复合金属改性生物炭对水体中低浓度磷的吸附性能

通过FeCl_3和KMnO_4溶液对果壳生物炭进行浸渍改性,探索复合改性生物炭(Fe:Mn=1:1)对低浓度磷的吸附性能.结果表明,铁锰复合改性生物炭对低浓度磷的吸附效果远远大于铁改性及锰改性; SEM和FT-IR测定表明,铁锰复合改性后生物炭表面可能存在铁锰氧化物和铁氢氧化物.在磷浓度为0. 5 mg·L~(-1)、温度为298 K、固液比(mg∶L)为500时,吸附量为0. 96 mg·g~(-1).当溶液的pH为4～10,均具有较高的去除率和吸附量.等温吸附实验数据符合Freundlich方程,为多层吸附.吸附热力学研究表明,ΔG~θ0、ΔH~θ 0和ΔS~θ 0,说明该吸附是自发、熵增加的吸热过程.吸附动力学分析发现,改性后生物炭在60 min内基本达到吸附平衡,吸附过程符合准二级动力学方程,以化学吸附为主.可为天然水体和污水处理厂低浓度除磷提供理论数据支撑.     

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.     

酿酒酵母对Ag^＋的吸附特性研究

为了深入探讨酿酒酵母吸附贵金属离子Ag+的特性,研究了吸附时间、离子浓度、初始pH值、温度对废弃酿酒酵母吸附Ag+的影响,并分析了动力学、热力学以及等温吸附特性.结果表明,酵母吸附Ag+的过程进行得很快,当Ag+初始浓度为1mmol·L-1、细胞浓度2 g·L-1条件下,反应10 min,Ag+可以达到平衡吸附量的86%以上.随后在24 h内吸附量缓慢增加,去除率基本维持在51%～55%左右.酵母吸附Ag+的过程可以用准一级和准二级动力学方程描述,后者模拟效果更好.酵母吸附Ag+的等温吸附过程可以用Langmuir方程描述,但Freundlich方程拟合效果较差.当Ag+初始浓度为0～8 mtool·L-1、酵母浓度2·L-1条件下,酵母吸附Ag+的Langmuir理论饱和生物吸附容量为0.385 mmol·g～.在pH 2.0-7.2范围内,吸附量随着溶液初始pH值升高而升高.10～40℃范围内,温度对酵母吸附Ag+的影响不如pH值的影响显著,特别是在低离子浓度下尤其如此.酵母吸附Ag+的较适宜温度为20～30℃.热力学分析表明,酵母吸附Ag+具有自发性、熵增特征.     

亚热带海湾表层沉积物对磷的吸附解析特征研究

磷在沉积物-水界面的吸附解析过程对水体富营养化具有重要影响,目前亚热带海湾沉积物对磷的吸附解析特征并不清楚,其自身的粒度组成和理化性质对沉积物磷吸附解析影响尚不明晰.本研究以3个主要入海河口区采集的表层沉积物为基础,通过吸附动力学和等温吸附试验,研究了不同粒径、pH和盐度等环境因子对磷吸附解析特征的影响规律.采用连续提取(SEDEX)法对沉积物吸附磷前后样品进行磷赋存形态分级,探讨沉积物对磷相应的吸附机制.结果表明：亚热带海湾入海河口区表层沉积物对磷的吸附动力学过程可用准二级动力学模型描述,等温吸附曲线符合Langmuir-交叉型模型.沉积物对磷的最大吸附量(Qm)范围为0.332～0.864 mg/g,沉积物磷的吸附/解吸平衡质量浓度(EPC₀)在0.076～0.150 mg/L之间.粒径较小的沉积物具有较强的磷吸附能力,海水酸碱度和盐度有利于沉积物磷吸附,吸附后的沉积物中可交换态磷(Ex-P)和铁结合态磷(Fe-P)含量明显增加,沉积物对磷的吸附过程同时存在物理吸附和化学吸附,且以物理吸附为主.研究显示,亚热带海湾表层沉积物较高含量的黏土矿物和高分子量的有机质...     

改性镁铝水滑石对黑臭水体中磷的去除效果研究

通过采样和调研江苏省盐城市、扬州市不同程度治理的黑臭水体,分析其水质及磷赋存特征,选用对磷酸盐高效吸附的镁铝水滑石,开展了改性水滑石对黑臭水体中磷的吸附行为研究.结果表明：①调研的黑臭水体中44%水样磷浓度超过《地表水环境质量标准》Ⅴ类水标准限值,易发生水华等次生灾害,控磷减磷措施十分必要;②在黑臭水体pH值范围内,pH值对改性水滑石吸附磷的影响较小,改性水滑石的磷吸附量随初始溶液中磷的浓度升高而增大,其吸附动力学过程更符合准二级动力学方程;③在黑臭水体采集水样中,改性水滑石依然表现出较好的磷吸附能力,磷酸盐去除率达到了94.4%,可以有效削减黑臭水体中磷污染程度.     

粉末活性焦对水中磷酸盐的吸附性能

以蒙东褐煤为原料,通过沉降炉炭化活化一步法制备了粉末活性焦（COKE）,其具有丰富的孔隙结构,以微孔为主,占据比表面积的79.3%.考察了活性焦对水中磷酸盐的吸附性能,并进一步研究了吸附时间、温度、初始pH值、初始磷酸盐浓度、活性焦投加量和共存离子对吸附过程的影响,以及吸附动力学、吸附等温线和热力学特征.结果表明：活性焦对水体中的磷酸盐具有良好的吸附性能.在30℃,pH=7的条件下,利用20.00g/L活性焦吸附1mg/L磷酸盐溶液,60min即可达到吸附平衡,此时吸附率可达89.4%.当吸附温度越高（10~40℃）,活性焦投加量越大,溶液pH值在6~7时,活性焦对水中磷酸盐的去除效果越好.共存离子的存在（NO₃^-、SO₄^2-、CO₃^2-）对活性焦吸附磷酸盐有抑制作用.活性焦对磷酸盐溶液的吸附过程较好符合Freundlich模型（R²>0.99）和准二级动力学模型（R²>0.99）,最大吸附容量为1.746mg/g（30℃）,并通过热力学分析发现此过程为自发的吸热反应.利用傅立叶红外光谱分析进一步表明,活性焦吸附磷酸盐主要依靠配位交换.与活性炭相比,活性焦性价比更高,具有良好的应用前景.     

岱海沉积物内源磷释放特征的研究

岱海沉积物及水体营养盐浓度较高,内源污染释放风险大,水体营养盐浓度逐年上升.通过分析岱海西南湖区、东北湖区及中心湖区沉积物磷吸附动力学特征和吸附等温特征,计算沉积物NAP（native adsorbed phosphorus,吸附解吸态磷）浓度和EPC₀（equilibrium phosphorus concentration,平衡磷浓度）,明确岱海各湖区沉积物磷的“源-汇”转换机制.结果表明:①准二级动力学模型能够较好地描述沉积物样品对磷的吸附动力学行为,且沉积物吸附磷的速率较快,最高吸附速率达11.45 g/（mg·min）,在8 h内沉积物对磷的吸附可趋于平衡状态.②修正后的Langmuir等温吸附模型（R2为0.907 6~0.974 2）能较好地描述沉积物对磷的吸附等温行为,且通过参数计算发现,岱海中心湖区的沉积物具有较高的磷吸附量,最大值为0.867 mg/g.③通过对比NAP含量、沉积物EPC₀与间隙水中SRP（soluble reactive phosphorus,可溶性活性磷）浓度,发现岱海中心湖区沉积物有较大的磷释放风险,西南湖区和东北湖区磷释放风险较小.④岱海中心湖区沉积物较高的NAP含量及pH导致该区内源磷释放风险加大.根据岱海沉积物磷释放呈现的区域性特征,在内源磷释放控制方面,可采取轻重结合的防控方式对岱海湖区进行重点防控.      

天然菱铁矿去除水中磷的性能研究

采用批次试验研究菱铁矿对水溶液中磷的吸附特性,考察了初始磷浓度、p H值、菱铁矿投加量、粒径、共存离子对吸附的影响,并探讨了吸附动力学和吸附热力学特征.结果表明,当磷溶液初始浓度为20 mg·L-1,初始p H为6.0时,菱铁矿对磷的吸附效果较好,吸附平衡时间为48h.菱铁矿投加量为0.5~10 g时,随着投加量的增加,菱铁矿对磷的吸附效能逐渐提高.相对于NO-3、Cl-而言,SO2-4、HCO-3对菱铁矿去除磷有微弱的抑制作用.动力学研究发现,菱铁矿对磷的吸附过程更符合准二级动力学模型,吸附平衡可由Freundlich等温线方程描述,饱和吸附量为83.5μg·g-1.最后分别计算了288、303和318 K下的吸附热力学参数,发现吉布斯自由能(ΔG)均为负,焓变(ΔH)及熵变(ΔS)为正,表明该吸附过程为自发的吸热反应.     

改性麦草秸秆对水中磷酸根吸附效果的研究

为实现农作物秸秆资源化,解决水体富营养化问题,将麦草秸秆化学改性成一种可以有效吸附水体中磷酸根的阳离子型吸附剂.考察了吸附剂投加量、磷酸根溶液初始pH、温度等因素对吸附效果的影响,分析了改性麦草秸秆对磷酸根的吸附动力学过程和吸附机理.结果表明,在吸附剂投加量为4 g·L-1和磷酸根溶液初始pH为4.0～7.5条件下,改性麦草秸秆对磷酸根的吸附效果最好,去除率均高于90%;改性麦草秸秆对磷酸根的吸附符合Freundlich等温模式,饱和吸附容量为2.38 mmol·g-1;吸附过程符合一级反应动力学方程,为快速反应过程;反应活化能为12.6 kJ·mol-1,反应速率对温度的变化不敏感.     

白果壳遗态Fe/C复合材料对水中磷的吸附特征

为研究PBGC-Fe/C-G（白果壳遗态Fe/C复合材料）对水中磷的吸附特征,以PBGC-Fe/C-G为吸附剂,对吸附剂投加量、溶液体系pH、初始磷质量浓度、温度和吸附剂粒径为影响因素进行静态吸附试验分析,并结合SEM、EDS、XRD和FT-IR等手段对吸附前、后材料进行表征,以揭示PBGC-Fe/C-G的吸附除磷机制.结果表明:①当初始磷质量浓度 < 10 mg/L、吸附剂投加量为0.2 g/（50 mL）、溶液为酸性（pH=3）、反应温度为45℃、吸附剂粒径 < 0.149 mm时,吸附效果最佳,吸附量达1.62 mg/g.②准二级动力学模型和Freundlich吸附等温模型能较好地模拟PBGC-Fe/C-G对磷的吸附过程.③热力学结果显示,ΔG < 0、ΔS>0和ΔH>0,说明PBGC-Fe/C-G对磷的吸附过程是自发、熵增的吸热过程.研究显示,PBGC-Fe/C-G吸附除磷主要通过配位作用、静电引力、等电荷离子交换和物理作用4种协同完成,其中Fe活性位与磷酸根离子的配位反应为主要的反应过程.      

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.