改性污泥基生物炭的性质与重金属吸附效果

为提高污泥基生物炭在高钙溶液体系中对重金属阳离子的吸附能力,将Fe₂O₃、MnO₂、ZnO与市政污泥以质量比1 ∶10（以过渡金属元素质量计）混合共热解,制备改性生物炭;表征改性生物炭的组成、官能团分布和表面性质,考察其对典型重金属阳离子Cd²⁺的吸附效果.过渡金属氧化物可促进污泥的热解,改性生物炭的H/C原子比均低于0.31,碳链裂解脱氢更彻底.改性生物炭中Fe、Mn保留较好,分别主要以单质和氧化物形态存在;而Zn流失较多.改性生物炭中的孔隙以介孔为主,平均孔径约3.8 nm,比表面积在50 m²·g^-1以上.初始浓度约200 mg·L^-1的Cd²⁺溶液中,Ca²⁺初始浓度从0 mg·L^-1升高到约200 mg·L^-1,Fe改性生物炭对Cd²⁺的吸附容量从43.17 mg·g^-1降至27.88 mg·g^-1,但仍较未改性生物炭高10 mg·g^-1以上,在含钙溶液体系中表现出了对Cd²⁺更强的吸附性能.Fe₂O₃较MnO₂和ZnO对市政污泥基生物炭吸附重金属的强化效果更好.     

低温地下水净化工艺中氨氮去除性能及机制

在东北某自来水厂,以中试滤柱开展了低温（5~6℃）高铁锰氨[Fe（Ⅱ）11.9~14.8 mg·L^-1、Mn（Ⅱ）1.1~1.5 mg·L^-1和NH₄⁺-N 1.1~3.2 mg·L^-1]净化工艺实验,以探究氨氮去除途径与生物滤柱的除氨性能.结果表明,滤柱在启动初期就对氨氮具有良好的去除效果,通过理论分析与实验验证可知,TN_loss是由铁氧化物对氨氮吸附造成,氨氮转化为硝氮的过程是生物硝化作用.氨氮质量浓度提高过程中,由于吸附位点有限,铁氧化物对氨氮的吸附量稳定在1 mg·L^-1左右,氨氮氧化去除量不断增加,其中在滤柱上部滤层的去除量远大于下部滤层,DO是限制氨氮氧化去除量进一步增加的限制因素.滤速提升过程中,铁氧化物对氨氮吸附时间缩短,吸附量有所减少,空床接触时间（empty bed contact time,EBCT）缩短,使得单位体积滤料中硝化菌硝化去除的氨氮减少,需要增加滤层厚度以提升氨氮去除效果.     

过氧化钙重塑底泥对水中磷酸盐的吸附作用

本研究模拟原位覆盖CaO₂流失后状态,以修复后表层2cm底泥为研究对象,通过扫描电子显微镜（SEM）和X射线能谱仪（EDX）对底泥修复前后表面进行观察和元素分析,发现CaO₂重塑明显改变了底泥结构,去除底泥表面附着的大部分有机物和铁锰氧化物,提高底泥颗粒孔隙率,增加底泥表面Ca²⁺含量;CaO₂重塑使底泥内源磷更加稳定,TP含量减少约20%,潜在活性磷含量减少约30%,Ca-P和Res-P含量明显增加,同时厌氧环境下重塑底泥磷释放量明显小于原始底泥,表明CaO₂重塑极大降低了底泥内源磷释放风险;Langmuir模型与Freundlich和Dubinin-Radushkevich模型相比,更适用于描述CaO₂重塑底泥对水中磷酸盐的等温吸附行为,CaO₂重塑明显提高底泥对水中磷酸盐的吸附能力,其最大磷吸附量由1.44 mg·g^-1增加到20.91 mg·g^-1,其对水中磷酸盐的吸附机制由化学吸附转变为物理化学吸附共同作用,此外准二级动力学模型可以较好地描述CaO₂重塑底泥对水中磷酸盐的吸附动力学过程,且CaO₂重塑显著提高底泥对水中的磷酸盐的吸附速率.     

多孔不锈钢基氧化铝膜去除水溶液中的Cr(VI)和Cd(II)

通过悬浮粒子浸涂法将合成的γ-Al₂O₃纳米粒子固载于316L多孔不锈钢表面以吸附水溶液中的Cr（VI）和Cd（Ⅱ）.扫描电镜（SEM）和X射线衍射（XRD）测试结果表明,γ相的Al₂O₃纳米粒子均匀地涂在了316L多孔不锈钢基体上,膜体表面沉积厚度约为20 μm.该膜对单一Cr（VI）和Cd（Ⅱ）吸附的最佳pH分别为3.0~4.0和8.0~9.0,吸附均符合动力学准二级模型和Langmuir吸附等温模型,最大吸附量分别为0.603 mg·g^-1和0.399 mg·g^-1.本研究可为水体中的高毒性重金属Cr（VI）和Cd（Ⅱ）去除提供一定的理论和技术参考.     

镁改性硅藻土回收废水氮磷产物对水中Pb2+和Zn2+的去除

通过使用镁改性硅藻土回收废水中的氮磷营养素,优化制备了一种复合材料（D-MAP）,并将其用于废水中重金属Pb²⁺和Zn²⁺的去除.研究探讨了材料投加量、反应时间、反应温度和溶液初始pH等因素对Pb²⁺和Zn²⁺在D-MAP上吸附的影响.D-MAP吸附去除Pb²⁺和Zn²⁺的最优条件为：D-MAP投加量分别为0.25 g·L^-1和0.30 g·L^-1,Pb²⁺和Zn²⁺初始浓度分别为300 mg·L^-1和60 mg·L^-1,溶液初始pH为5.0.在此条件下,其对Pb²⁺和Zn²⁺去除率分别可达78.67%和89.66%.动力学和热力学的结果表明,D-MAP对Pb²⁺和Zn²⁺的吸附更符合准二级动力学模型;其吸附等温线可用Langmuir模型描述,吸附是自发吸热的过程.Langmuir等温拟合结果指出,D-MAP对Pb²⁺和Zn²⁺的最大吸附容量分别为901.0 mg·g^-1和206.2 mg·g^-1.使用SEM/EDS、XRD和FT-IR等手段对吸附Pb²⁺和Zn²⁺前后的吸附剂进行表征,结果表明,D-MAP是一种鸟粪石-硅藻土复合材料,可通过与Pb²⁺和Zn²⁺生成Pb₁₀（PO₄）₆（OH）₂和Zn₃（PO₄）₂·2H₂ O去除废水中Pb²⁺和Zn²⁺.D-MAP对Pb²⁺和Zn²⁺的去除效果随着pH的增加而增加,且最终产物形态随pH不同产生变化.     

镧负载沸石壳聚糖复合吸附剂高效除磷性能研究

本研究制备合成一种新型可高效除磷的镧负载复合吸附剂材料（La-MZ/CTS）,考察了材料的表面特性以及投加量、初始溶液pH、共存阴离子等因素对除磷效果的影响.SEM、BET和EDS分析说明负载镧后,材料表面均匀覆盖了La（OH）₃并且表现出较大的孔径和比表面积,分别为16.681 nm、32.342 m²·g^-1.材料对磷酸根的最大吸附量可以达到27.9 mg·g^-1,与负载前的材料相比提高了近10倍.在pH为6时,La-MZ/CTS的吸附性能最佳.溶液中共存F^-和CO₃^2-会抑制该材料除磷效果,材料对于磷的吸附容量分别下降8.9%和16.3%.该材料吸附动力学过程符合准二级动力学模型,吸附等温线拟合结果表明Freundlich拟合方程能较好地描述其对磷酸盐的吸附过程,表明材料的吸附过程为多分子层化学吸附.此外,镧在整个吸附反应过程中的溶出量低于ICP检测限,进一步表明La-MZ/CTS是一种稳定性较好的高效除磷吸附剂.     

高炉水渣负载硫化纳米零价铁对水中土霉素的去除

利用液相还原法制备了一种高炉水渣负载硫化纳米零价铁（S-nZVI@BFS）材料,并将其用于废水中土霉素（OTC）的去除.本研究通过SEM、XRD和BET等手段分析了S-nZVI@BFS的表面结构特征,探讨了反应时间、OTC初始浓度、溶液初始pH和共存六价铬［Cr（Ⅵ）］等对其去除OTC的影响.结果表明,S-nZVI@BFS表面均匀负载了硫化纳米零价铁（S-nZVI）,S-nZVI@BFS的比表面积和孔容分别为141.986 m²·g^-1和0.388 cm³·g^-1.S-nZVI@BFS表面活性点位的利用率随OTC初始浓度的增加而显著提高,当OTC初始浓度从10 mg·L^-1增加到100 mg·L^-1时,S-nZVI@BFS对OTC的去除量从20.12 mg·g^-1增加到202.74 mg·g^-1.S-nZVI的等电点为7.2,较低pH有利于S-nZVI@BFS对OTC的去除,当pH从3增加至11时,S-nZVI@BFS对OTC的去除量从99.78 mg·g^-1降低至41.12 mg·g^-1,降解机制由Fendon氧化和络合沉淀作用向静电吸附转移.Cr（Ⅵ）与OTC在S-nZVI@BFS去除体系中存在明显竞争关系,Cr（Ⅵ）对OTC的去除存在抑制作用,且浓度越高,抑制作用越显著.     

NaHCO3活化荞麦皮生物炭对碘帕醇的吸附

采用NaHCO₃活化荞麦皮生物炭,优化得到生物炭0.25N-BC[m（NaHCO₃）：m（荞麦皮）=0.25：1],通过SEM、BET、XRD、Raman、FTIR和XPS等方法进行表征,分析NaHCO₃对生物炭理化性质的影响,探究其对非离子型碘代X射线造影剂碘帕醇（IPM）的吸附性能和机制.结果表明,与荞麦皮生物炭相比（BC）,NaHCO₃活化生物炭的结构缺陷程度更高（比表面积和孔体积分别由480.40 m²·g^-1和0.29 cm³·g^-1增至572.83 m²·g^-1和0.40 cm³·g^-1,I_D/I_G是BC的1.22倍）,表面含碳和含氧官能团数量发生显著变化,极性增强[（N+O）/C由0.15增至0.24],能够有效吸附IPM,0.25N-BC对IPM最大吸附量达到74.94 mg·g^-1,是BC （7.88 mg·g^-1）的9.51倍.拟二级吸附动力学和Langmuir、Freundlich等温线模型可很好地拟合0.25N-BC对IPM的吸附,吸附过程主要以化学吸附和单层、非均质多层吸附为主;孔隙填充、氢键、π—π和n—π相互作用是0.25N-BC吸附IPM的主要机制.对比不同碱[KOH、Na₂CO₃、NaHCO₃、KHCO₃和Ca （HCO₃）₂]活化荞麦皮生物炭对IPM的吸附,0.25N-BC吸附效率高,达到吸附平衡时间短,能有效去除实际水体（二沉池出水和湖水）中IPM的残留,并具有良好的循环使用性能,吸附-解吸3次后对IPM的去除率仍保持在74.91%.研究表明NaHCO₃活化荞麦皮生物炭是一种绿色有效,可持续去除含碘有机物的优良吸附剂.     

FeCl3改性污泥生物炭对水中吡虫啉的吸附性能研究

以脱水污泥为原料,制备污泥生物炭（SBC）和FeCl₃改性污泥生物炭（Fe-SBC）处理低浓度吡虫啉（IMI）废水（浓度为10 mg·L^-1）,考察SBC和Fe-SBC对IMI的吸附性能及影响因素,并探究其吸附机理.采用SEM、XRD、FTIR、BET及元素分析等探得污泥生物炭FeCl₃改性成功.Fe-SBC对IMI的最大吸附量为4.915 mg·g^-1,是SBC的1.97倍,表现出更好的IMI吸附性能.pH和离子强度的变化对Fe-SBC的吸附性能影响较小,最大波动幅度分别为4.4%和7.8%.两种生物炭对IMI的吸附均符合准二级动力学模型,Freundlich模型可以更好地描述其等温吸附曲线.热力学研究表明,SBC吸附IMI是非自发吸附,而Fe-SBC是自发吸附.Fe-SBC对IMI的吸附机理包括静电作用力、氢键作用力及π-π键相互作用力.多次热解再生后的Fe-SBC对IMI的去除率仍可达93.088%.     

MIL-125(Ti)/NH2-MIL-125(Ti)材料的制备及其对铀酰离子吸附性能的研究

寻找具有高效、高吸附量、高选择性的吸附剂处理放射性的含铀废水,对环境保护具有现实意义.通过溶剂热法合成两种金属有机框架材料MIL-125和NH₂-MIL-125,并用X-射线衍射仪（XRD）、扫描电镜（SEM）、傅里叶变换红外光谱仪（FT-IR）、热重分析仪（TGA/DSC）等仪器对两种材料的结构和形貌分别进行表征,探究不同的初始pH、初始铀浓度、吸附时间等条件下两种材料分别对UO₂²⁺吸附性能的影响.结果表明：本实验成功合成了MIL-125和NH₂-MIL-125两种材料;当初始pH分别为5和8时,MIL-125和NH₂-MIL-125材料对UO₂²⁺的吸附效果最好.通过Langmuir和Freundlich方程进行热力学拟合可知,两种材料的吸附过程更符合Langmuir方程,在25℃时MIL-125、NH₂-MIL-125对UO₂²⁺的最大吸附量分别为264.4 mg·g^-1和327.3 mg·g^-1,最佳吸附时间分别为480 min和70 min.     

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.