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.     

Ca/Mg负载改性沼渣生物炭对水中磷的吸附特性

为处理含磷废水和实现沼渣资源化利用,将农业废弃物沼渣制备成生物炭(ZZs),通过Ca Cl2和MgCl2溶液对其进行浸渍改性,探究改性沼渣生物炭(CMZZs)对水体中磷的吸附特征.结果表明,改性后沼渣生物炭钙镁含量分别是改性前的1. 3和15. 4倍; SEM-EDS、BET、FTIR和XRD等测定表明,改性未改变生物炭表面化学官能团种类,但改性后生物炭出现新的衍射峰,与标准卡片对比后认为可能存在Mg(OH)_2、MgO等物质.当温度为303 K,溶液pH为9. 0时,CMZZs最大吸附量为76. 92 mg·g~(-1),是改性前的30. 1倍.等温吸附实验数据符合Freundlich方程,为多层吸附.吸附动力学分析发现,改性后生物炭在100 min内基本达到吸附平衡,吸附过程符合假二级动力学方程,以化学吸附为主.上述结果说明钙镁改性沼渣生物炭对于去除水中磷具有潜在价值.     

Ca/Mg负载改性沼渣生物炭对水中磷的吸附特性

为处理含磷废水和实现沼渣资源化利用,将农业废弃物沼渣制备成生物炭(ZZs),通过CaCL2和MgCL2溶液对其进行浸渍改性,探究改性沼渣生物炭(CMZZs)对水体中磷的吸附特征。结果表明,改性后沼渣生物炭钙镁含量分别是改性前的1.3和15.4倍;SEM-EDS、BET、FTIR和XRD等技术表明,改性未改变生物炭表面化学官能团种类,但改性后生物炭出现新的衍射峰,与标准卡片对比后可能存在Mg(OH)2、MgO等物质。当温度为303K,溶液pH为9.0时,CMZZs最大吸附量为76.92mg·g-1,是改性前的30.1倍。等温吸附实验数据符合Freundlich方程,为多层吸附。吸附动力学分析发现,改性后生物炭在100min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。上述结果说明钙镁改性沼渣生物炭对于去除水中磷具有潜在价值。     

添加生物炭对西北黄土吸附克百威的影响

研究了不同温度下制得的生物炭对西北黄土吸附农药克百威的影响,并对溶液p H值和初始浓度对吸附的影响进行了探讨.结果表明,克百威在添加生物炭黄土上的动力学吸附过程较好地符合准二级吸附动力学模型;热力学吸附较好地符合Freundlich等温吸附模型;随着系统温度的升高,添加生物炭的黄土对克百威的吸附量增大,且其对克百威的吸附自由能变(ΔGθ)小于0,吸附焓变(ΔHθ)及吸附熵变(ΔSθ)均大于0,表明吸附是一个自发吸热且体系混乱程度增大的等温吸附过程.溶液p H值和克百威的初始浓度对添加生物炭的土样吸附影响较明显.当p H值为4~7时,添加生物炭的土样饱和吸附量随p H升高呈缓慢降低,当p H值大于7时,吸附容量随p H升高呈明显降低趋势.克百威初始浓度从20 mg·L-1增至50 mg·L-1的过程中,吸附量快速上升,初始浓度大于50 mg·L-1时,吸附量随初始浓度的升高而缓慢增加并逐渐趋于平衡.     

芦苇基和污泥基生物炭对水体中诺氟沙星的吸附性能

以芦苇秸秆和市政污水处理厂污泥为原料,在500℃的条件下制备了芦苇基和污泥基生物炭.利用比表面积测定法(BET)、扫描电镜(SEM)、能谱分析(EDS)和红外光谱(FTIR)研究了生物炭的结构与性质,并通过单因素实验研究p H、吸附时间、温度、诺氟沙星(NOR)初始浓度对吸附效果的影响,初步讨论了吸附机制.结果表明,NOR在芦苇基和污泥基生物炭上的吸附在12 h分别达到总吸附量的70%、60%以上;芦苇基和污泥基生物炭对NOR的饱和吸附量分别为2.13 mg·g-1和2.09 mg·g-1;降低溶液p H有利于NOR的吸附;生物炭对NOR的吸附行为符合准二级动力学方程,其等温吸附曲线符合Langmuir方程.对吸附过程吉布斯自由能(ΔG)、焓(ΔH)以及熵(ΔS)的计算证明生物炭对NOR的吸附是自发的吸热反应;红外光谱分析表明,生物炭上较多含氧官能团为NOR的吸附提供了吸附点,有利于NOR分子与生物炭间形成作用力较强的氢键,氢键为NOR吸附在生物炭上的主导作用力.     

牛粪生物炭对磷的吸附特性及其影响因素研究

以牛粪生物炭为吸附剂,采用平衡吸附法研究了牛粪生物炭对磷的吸附特征.研究了pH值、共存离子、反应温度、投加量、热解温度等对牛粪生物炭吸附磷的影响.结果表明,牛粪生物炭吸附磷的最佳初始pH值为7.0;共存离子的存在对生物炭吸附磷的影响有限;反应温度升高不利于磷的吸附;当投加量为0.1g时,对磷的去除率较为理想;热解温度升高不利于对磷的吸附.通过对实验数据进行动力学、吸附等温线及热力学分析,发现牛粪生物炭对磷的吸附动力学数据符合拟二级吸附动力学方程,Langmuir-Freundlich(R2=0.9705)和Temkin(R2=0.9556)方程能很好地描述磷在牛粪生物炭上的吸附行为.热力学分析结果显示25,35,45℃下的吉布斯自由能变化(ΔG0)分别为-17.43,-15.98,-15.89kJ/mol,表明牛粪生物炭对磷的吸附是自发的过程.     

不同热解及来源生物炭对西北黄土吸附敌草隆的影响

以西北黄土为研究对象,采用批量法研究不同温度下制得的生物炭对西北黄土吸附敌草隆的影响.结果表明,敌草隆在添加不同质生物炭黄土上的动力学吸附过程较好地符合准二级吸附动力学模型,且吸附过程主要分为快吸附(0~8 h)和慢吸附(8~12 h)两个阶段,在12 h左右达到平衡;热力学较好地符合Freundlich等温吸附模型;添加生物炭的黄土对敌草隆的吸附量随着温度的升高而增大,且吸附过程中ΔG~θ小于0,ΔH~θ和ΔS~θ大于0;不加生物炭的黄土对敌草隆吸附量则随着温度的升高而降低,且吸附过程中ΔG~θ和ΔH~θ小于0,ΔS~θ大于0;在体系温度范围内,E(吸附平均自由能)为1.29~5.00 k J·mol-1,表明无论是否添加生物炭,黄土对敌草隆的吸附都以物理吸附为主.其影响因素分析结果显示,随着生物炭热解温度的升高,溶液中敌草隆的平衡浓度降低,平衡吸附量增大;添加生物炭的黄土对敌草隆吸附量在0.5~6 mg·L-1浓度范围内快速上升,之后吸附量随初始浓度的升高缓慢增加并逐渐趋于平衡;溶液pH对黄土吸附敌草隆有一定影响,但影响不大.     

酸碱改性生物炭对水中磺胺噻唑的吸附性能研究

以马铃薯茎叶为原料,采用限氧裂解法制备生物炭,通过H2SO4和KOH处理制备酸、碱改性生物炭.应用比表面积法(BET)、扫描电镜(SEM)和红外光谱(FTIR)研究了改性前后3种生物炭的结构与性质,并通过单因素实验研究了吸附时间、温度、磺胺噻唑初始浓度、p H值等因素对原始及酸碱改性3种生物炭吸附磺胺噻唑效果的影响,初步探讨了吸附机制.结果表明,3种生物炭对磺胺噻唑的吸附行为符合准二级动力学方程;酸改性生物炭对磺胺噻唑的吸附等温线符合Temkin模型,原炭和碱改性生物炭的吸附等温曲线符合Freundlich模型.酸改性极大的提高了生物炭对磺胺噻唑的吸附能力,最大吸附量为7.69 mg·g-1,是原炭吸附量的2.4倍;溶液p H对3种生物炭吸附磺胺噻唑影响不明显.热力学研究表明,酸改性生物炭对磺胺噻唑的吸附为自发的吸热反应.FTIR分析表明,酸改性生物炭表面有更多含氧官能团,为磺胺噻唑的吸附提供了吸附点.氢键、范德华力及偶极距力作用对生物炭吸附磺胺噻唑起到主要作用.     

载氧化镁水生植物生物炭的特性表征及对水中磷的吸附

为去除富营养化水体中的磷并实现水生植物的资源化利用,以水生植物芦苇和互花米草为原材料,通过MgCl_2改性制备了不同Mg~(2+)和植物配比的共12种生物炭,考察对水体中磷的吸附能力及镁改性前后生物炭特性的差异.结果表明,当Mg~(2+)与芦苇、Mg~(2+)与互花米草的质量比为0.48、0.36时,制得的两种生物炭对20 mg·L~(-1)磷的吸附能力最强,分别为8.52 mg·g~(-1)和9.21 mg·g~(-1),是未改性时的79倍和66倍;对溶液中20mg·L~(-1)磷的去除率分别达到85.2%和92.1%.改性后芦苇和互花米草生物炭C、H、N含量减少,Mg含量分别增加到22.77%和23.46%.芦苇生物炭改性后比表面积减小了118.71 m~2·g~(-1),互花米草生物炭增加了22.59 m2·g~(-1);二者孔容和平均孔径均有所增加.改性前后生物炭的表面官能团种类相同.XRD测试指出MgO为改性生物炭的复合纳米颗粒中最主要的晶相;SEM展现了布满MgO的改性生物炭表面及孔道.机理分析表明,MgO是生物炭吸附磷的关键.     

铁锰复合氧化物包覆海砂的吸附除磷研究

利用铁锰复合氧化物包覆海砂制备了一种用于污水除磷的新型颗粒状吸附剂,并对其表面特性与磷吸附行为进行了研究.扫描电镜(SEM)分析结果表明,包覆后海砂颗粒表面凹凸不平且多孔,BET比表面积由0.06增至2.52 m2·g-1.磷吸附实验结果表明,包覆后海砂对磷的吸附能力显著提高,最大吸附容量为1.01~1.23 mg·g-1,优于多数文献报道的负载改性砂颗粒吸附剂;吸附动力学更符合准二级动力学方程,推测磷在包覆海砂表面发生了化学吸附;溶液p H对磷吸附有一定影响,离子强度则影响不大;共存阴离子对磷吸附影响的大小顺序为Si O2-3CO2-3F-SO2-4Cl-.     

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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