水合氧化铝负载的磁性核/壳结构Fe3O4@SiO2纳米颗粒对水中磷的去除及再利用

在磁铁矿纳米颗粒表面包被硅壳后再包被水合氧化铝,制备了具备核壳结构的磁性纳米颗粒除磷吸附剂(磁性氧化铝),通过XRD、TEM、VSM、BET比表面积测定进行了表征.XRD和TEM结果显示了核壳结构的存在,其饱和磁化强度达56.00 emu·g~(-1),比表面积达47.27 m~2·g~(-1).Langmuir模型计算的磷最大吸附量为12.90 mg·g~(-1),且在25℃和50℃下均保持稳定,反应快速,40min磷去除率达96%以上.磁性纳米吸附剂对磷的吸附与pH关系密切,在p H为5~9时磷去除率达90%以上.采用实际污水实验,最佳投量为1.25 kg·t~(-1).吸附-脱附-再生实验结果表明,磷吸附率随循环次数增加稍有下降,吸附的磷可以通过1 mol·L~(-1)的NaOH脱附,脱附率为90%左右,且吸附剂可以进行再生,具有反复利用和回收磷资源的潜力.     

3种吸附剂对污水磷污染去除性能与机制比较

为探索高效利用膨润土、红壤和炉渣去除农业污水磷污染的可行性,对比分析了3种吸附剂对人工合成含磷污水的吸附去除特性,结合SEM、XDS和BET等测试结果以及等温吸附、吸附动力学及Ca2+释放量探讨了3种材料对磷的吸附机制.结果表明,炉渣对磷的吸附能力高于膨润土和红壤,吸附过程均适合Langmuir等温吸附方程(R2 0. 96),对磷的理论饱和吸附量为:炉渣(16. 87 mg·g~(-1))红壤(1. 21 mg·g~(-1))膨润土(0. 92 mg·g~(-1)).炉渣对磷的吸附动力学特征符合Elovich方程(R2=0. 966),而膨润土和红壤对磷的吸附特征则更适合准二级动力学方程(R2为0. 982和0. 959).炉渣的Ca2+释放量(10. 46 mg·g~(-1))显著大于膨润土(0. 31 mg·g~(-1))和红壤(0. 03 mg·g~(-1))(P 0. 05).红壤对磷的吸附量随着p H的升高而降低;膨润土在初始p H为7. 0时,吸附量最低;但初始p H值对炉渣去除磷的影响不大.相比红壤和炉渣,膨润土解吸较快,易于进行重复利用.综上所述,吸附材料的磷吸附能力主要与其结构、化学组成、Ca2+释放能力及溶液初始p H值等有关,炉渣较膨润土和红壤对磷酸盐有着更强的去除能力,适合处理农村污水磷污染.     

紫外辐照改性生物炭对VOCs的动态吸附

采用365 nm紫外光辐照改性椰壳生物炭,以提升对挥发性有机污染物(VOCs)的吸附性能.选取苯和甲苯两种典型的VOCs为吸附质,考察了改性前后生物炭的吸附穿透曲线.结果表明,紫外辐照改性后的生物炭其吸附性能显著增加,对苯和甲苯的饱和吸附量分别由7.27 mg·g~(-1)和7.98 mg·g~(-1)提升至122.80 mg·g~(-1)和236.36 mg·g~(-1),吸附穿透时间也由1 min和2 min大大延长至390 min和620 min.生物炭表面理化特征分析表明,紫外辐照增大了生物炭表面含氧官能团的含量和外比表面积,这可能是改性生物炭吸附性能提升的关键因素.Yoon-Nelson、Thomas和BDST模型均能很好地模拟改性生物炭对不同浓度苯和甲苯的吸附过程,其相关系数大于0.992.热重分析结果表明,紫外辐射对生物炭的热稳定性影响甚微.改性生物炭吸附饱和后,可经热再生后重复利用,对甲苯的吸附重复利用5次后仍有较高的吸附能力.     

真菌预处理优化制备微介多级孔炭及其吸附甲苯的研究

提出采用黄孢原毛平革菌对生物质前体物进行预处理的制备策略,从而研发孔结构可调的多级孔炭材料模板.选用荷叶作为生物质原材料,探讨菌种投加量、培养时间对多级孔炭材料前驱体的影响,并采用水蒸气物理活化法,分析活化温度和活化时间对炭材料比表面积、孔径分布和表面官能团的综合作用.最后,通过Raman、XRD、BET、FTIR、TGA、SEM、EA等手段表征其物理化学性质,并考察真菌预处理对炭材料的甲苯吸附性能的影响.结果表明,在生物质荷叶质量30 g、菌种投加量4 mL、培养时间7 d、活化温度800℃、活化时间90 min条件下制备的微介多级孔炭材料,在含有较多介孔的前提下比表面积可达937 m~2·g~(-1),总孔容为0.68 cm~3·g~(-1).动态模拟吸附实验发现,经预处理的炭材料在甲苯浓度905 mg·m~(-3)下对其饱和吸附容量为304 mg·g~(-1),是未经真菌调控荷叶吸附容量的1.83倍,吸附性能的提升主要归因于比表面积、孔容及表面酸性基团增大的作用.经真菌预处理调控的炭材料对甲苯的吸附符合Langmuir吸附等温线,属于单分子层吸附.     

负载铁锰氧化物的玉米芯炭对Pb2+的吸附作用

采用两步浸渍-草酸盐热解法制备了均匀负载铁锰氧化物的磁性玉米芯炭(MnFeO_x@CCBC),通过X射线衍射(XRD)、扫描电子显微镜(SEM)、比表面积分析仪和pH漂移实验等表征,证明制备的MnFeO_x@CCBC材料表面由MnFe_2O_4和无定形态的δ-MnO_2或水合氧化锰组成,pH_(ZPC)约为6.0,比表面积为3.9 m~2·g~(-1).同时,比较研究了MnFeO_x@CCBC和原始玉米芯炭(CCBC)对Pb~(2+)的吸附动力学和热力学行为.结果表明:吸附过程均符合准二级动力学方程和Langmuir等温吸附模型,在实验条件下,MnFeO_x@CCBC对Pb~(2+)的吸附速率和吸附量都明显优于CCBC,准二级动力学速率常数大3.3倍,理论平衡吸附量高6.95倍;在30℃时,MnFeO_x@CCBC和CCBC的饱和吸附量分别为99.60和15.66 mg·g~(-1);Pb~(2+)的吸附过程是熵驱动和吸热的.傅里叶变换红外光谱(FTIR)和X射线光电子能谱(XPS)等分析表明,MnFeO_x@CCBC的主要吸附位是Mn—OH,其主要吸附机理是Pb~(2+)对Mn—OH中H~+的置换,并形成内层表面络合物.     

活性炭/高分子复合水凝胶对水中亚甲基蓝和Cu(Ⅱ)的去除性能

采用活性炭/海藻酸钠-聚乙烯醇复合水凝胶(CAP)为吸附剂,以水溶液中的亚甲基蓝(MB)和Cu~(2+)为目标污染物,考察了固液比、p H、温度、反应时间、MB和Cu~(2+)的初始浓度等因素对吸附过程的影响.通过SEM、FTIR、BET等手段对CAP物化性质进行了表征.结果表明,CAP内部呈现互穿的三维网络多孔结构,成功复合了活性炭,具有丰富的—COOH和—OH官能团,比表面积可达112.7 m~2·g~(-1).CAP对MB和Cu~(2+)的吸附量随着固液比、温度的增大而降低,随着溶液初始p H的升高而增大;吸附属于Langmuir单层吸附,对MB和Cu~(2+)的最大吸附量分别为1 940.75 mg·g~(-1)和190.48 mg·g~(-1);反应时间在5 h内吸附量可达最大吸附量的90%,吸附动力学过程符合准二级动力学方程;活性炭/高分子复合水凝胶经过5次吸附-脱附循环再生后,仍能保持优异的吸附性能.     

磷酸水热预处理制备高比表面积高介孔率活性炭

以锯末为原材料,采用磷酸水热预处理后活化的工艺制备高介孔率活性炭,以比表面积和孔容为评价标准,通过单因素实验探究了酸料比、活化温度、活化时间对活性炭比表面积及总孔容的影响规律,验证了该工艺的可行性.最优条件下所制备的活性炭比表面积为2579 m~2·g~(-1),介孔率达到96.6%,充分说明磷酸水热预处理工艺能够显著提高活性炭介孔孔容占比.亚甲基蓝(MB)吸附实验数据与Redlich-Peterson模型拟合度较好,样本活性炭对MB的吸附为单分子层吸附,最大单层吸附量为618.35 mg·g~(-1),接近于实验测试值632.79 mg·g~(-1),表明该方法制备的活性炭具有良好的MB吸附性能.     

锆改性硅藻土吸附水中磷的研究

采用锆对硅藻土进行改性所得锆改性硅藻土,其氧化锆质量分数占12.39%,经XRD鉴定为无定形.SEM结果显示,改性后硅藻土表面出现粗糙多孔的絮状物.相比硅藻土,锆改性硅藻土的比表面积由14.00 m~2·g~(-1)扩大到75.22 m~2·g~(-1).XPS谱图显示,氧化锆与硅藻土之间以化学键方式,而非物理沉积方式结合.锆改性硅藻土对磷的等温吸附线更符合Langmuir模型,拟合得到最大吸附量为10.56 mg·g~(-1).锆改性硅藻土的吸附量按照氧化锆的质量分数计算为81.67 mg·g~(-1)ZrO_2,高于文献报道的纯氧化锆吸附剂.锆改性硅藻土对磷的吸附随pH的上升而下降,结合吸附前后材料的Zr3d高分辨XPS图谱,确定锆改性硅藻土对磷的吸附为配体交换过程.氯离子、硫酸根离子和硝酸根离子共存不会抑制磷的吸附,而碳酸氢根离子具有一定的抑制作用.对磷浓度为2 mg·L~(-1)的富营养化湖水,锆改性硅藻土投加量大于1.25 g·L~(-1)时,反应后磷浓度即可满足《地表水环境质量标准》规定的湖库Ⅲ类标准.     

磁性高分子复合水凝胶的制备及其对水中铜离子的吸附性能

以海藻酸钠和聚乙烯醇为骨架负载磁性纳米Fe_3O_4颗粒合成了两种磁性高分子复合水凝胶材料:一种是以Ca~(2+)交联制备的磁性海藻酸钙单网络水凝胶(SAPFe),另一种是以海藻酸钙和聚乙烯醇经循环冷冻解冻制成的磁性双网络水凝胶(DAPFe).利用SEM、FTIR、BET对合成的材料进行表征,并研究了SAPFe和DAPFe对Cu~(2+)的吸附性能.结果表明,DAPFe比表面积达89.01 m~2·g~(-1),平均孔径为2.2 nm,DAPFe比SAPFe具有更低的含水率、更高的交联程度、更发达的孔隙结构和更高的比表面积.DAPFe对Cu~(2+)的最大吸附量可达207.01 mg·g~(-1),远大于SAPFe(173.01 mg·g~(-1)).SAPFe和DAPFe对Cu~(2+)的吸附等温线均符合Langmuir模型,吸附动力学符合准二级吸附动力学模型.通过分析SAPFe和DAPFe吸附Cu~(2+)前后官能团的变化,发现磁性高分子复合水凝胶具有丰富的羧基和羟基功能性官能团,并通过与Cu~(2+)产生螯合作用实现去除.     

石墨烯凝胶电极的制备及电吸附Pb2+的性能

电吸附去除水中重金属离子具有吸附容量高和电极可再生的优点.本文采用高温水热法还原氧化石墨烯(GO)得到石墨烯水凝胶(GS)并经压片制得GS电极.本文对GS电极的电化学性能进行了测试,考察了GS电极电吸附Pb~(2+)的动力学和热力学特性,以及电极的脱附和循环使用情况.结果表明,GS电极的电化学性能优异,其单位质量比电容高达200.4 F·g~(-1)(1 A·g~(-1));提高电压有利于GS电极电吸附Pb~(2+),电压为-1.2 V时,GS电极对Pb~(2+)的去除率达96.4%;GS电极电吸附Pb~(2+)的饱和吸附量达461.20 mg·g~(-1),是不加电时饱和吸附量的2倍;施加反向电压可以实现Pb~(2+)的脱附和电极再生,电吸附-脱附15次后,电极对Pb~(2+)的去除率保持在95%以上.     

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.     

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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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.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.