垂直流人工湿地不同填料长期运行效果研究

在高水力负荷(2400~3400mm/d)条件下,以沸石、无烟煤、页岩、蛭石、陶瓷滤料、砾石、钢渣和生物陶粒为填料,进行垂直流人工湿地模拟柱净化污水实验(历时25个月).结果表明,随着系统的运行,各填料对COD的去除能力均有不同程度提高.沸石对污水中氮素的处理能力保持在较高的水平,对TN和NH4+-N的平均去除率分别高达82.03%和91.32%.钢渣对TP和可溶性反应磷(SRP)的平均去除率分别高达89.61%和96.77%,且净化效果稳定;无烟煤第2阶段对磷素的净化能力低于钢渣,之后与钢渣无显著性差异.在垂直流人工湿地中,针对水质特性选择长期高效的填料,如沸石、无烟煤和生物陶粒,在高水力负荷条件下可获得更好的处理效果.     

人工湿地不同基质和粒径对污水净化效果的比较

为研究人工湿地基质类型和粒径对水质净化效率的影响,选择了1~2、2~4、4~8 mm的沸石,2~4、4~8、8~16mm的砾石和2~4、3~5、6~8 mm的无烟煤基质,在无植物人工实验柱中开展单一基质的水质净化实验.结果表明,相同类型不同粒径的基质对COD、TN、TP的去除效果不同.4~8 mm沸石和砾石、6~8 mm无烟煤对COD的去除率最高,分别为53.74%、60.76%、62.93%;人工实验柱中氮素的去除以反硝化作用为主,粒径对TN去除效果的影响表现为小粒径更优;砾石和无烟煤的TP去除率也表现为小粒径更高,但沸石的TP去除率随着粒径的增大而增大.基质类型对COD、TP、TN的去除效果也存在差异.无烟煤对COD、TP、TN均有较好的去除效果,平均去除率在60%以上;沸石对TN的去除效果最好,TP去除率不高;砾石对COD有较高的去除率,对TP的去除效果一般.     

垂直流人工湿地MgFe-LDHs覆膜改性基质净化效果研究

选取生物陶粒、无烟煤、沸石3种垂直流人工湿地常用基质,采用金属摩尔比(M2+ : M3+)为2:1的MgCl2溶液和FeCl3溶液在碱性条件下共沉淀即时生成MgFe-LDHs,并将其覆膜于所选3种垂直流人工湿地基质表面;构建模拟基质试验柱,对改性前后的6种基质进行垂直流人工湿地模拟柱净化受污染湖水的小试试验,并进行对比分析.结果表明:该种针对垂直流人工湿地典型基质的MgFe-LDHs覆膜改性方式可行;改性后的3种基质对CODCr、氨氮、总磷的净化效果均有不同程度的提高;其中,无烟煤基质的覆膜改性性能最优,改性后的无烟煤基质对CODCr、氨氮、总磷的平均去除率分别超过了80%、60%和90%.     

人工湿地常用生物陶粒基质LDHs覆膜改性及其除磷效果研究

分别利用3种二价金属化合物和3种三价金属化合物,采用水热共沉淀法在碱性条件下对人工湿地中常用的生物陶粒基质进行层状双金属氢氧化物(LDHs)覆膜改性,并将9种不同类型的LDHs覆膜改性生物陶粒基质和普通生物陶粒基质分别填充于10个垂直流人工湿地模拟实验柱中,进行除磷净化实验.结果表明,9种不同类型的改性生物陶粒基质均能有效提高磷素的净化效果;Zn系LDHs改性生物陶粒对总磷、溶解性总磷、磷酸盐均有很好的处理效果,其中Zn Fe-LDHs、Zn Co-LDHs和Zn Al-LDHs对总磷的平均去除率均在92%以上,对溶解性总磷和磷酸盐的平均去除率均超过95%;其对磷素的净化机理主要集中于物理化学作用,同时还应与其对微生物生长的促进作用有关.     

常见基质对暴雨径流中磷素去除效果的比较研究

选取沙子、土壤、沸石、白矾石、陶粒、钢渣、石灰石、蛭石和碎石9种常见的基质,通过吸附和解吸实验、静态吸附实验和动态模拟实验,较为系统地研究了这些基质的吸附特性以及去除暴雨径流中低浓度磷素污染物的特性,并分析了影响基质去除磷素的影响因子.结果表明,9种供试基质对磷酸盐的动态去除效率要比其他形态磷高,对磷素的平衡吸附量大小顺序为：沸石、土壤、蛭石 ＞陶粒、钢渣、石灰石 ＞碎石、沙子、白矾石,对磷素的动态吸附能力为：沸石、石灰石、白矾石、土壤＞钢渣、碎石、沙子＞陶粒、蛭石.另外,蛭石、陶粒和钢渣在对暴雨径流中磷素的静态和动态吸附过程中出现了磷释放现象,其它基质对磷酸盐的动态吸附能力较强,去除率介于30%～87%.综合分析以上多种因素,为了去除暴雨径流中的低浓度磷素,沸石、石灰石和土壤是比较理想的工程基质材料.     

层状双金属氢氧化物覆膜改性人工湿地无烟煤基质除磷

分别选取MgCl2、ZnCl2、CaCl2、CoCl3、FeCl3、AlCl3等6种金属化合物合成9种不同类型层状双金属氢氧化物(LDHs),利用其对垂直流人工湿地无烟煤基质进行LDHs覆膜改性;构建模拟基质试验柱,对改性前后的无烟煤基质进行模拟垂直流人工湿地净化污水试验.结果表明:相对于原始无烟煤基质,各种LDHs覆膜改性基质对总磷、溶解性总磷、颗粒态磷和磷酸盐的去除率均有不同程度的提高;Zn2+参与合成的改性基质对总磷、溶解性总磷、颗粒态磷和磷酸盐均有很好的去除效果,其中ZnCo-LDHs和ZnAl-LDHs改性基质对总磷和溶解性总磷的平均去除率超过95%,对磷酸盐平均去除率达到98%以上.     

人工浮岛基质对富营养水的修复作用研究

实验选取页岩陶粒、活性炭、膨胀蛭石为生态浮岛的填充基质,以空心菜为植物组建了三组浮岛进行平行实验,比较了三种不同基质在同一条件下对水中总氮、总磷、COD的吸附净化效果。结果表明植物在以页岩陶粒为基质的人工浮岛中生长最好,对于TN的去除效果,活性炭和膨胀蛭石均可达60%以上,页岩陶粒的去除率最高为53%;对TP和COD的去除能力大小顺序为:活性炭(均达75%左右)>页岩陶粒>膨胀蛭石。可见活性炭的截污能力更强,而页岩陶粒的性价比较高。     

人工湿地系统中填充基质对磷的吸附能力

人工湿地中填充基质对磷的吸附、沉淀作用是湿地系统的主要除磷机制,探明基质对磷的吸附能力对人工湿地系统设计至关重要. 分别利用吸附试验和柱吸附试验考察了宝钢钢渣、首钢钢渣、水淬渣和陶粒4种基质对磷的吸附能力,同时进行了浸出液毒性鉴别试验. 吸附试验表明,基质对磷的吸附符合Langmuir和Freundlich模型(R2为0.956～0.989),采用Langmuir模型预测的基质磷吸附量为2.274～3.637 mg/g. 在为期144 d的柱吸附试验中,填充宝钢钢渣和首钢钢渣的试验柱对磷有良好的去除效果,而填充水淬渣和陶粒的试验柱在90 d左右达到吸附饱和状态.在试验期内,基质的累积磷吸附量:宝钢钢渣为7.921 mg/g,首钢钢渣为7.495 mg/g,水淬渣3.317mg/g,陶粒为1.627 mg/g. 浸出液毒性鉴别试验表明,4种基质均有较高的环境安全性,由于2种钢渣和水淬渣具有较高的磷去除效率和便宜的价格,在湿地系统中具有广泛的应用价值.      

7种人工湿地填料对磷的吸附特性比较

研究了活性炭、牡蛎壳、蛭石、火山岩、煤渣、钢渣和河砂7种人工湿地填料对模拟废水中磷的去除效果。各材料对磷去除率大小为:钢渣>煤渣>牡蛎壳>活性炭>(沸石、火山岩、河砂)。同时对比研究了7种材料对实际生活废水中磷的去除效果,各材料对实际废水中磷的去除率低于对模拟废水中磷的去除率,其中钢渣的去除率最高。7种材料对模拟废水中磷的去除过程均符合准二级动力学关系。选择钢渣、煤渣和牡蛎壳作为人工湿地备选填料,研究不同初始磷浓度、不同粒径下钢渣、煤渣和牡蛎壳对磷去除效果,结果表明,钢渣、煤渣和牡蛎壳对磷的去除率随初始磷浓度和材料粒径的增大而减小。     

不同合成条件对ZnAl-LDHs覆膜改性生物陶粒除磷效果的影响

采用3种Zn~(2+)/Al~(.+)金属浓度比的ZnCl_2和AlCl_3溶液,在两个不同pH值条件下,利用水热-共沉淀法对生物陶粒基质进行层状双金属氢氧化物(LDHs)覆膜改性.将生成的不同类型ZnAl-LDHs覆膜改性基质与原始生物陶粒基质分别填充于实验柱中,构建模拟垂直流人工湿地小试系统;对改性前后的7种基质进行磷素净化效果、等温吸附实验和解吸附实验研究,通过实验数据结合主成分分析,探讨ZnAl-LDHs覆膜改性生物陶粒除磷效果提升的影响因素.结果表明,pH=11的ZnAl-LDHs改性方式对磷素净化效果具有更为明显的提升功能;其中ZnAl-LDHs(pH=11,1∶1)改性生物陶粒基质相比于原始基质,对TP、TDP、SRP平均去除率的增幅超过70%,其最大理论吸附量达到原始生物陶粒的3倍.合成ZnAl-LDHs时的pH值和Zn~(2+)/Al~(3+)金属浓度比对改性生物陶粒的结构形态与覆膜效果有着不同程度的影响,其中合成时的pH值是ZnAlLDHs覆膜改性生物陶粒除磷效果的主要影响因素.通过合理调控制备ZnAl-LDHs覆膜改性生物陶粒时的pH值及Zn~(2+)/Al~(3+)金属浓度比,可以达到有效提高ZnAl-LDHs覆膜改性生物陶粒除磷效果的目的.     

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.