石英砂负载氧化铁吸附除锑、磷的XRD、FTIR以及XPS研究

通过XRD、FTIR以及XPS方法研究了石英砂负载氧化铁(IOCS)吸附锑、磷的机理.研究结果表明,IOCS表面氧化铁的晶型为α-Fe2O3;OH-及Fe-O键可以在FTIR谱图上检测到.XPS测定结果表明,IOCS吸附锑过程中氧原子及铁原子发生了电子转移,而IOCS吸附磷的过程几乎没有发生电子转移.XPS的价带谱研究表明,IOCS与锑的结合强度大于IOCS与磷的结合强度.由于锑、磷的吸附,导致IOCS表面铁原子的浓度有所降低;XPS溅射结果表明,锑较磷更能与深层的氧化铁发生反应.     

涂铁砂吸附镉的动力学研究

研究了10℃,20℃,40℃的温度下,涂铁砂(Iron oxide coated sand,简称IOCS)对镉的吸附动力学。镉在IOCS表面的吸附可分为两个阶段,吸附反应的前60min为快速吸附阶段,60min后,吸附速率明显变慢。温度升高加快了镉在IOCS表面的吸附速率。用Elovich动力学模型,准一级反应模型,准二级反应模型,二级反应模型和粒内扩散动力学模型对实验数据进行回归分析,准二级反应模型能更好地描述镉在IOCS表面的吸附,各吸附模型的模拟优劣顺序为:准二级模型>二级模型>Elovich模型>准一级模型>粒内扩散模型。     

磺胺嘧啶在覆铁石英砂中迁移特征及数值模拟

为了探讨磺胺类抗生素在土壤中的迁移特征,以磺胺嘧啶（SDZ）为研究对象,以石英砂（QS）为介质,采用高温加热法制备覆铁石英砂（IOCS）,通过土柱出流实验,研究不同铁含量和离子强度对SDZ在IOCS中迁移的影响,并利用Hydrus-1D软件对结果进行模拟.土柱出流实验结果表明,随着IOCS表面铁含量增加,其表面粗糙度越大,且表面携带的正电荷越多,SDZ越容易吸附在IOCS表面,其相对浓度峰值越低,不利于SDZ的迁移;离子强度的增加,促进了SDZ在QS和IOCS中的迁移,这主要是受静电作用、表面络合作用和竞争吸附作用的控制.模拟结果显示,非平衡单点吸附模型（OSM）可以较好地模拟不同铁含量和离子强度下SDZ的迁移过程,拟合曲线与实测曲线几乎重合,R²>0.97,RMSE<0.032,拟合效果较好;反演所得吸附分配系数k_F随着铁含量的增加而增加,随离子强度的增加而减小;阻滞因子R_d与其呈现相同的变化趋势;吸附特征参数β>1,而一阶动力学速率常数α均较小.     

氧化铁改性沸石对Se(Ⅳ)的吸附性能及试验废物再利用研究

为解决天然沸石去除废水中Se（Ⅳ）能力低的问题,采用氯化铁对天然沸石进行改性,制备表面负载氧化铁的改性沸石,即氧化铁改性沸石,并将其应用于去除水体中Se（Ⅳ）.首先对比天然沸石和氧化铁改性沸石的结构特征,研究二者对Se（Ⅳ）溶液的吸附特性,并通过X射线荧光光谱（XRF）、X射线衍射图谱（XRD）、扫描电镜（SEM）和氮气吸附孔径分布测试（BET）对二者进行表征;其次进行吸附试验,考虑接触时间、pH、吸附剂投加量、初始溶液反应浓度的影响,并通过天然沸石和氧化铁改性沸石的吸附动力学及吸附等温线对吸附的机理进行阐述.结果表明:①氧化铁改性沸石表面形成细碎的球状颗粒,分布在沸石的表面.②氧化铁改性沸石能够高效地吸附水体中的Se（Ⅳ）,且在pH为3时吸附效率最高,其对Se（Ⅳ）溶液的去除率最高达97.7%,其理论最大吸附量为46.901 mg/g.③氧化铁改性沸石对Se（Ⅳ）的吸附过程符合准二级动力学模型和Langmuir等温吸附模型.④添加负载Se（Ⅳ）后的氧化铁改性沸石土壤均达到富硒土壤标准（>0.4 mg/kg）.研究显示,氧化铁改性沸石吸附Se（Ⅳ）的效果较好,显著优于天然沸石的吸附效果,且吸附Se（Ⅳ）废水后的废弃氧化铁改性沸石还可应用于土壤改良方向.      

焙烧温度对铁覆膜砂IOCS吸附Cr(VI)的影响

采用序批试验研究了焙烧温度对铁覆膜砂(Iron Oxide Coated Sand,IOGS)吸附6价铬Cr(VI)的吸附平衡和吸附速率的影响.结果表明,铬在IOCS上的吸附平衡符合Langmuir吸附模型.低温制备IOCS具有较高吸附容量且对pH不敏感.110℃制备IOGS在pH 7的最大吸附容量(0.181 mg·g-1)远高于660℃制备10CS(0.023 m8·8-1).吸附过程符合准二级动力学模型.吸附速率随焙烧温度提高而下降.     

环丙沙星在潮土中的吸附特性

为了探明环丙沙星在潮土中的吸附特性,采用静态吸附试验,研究了环丙沙星在潮土中的吸附动力学、等温吸附特性以及pH值对其吸附过程的影响.结果表明,环丙沙星在潮土中的吸附过程可分为快速吸附和慢速平衡2个阶段.整个吸附过程符合二级反应动力学方程,吸附常数为1.138×10-3～2.849×10-2kg.(min.mg)-1.环丙沙星的吸附等温线能够较好地符合Freundlich方程和Langmuir方程,其中Freundlich方程的拟合效果更佳,吸附容量(lgKf)为2.725.研究发现,在pH值为4～9条件下,环丙沙星的吸附参数对数值lgKd呈随pH的增加先增加后降低的趋势,当pH值为5时,潮土对环丙沙星的吸附效果最好,lgKd为3.11,强酸性和碱性条件均不利于潮土对环丙沙星的吸附.由此推断阳离子吸附可能是潮土对环丙沙星吸附的重要机制之一.     

水合氧化铁对废水中磷酸根的吸附-解吸性能研究

以FeCl₃为原料制备水合氧化铁吸附剂,研究其对废水中磷酸根的吸附-解吸性能.结果表明,随着溶液pH的降低,水合氧化铁对磷酸根的吸附能力不断提高,其吸附动力学曲线符合二级动力学模型,吸附等温线符合Langmuir吸附模型.被吸附的磷酸根在50 g/L的NaOH溶液中进行解吸,解吸率>98%.解吸率与单位水合氧化铁的吸附饱和程度没有相关性.利用水合氧化铁对城市某污水处理厂污泥浓缩池上清液进行磷的吸附和解吸实验,结果表明该工艺对磷的回收率>90%.根据实验结果设计了城市污水中磷去除和回收工艺流程,该流程包括：吸附过程、解吸再生过程、富磷解吸液中磷回收等过程.     

磁性硅藻土负载纳米过氧化钙对水中磷酸盐吸附

本研究以磁性硅藻土为载体,负载纳米过氧化钙(CaO_2),制备了一种可高效吸附磷酸盐且可回收的复合材料(MDCP),并利用SEM、EDX-mapping、XRD、XDS和VSM等技术对MDCP的微观形貌、内部结构、晶体组成以及元素组成进行了表征.结果表明,MDCP表面成功负载了CaO_2,并具有良好的磁性. MDCP对水中磷酸盐的吸附数据符合Langmuir等温吸附模型,根据Langmuir模型确定当T=20℃时MDCP对水中磷酸盐的最大单位吸附容量为191. 84 mg·g~(-1).吸附等温线与吸附动力学的结果表明,MDCP对磷酸盐的吸附过程属于化学吸附. pH对MDCP吸附磷酸盐具有显著的影响,MDCP对磷酸盐的有效吸附pH范围为4～10,且MDCP对溶液pH具有调节效果,可使溶液pH保持在7～9的水平.当溶液共存Cl-、SO_4~(2-)、CO3_~(2-)、HCO_3~(2-)、F-和NO_3~-等阴离子时,MDCP对水中磷酸盐仍具有良好的选择吸附性.回收后的MDCP可用HCl溶液对其吸附的磷酸盐进行解吸,解吸后的MDCP再次负载CaO_2后对磷酸盐去除率仍可达到初次吸附量的70%.     

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...     

Zn系LDHs负载改性石英砂和沸石对Cr(Ⅵ)吸附效果对比及其作用机理研究

为提升人工湿地常用填料对受污染水体中Cr(VI)的吸附性能,采用水热-共沉淀法在碱性条件下制备了Zn系LDHs涂层负载改性沸石和石英砂填料,并运用场发射扫描电子显微镜(SEM)、能谱分析仪(EDS)和BET等手段对改性前后填料的表面形态和化学成分进行了表征.最后,通过等温吸附试验、动力学吸附试验、吸附热力学试验对Zn系LDHs改性填料和天然填料的Cr(VI)吸附效果及其作用机理进行了对比研究.结果表明,通过Zn系LDHs涂层负载,沸石和石英砂对Cr(VI)的吸附类型由以物理吸附为主的多分子层吸附向以化学吸附为主的单分子层吸附转换,有利于吸附水中的Cr(VI);热力学相关参数ΔS~00,ΔG~00,ΔH~00,表明对Cr(VI)的吸附是自发放热过程.相比于天然沸石和石英砂,Zn系LDHs负载改性沸石和石英砂的表面物化性状发生明显变化,最大饱和吸附容量明显提高,尤其是石英砂的最大饱和吸附容量从21 mg·kg~(-1)提升到125 mg·kg~(-1).改性同种天然填料时,ZnAl-LDHs负载改性的效果更佳;而相对于天然沸石的改性,Zn系LDHs负载改性能更有效地提高石英砂对Cr(VI)的吸附能力.因此,本实验中ZnAl-LDHs负载改性石英砂可推荐用于实际人工湿地中Cr(VI)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.     

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.     

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.     

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.     

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

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Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.