右便能完成;2动力学的结果表明,当初始浓度为0.5 mg·L~(-1)时,磷去除在前10 h内便完成很大部分,推测其去除行为主要由表面吸附进行;当初始浓度为2.5 mg·L~(-1)时,磷去除主要是靠后期的磷沉淀方式来完成.3当初始磷浓度≤2.5 mg·L~(-1)时,反应时间设为10 h,磷的去除过程可用Langmuir等温吸附模型来较好地拟合,推测在该条件下,表面吸附是磷去除过程中的主导作用方式.4加入邻苯二甲酸的情况下,当初始磷浓度2.5 mg·L~(-1)时,磷的去除率下降了一些,这是因为此时磷去除主要通过表面吸附完成,而邻苯二甲酸与磷共同竞争表面上的吸附位点;当初始磷浓度2.5 mg·L~(-1)时,磷的去除率增大了一些,这是因为邻苯二甲酸的加入促进了钙浓度的增加,从而促进磷通过钙以沉淀的形式去除.     

新型材料磁性氧化锆的除氟效能

采用一步共沉淀法制备了磁铁矿纳米颗粒为核和水合氧化锆为壳的磁性氧化锆材料,研究了其除氟性能.结果表明,磁性氧化锆对氟的Langmuir最大吸附量为35. 46 mg·g~(-1),远高于磁铁矿、活性氧化铝和活性炭.磁性氧化锆对氟的吸附过程较快且吸附动力学数据符合准二级动力学模型,吸附过程为吸热反应.磁性氧化锆对氟的吸附量随pH升高而降低. Cl~-、NO_3~-和SO_4~(2-)的共存对磁性氧化锆除氟没有明显影响,而HCO_3~-和CO_3~(2-)明显抑制氟的吸附.磁性氧化锆吸附的氟可通过1mol·L~(-1)NaOH成功脱附,脱附率99. 5%～99. 6%.脱附后的磁性氧化锆经过再生处理可继续使用.磁性氧化锆对实际井水中的氟的去除效果低于纯水,但适当增加投加量仍可以达到饮用水标准对氟浓度的要求.磁性氧化锆制备简单、使用后可从水中磁分离从而可反复使用,因此是一种有较好应用前景的除氟材料.     

MgO改性莲蓬壳生物炭的制备及其磷吸附特性

为了研究生物炭作为磷吸附剂的潜在应用特性,本文通过将MgO与莲蓬壳混合物快速热解制备纳米MgO-生物炭吸附剂.采用XRD、BET、SEM和TEM对其理化特性进行表征,并进行了吸附实验.结果表明,MgO主要以薄片状和颗粒状的形态负载在炭表面,使吸附活性位点增加,MgO-生物炭MBC3吸附量是未负载MgO生物炭MBC1的14倍,热解通10%CO_2载气,MBC9的吸附量进一步增加为MBC1的16倍.准二级动力学能更好地描述吸附过程,磷酸根在MgO-生物炭上的吸附是以化学吸附为主导.MBC3和MBC9的Langmuir最大吸附量分别可达到283. 26 mg·g~(-1)和297. 96 mg·g~(-1). MgO-生物炭是一种高效的磷吸附剂,可用来治理水体富营养化问题.     

改性芦苇生物炭对水中低浓度磷的吸附特征

为吸附处理低浓度含磷废水和实现芦苇资源化利用,将湿地植物芦苇制备成生物炭,通过负载氯化铁进行改性,探究了改性芦苇生物炭对水体中磷的吸附特征.结果表明,改性后芦苇生物炭的含铁量为11.98 mg·g~(-1),是改性前的44.7倍;改性芦苇生物炭p H_(pzc)为7.49,当溶液p H为7.0时,吸附效果最好;在磷溶液浓度为4.0 mg·L~(-1)、温度为298K时,改性芦苇生物炭平衡吸附量为0.658 mg·g~(-1),是未改性生物炭吸附量的34.6倍.研究不同温度下的吸附等温线,Langmiur方程很好地拟合不同温度的吸附等温线,该吸附是单层吸附,温度升高有利于吸附.吸附热力学研究表明,ΔG~θ0、ΔH~θ0和ΔS~θ0,说明该吸附是自发、熵增的吸热过程.假二级方程很好地拟合改性芦苇生物炭吸附磷的动力学数据,初始吸附速率随初始浓度的增大而增大,该吸附主要受颗粒内扩散控制.该研究为改性芦苇生物炭用于污水处理厂和水体深度除磷提供基础数据.     

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.     

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.     

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.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.