还原氧化石墨烯支撑纳米零价铁对含Sb(Ⅲ)废水的处理

针对含重金属Sb(III)废水处理问题,采用液相还原法制备出高效的还原氧化石墨烯负载纳米零价铁(nZVI/rGO)复合吸附材料,并采用多种技术手段对所制备的nZVI/rGO复合材料进行表征.同时,复合材料中nZVI的负载量、吸附剂投加量、初始pH值以及反应温度等因素对废水中Sb(Ⅲ)吸附去除效果的影响被全面考察,并进一步对吸附过程进行吸附等温线和吸附动力学拟合.结果表明,在25℃,pH为3.0时,当nZVI负载量为70wt%,nZVI/rGO投加量为0.5g/L时,Sb(Ⅲ)的去除率最高,140min内可达99.7%.该吸附过程符合准二级动力学模型与Langmuir等温吸附模型,因此nZVI/rGO被证实是一种高效的Sb(III)吸附材料.     

硫化零价铁的制备及去除头孢噻肟机理研究

采用后置硫化法制备了硫化纳米零价铁(S-nZVI),并采用X射线光电子能谱(XPS)、X射线衍射(XRD)和透射电镜(TEM)等方法表征了材料表面形貌及元素化学形态等特性.同时,以头孢噻肟为目标污染物,考察了S-nZVI对其去除效率及去除机理等.结果表明,S-nZVI颗粒呈球形,平均粒径为56 nm,材料表面形成一层不连续的低密度FeS/FeSn.硫化率、Fe~(2+)和溶液p H均能影响S-nZVI对头孢噻肟的去除.S/Fe=1/4(质量比),S-nZVI投加量为0.5 g·L~(-1),溶液pH为8时,120 min内头孢噻肟的去除率为82.2%,远大于nZVI的去除率(23.4%).最后,采用液相色谱-电喷雾质谱分析了头孢噻肟的降解产物,发现头孢噻肟的降解主要是由酯基取代反应和内酰胺键的开环反应引起的.     

羟胺强化亚铁活化过硫酸盐降解对乙酰氨基酚的研究

采用羟胺(HA)强化Fe~(2+)/过硫酸盐(PS)体系降解对乙酰氨基酚(ACT),考察了Fe~(2+)、PS、HA投加浓度以及反应初始pH值对ACT降解效果的影响.结果表明,在反应时间为30 min,亚铁浓度为0.05 mmol·L~(-1), PS浓度为0.8 mmol·L~(-1)和初始pH为3.0的条件下,0.5 mmol·L~(-1) HA可将ACT的去除率从13%提高到90%.适量增加Fe~(2+)或HA浓度可以提高ACT的降解率,但是过高的Fe~(2+)和HA浓度会抑制ACT的降解.ACT的降解率随着PS浓度升高而提升,当PS浓度达到1.2 mmol·L~(-1)时,30 min内ACT几乎可以完全降解.ACT的降解效果随着pH的升高而降低.EPR实验表明Fe~(2+)/PS/HA体系中主要的自由基是SO■和HO~·.Na_2SO_3、NaNO_2和Na_2S_2O_3等常见的还原剂均能够强化Fe~(2+)/PS体系对ACT的降解效果,但是其对Fe~(2+)/PS体系的强化效果均比HA低.     

沸石负载纳米零价铁去除水中Sb(Ⅲ)和Sb(Ⅴ)的研究

锑矿开采和含锑化合物的应用在一定程度上会造成环境锑污染的加重,对人体健康和生态系统带来风险,为缓解这一现象,采用液相还原负载的方式制备沸石负载纳米零价铁(Z-ZVI)复合材料,探究其对Sb(Ⅲ)和Sb(Ⅴ)的去除效果;采用扫描电子显微镜(SEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)对反应前后复合材料进行表征,并探究不同材料配比、溶液初始pH及无机阴离子对Sb(Ⅲ)和Sb(Ⅴ)吸附效率的影响.结果表明：(1)沸石负载后的纳米零价铁(Z-ZVI)具有较高的比表面积(54.54 m²/g)和反应活性,能够有效吸附、还原高价锑.(2)在pH=7、1.0 g/L Z-ZVI的条件下,反应4 h对20 mg/L Sb(Ⅲ)和Sb(Ⅴ)的吸附率分别达到88%和62%,吸附过程符合准二级动力学方程和Freundlich等温吸附模型.(3)Sb(Ⅲ)的去除率受pH变化的影响不大,但Sb(Ⅴ)的去除率随初始pH的升高而下降,溶液反应终点pH相比初始pH均有所上升.(4)XRD和XPS表征发现,Sb的去除过程中同时存在吸附和还原作用,Fe⁰氧化过程中...     

超声/Fe0/EDTA体系对印染污泥中多环芳烃的降解

Fe~0/EDTA类芬顿体系能产生氧化能力极强的羟基自由基(·OH),已被广泛应用于有机污染物的去除.提高·OH的生成速率和浓度是高效降解有机污染物的关键.因此,本文利用超声/Fe~0/EDTA体系处理印染污泥,探讨了不同反应参数对体系中产生·OH的影响,考察了该体系对印染污泥中多环芳烃(PAHs)的去除效果.结果表明,在pH为3.0,超声功率为540 W,Fe~0投加量为15 g·L~(-1),EDTA浓度为2.0 mmol·L~(-1)的最佳条件下,·OH浓度高达862μmol·L~(-1).印染污泥中的铁絮凝剂可作为超声/Fe~0/EDTA体系中Fe~(2+)和Fe~(3+)的来源,促使该体系循环产生H_2O_2和·OH.超声/Fe~0/EDTA体系产生的·OH能快速有效地降解印染污泥中的PAHs,∑_(16)PAHs的平均去除率达到77%,同时有机质含量下降了10.1%.     

天然黄铁矿吸附去除水中Sb(Ⅴ):性能与机制

比较了3种铁矿石(黄铁矿、赤铁矿和磁铁矿)对于五价锑[Sb(Ⅴ)]的吸附效果,选用效果最好的黄铁矿作为Sb(Ⅴ)的吸附剂,考察了黄铁矿粒径、投加量和pH对吸附效果的影响.结果表明,当Sb(Ⅴ)初始浓度在90～100μg·L~(-1)时,黄铁矿粒径200M(过200目筛,0.074 mm)、投加量1 g·L~(-1)和pH=7时吸附效果最好,对Sb(Ⅴ)的去除率在80%以上;离子竞争实验结果表明,PO_4~(3-)对吸附Sb(Ⅴ)有抑制作用,而SO_4~(2-)和CO_3~(2-)对吸附Sb(Ⅴ)无明显不利影响,这可能是因为PO_4~(3-)会与Sb(Ⅴ)竞争黄铁矿表面的活性配位吸附点;准二级动力学模型和Langmuir模型能更好地模拟吸附过程,表明吸附过程是单层吸附行为,主要作用是化学吸附;红外分析表明黄铁矿对Sb(Ⅴ)的去除过程是配位离子交换反应; EDS与XPS数据证实锑被吸附到黄铁矿表面,并且没有被还原成毒性更高的三价锑[Sb(Ⅲ)].     

类芬顿调理污泥用于微生物电解池产氢与磷回收的研究

为提高微生物电解池(MEC)利用剩余污泥产氢气和磷回收的效率,采用Fe~(3+)、原儿茶酸(PCA)和H_2O_2体系预调理污泥,探究中性PCA/Fe~(3+)/H_2O_2体系的试剂投加量对污泥液相总磷含量和溶解性化学需氧量(SCOD)的影响.在单因素试验的基础上,通过表面响应法(RSM)优化得到Fe~(3+)和H_2O_2投加量分别为12.96 mmol·L~(-1)和0.45 mol·L~(-1),液相总磷含量和SCOD含量实际值分别为(60.14±0.08) mg·L~(-1)和(3357.67±66.37) mg·L~(-1),模拟效果显著.与未处理的剩余污泥MEC反应器出水相比,经过调理后的剩余污泥MEC反应器出水中的总化学需氧量(TCOD)、多糖和蛋白质的去除率分别提高了30.03%、50.16%和97.31%,氢气转化率提升了1.31倍,有效提升了MEC产氢效率.通过鸟粪石结晶回收MEC污泥上清液中的磷,发现在初始pH值为10、Mg~(2+)浓度为0.056 mol·L~(-1)和NH~+_4浓度为0.08 mol·L~(-1)时效果最佳.鸟粪石晶体质量浓度最高可达7.6 g·L~(-1),晶体纯度最大为88.30%,上清液中77.55%的磷以鸟粪石的形式得到回收.在本研究最优化条件下进行中性PCA/Fe~(3+)/H_2O_2体系调理剩余污泥微生物电解池产氢与磷回收全过程中产出经济价值达到2.36元.实验研究最终表明,经过Fe~(3+)/PCA/H_2O_2体系调理污泥可促进污泥中磷的释放和MEC处理污泥的产氢效率,为探究污泥资源化提供了新的研究思路.     

零价纳米铁吸附去除水中六价铬的研究

利用液相还原法制备的零价纳米铁(nZVI)进行了去除水中Cr(Ⅵ)的实验研究.结果表明,nZVI对Cr的去除效果明显优于还原铁粉和粉末活性碳;pH值越小、初始Cr浓度越低、nZVI放置时间越短及投加量越大均有利于水中Cr(Ⅵ)的去除,最佳去除率近100%;反应动力学拟合结果表明,nZVI去除六价铬符合准二级动力学模型;反应后nZVI颗粒的扫描电镜及电子能谱结果显示Cr占12.02%(wt),结合对反应溶液中Cr(Ⅵ)和Cr(Ⅲ)分析,说明吸附、还原与共沉淀可能是nZVI去除水中六价铬的主要机理.     

TiO2/膨润土复合材料对Hg2+的吸附性能研究

利用纳米TiO_2对膨润土进行复合改性,制备TiO_2/膨润土复合材料.采用电镜扫描、X-射线衍射表征改性前后膨润土的结构和形貌.通过室内模拟实验,以膨润土为对照,研究不同添加量、pH、吸附时间及初始Hg~(2+)浓度等条件下,TiO_2/膨润土复合材料对Hg~(2+)的吸附特性与性能,同时通过正交试验,探究TiO_2/膨润土复合材料吸附Hg~(2+)的最优条件.结果表明,改性后的膨润土颗粒明显变小,且颗粒疏松多空孔,层间距增大.相比于膨润土,TiO_2/膨润土复合材料吸附性能得到极大提高.TiO_2/膨润土复合材料对Hg~(2+)的吸附率均随着添加量、pH、吸附时间的增大而增大,添加量为1.5 g·L~(-1)、pH为7.0、吸附时间为120 min时,吸附率达98.0%以上.但TiO_2/膨润土复合材料对Hg~(2+)的吸附率随着初始Hg~(2+)浓度的增大而减小.通过4种动力学模型拟合发现,吸附过程符合假二级动力学方程,吸附以化学吸附为主.吸附等温线更符合Langmuir等温方程,属于典型的单分子层吸附,最大吸附量为20.66 mg·g-1.吸附Hg~(2+)的最优实验条件:添加量为2.0 g·L~(-1),pH为8.0,初始Hg~(2+)浓度为45 mg·L~(-1),吸附时间为16 h,此时吸附率99.9%,平衡浓度为0.034 mg·L~(-1).     

鸟粪石-沸石复合材料对水中镉的吸附性能研究

研究以氧化镁负载沸石回收污水中氮磷得到的鸟粪石-沸石复合材料(STR-NZ)为吸附剂,用于对水体中重金属镉的吸附去除.实验采用SEM-EDS、XRD和FTIR等手段对STR-NZ材料进行表征,并考察了投加量、初始pH和反应时间等对STR-NZ材料去除水中Cd~(2+)的影响.结果表明:氧化镁负载沸石材料主要以鸟粪石沉淀的方式实现对水中磷酸盐和氨氮的回收;STR-NZ对水溶液中Cd~(2+)的吸附量随pH的增大呈先增加后趋于平衡的趋势,当Cd~(2+)的初始浓度为50 mg·L~(-1)时,STR-NZ的最佳投加量为0.2 g·L~(-1),Cd~(2+)最大吸附量为249.35 mg·g~(-1), STR-NZ对Cd~(2+)的吸附动力学符合准二级动力学模型,对Cd~(2+)的等温吸附符合Langmuir等温吸附模型,STR-NZ主要通过Cd_5(PO_4)_3(OH)沉淀的方式实现对水中Cd~(2+)的去除.     

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.     

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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