铅在棉秆基活性炭上的吸附动力学与热力学

以棉秆与棉秆纤维为原料,利用磷酸活化法制备了低成本的高比表面微孔棉秆基活性炭,通过静态实验研究了活性炭对水溶液中铅的吸附特性,测定了溶液pH值、吸附时间、溶液温度对吸附的影响,探讨了吸附动力学、热力学及吸附机制.根据低温液氮(N2/77K)吸附测定数据,以BET方程、BJH法及H-K法对活性炭孔结构进行了表征,以Boehm滴定、FTIR、零电荷点pHPZC测定及元素分析定量表征活性炭表面含氧官能团.结果表明,以棉秆和棉秆纤维为原料制备的活性炭的比表面积分别为1570和1731m2·g-1,含氧酸官能团含量分别为1.43和0.83mmol·g-1,均高于商业活性炭ST1300.静态吸附实验表明,棉秆基活性炭对铅有较大的吸附容量和吸附效率,最大吸附量超过120mg·g-1,溶液pH对吸附有较大的影响,吸附量随时间增大而增大,在5min内可达饱和吸附量的80%;吸附动力学数据符合假二级方程,Freundlich方程能更好地描述等温吸附行为;热力学研究表明,吸附吉布斯自由能(ΔG0)0,而焓变(ΔH0)0,说明吸附为吸热的自发反应过程,升温有利于吸附,离子交换可能在吸附过程中起了重要作用.     

高比表面生物质炭的制备、表征及吸附性能

以废弃生物质互花米草与棉秆为原料,采用KOH活化制备了高比表面积微孔生物质活性炭.研究了原料类别、浸渍比、炭化温度及保温时间对炭组成与吸附性能的影响,利用氮气吸附、X-射线衍射、红外光谱FT-IR、扫描电子显微镜SEM等技术对活性炭表面物化性质进行了分析,并通过BET方程、DFT密度函数理论及Horvath-Kawazoe方程对比表面积与孔分布进行了表征测定.结果表明,氢氧化钾活化制备互花米草与棉秆活性炭的适宜条件为浸渍比3:1、活化温度800℃、活化时间1.5 h.在此条件下制得的互花米草活性炭与棉秆活性炭的得率为16.36%和11.22%,BET比表面积高达2 825 m2.g-1和2 135 m2·g-1,孔容积分别为1.374 mg·g-1和1.038 cm3·g-1;孔径分布狭窄,95%的孔集中在3 nm以内.该条件下制备的互花米草与棉秆活性炭吸附性能好,对碘的吸附值分别为1 797 mg·g-1和1 251 mg·g-1,亚甲基蓝吸附值为495 mg·g-1和478mg·g-1,均超过了国家水处理用活性炭一级品标准;2种生物质炭样品对水中2,4-二硝基苯酚的Langmuir最大吸附量分别为932 mg.g-1、747 mg·g-1,均优于普通活性炭与活性炭纤维.     

高比表面植物基活性炭吸附水中对硝基苯胺的性能及影响因素

以互花米草与棉秆为原料,以KOH为活化剂,制备了2种低成本高比表面微孔植物基活性炭SA-AC和CS-AC,通过静态实验研究了其对水溶液中对硝基苯胺的吸附特性,测定了溶液pH值、吸附剂剂量、溶液温度对吸附的影响,并探讨了等温吸附行为及其热力学性质.结果表明,在KOH与炭化料的质量比(剂料质量比)为3∶1、活化温度为800℃、活化时间为1.5 h条件下,活化制备的互花米草活性炭SA-AC和棉秆活性炭CS-AC的比表面积分别为2 825 m2.g-1和2 135 m2.g-1,微孔容积分别为1.192 cm3.g-1和1.011 cm3.g-1,对水溶液中对硝基苯胺的Langmuir最大吸附量分别为719和716 mg.g-1,远高于商业活性炭ST1300.溶液pH值和温度对吸附有较大影响,在低温及中性条件下有利于制备活性炭对水溶液中对硝基苯胺的吸附.Freundlich与Redlich-Peterson模型能很好地描述对硝基苯胺在2种活性炭上的吸附行为;热力学研究表明,吸附标准吉布斯自由能变ΔG0与标准焓变ΔH0均为负值,表明对硝基苯胺在这2种活性炭上的吸附属于自发的放热吸附过程;吸附标准熵变ΔS00,说明对硝基苯胺在活性炭表面上的迁移比在溶液中受到了更大的限制.     

活性炭纤维的改性及对Cu~(2+)吸附性能影响的研究

采用硝酸、磷酸、磷酸二氢铵和硝酸铜水溶液对聚丙烯腈基活性炭纤维(PAN-ACF)进行浸渍改性,制备了4种改性活性炭纤维(ACF1-ACF4)。测定了改性活性炭纤维表面含氧酸性官能团、零电荷点、比表面积和孔容,评价了改性纤维对铜离子的吸附性能。结果表明改性后活性炭纤维表面含氧酸性官能团明显增加,其零电荷点相应降低,比表面积和微孔孔容增大。改性活性炭纤维对Cu2+的吸附容量显著提高,其中ACF2吸附性能最佳,其吸附容量从改性前的4.80 mg/g增加到17.32 mg/g,提高了3.6倍。     

活性炭孔结构和表面化学性质对吸附硝基苯的影响

通过对活性炭HNO3氧化及随后的N2:气氛中热处理,研究了活性炭性质对其吸附硝基苯性能的影响.以低温液氮(N2/77K)吸附测定活性炭的比表面积和孔容、孔径分布,以SEM观测活性炭表面形貌,以Boehm滴定、FTIR、零电荷点pHpzc测定及元素分析定量表征活性炭表面含氧官能团变化.结果表明, HNO3氧化可以显著改变活性炭表面化学性质,增加活性炭表面酸性含氧官能团数量,对活性炭孔隙结构影响不大.随后N2:气氛中热处理可以造成活性炭表面酸性含氧官能团分解,外表面积增大,微孔烧蚀为中孔.硝基苯在活性炭上的吸附基本符合Langmuir方程,改性后活性炭对硝基苯的吸附容量明显改变, ACNO-T、ACraw、ACNO吸附容量分别为1011.31、483.09、321.54 mg·g-1.较大的外表面积、适宜数量的中孔以及较少的酸性含氧官能团是ACNO-T对硝基苯表现出较高吸附容量的主要原因.     

响应面法优化制备污泥基活性炭

利用响应面法进行试验设计,选定炭化温度、升温速率、炭化停留时间及保护气体流量为影响因素,对利用污水厂二次污泥制备污泥基活性炭的工艺条件进行优化.通过响应面法得到了污泥基活性炭的碘吸附值与4种因素之间的非线性回归方程,确定了制备污泥基活性炭的最优工艺条件为:炭化温度530℃、升温速率17℃·min-1、炭化停留时间22 min、保护气体流量280 m L·min-1.在最优条件下,制备的污泥基活性炭碘吸附值为675.9 mg·g-1,比表面积为639.5 m2·g-1,平均孔径为4.1 nm,中孔孔径为3~5 nm;羧基、内酯基和酚羟基含量分别为1.625、0.125和0.375 mmol·g-1,更适合吸附大分子污染物和金属离子.     

KOH活化微孔活性炭对对硝基苯胺的吸附动力学

以互花米草为原料,经过碳化、KOH活化两步法制备了低成本、高比表面的微孔活性炭SAAC.通过静态实验研究了活性炭SAAC对水溶液中对硝基苯胺的吸附特性,并从动力学角度探讨了吸附机理.结果表明,微孔活性炭SAAC对对硝基苯胺吸附动力学数据符合准二级方程,吸附速率在前25min由内扩散控制,而后由膜扩散与内扩散共同控制.Freundlich方程能更好地描述对硝基苯胺在活性炭SAAC上的等温吸附行为;在15℃时,活性炭SAAC对对硝基苯胺的Langmuir最大吸附量为719mg/g.     

壳聚糖改性污泥活性炭的脱硫脱硝性能

用壳聚糖改性污泥活性炭,测试分析了改性污泥活性炭的脱硫脱硝性能.同时,用N2吸脱附法、电子扫描电镜、傅立叶变换红外光谱及X衍射等技术对改性污泥活性炭进行了表征,研究了改性条件对污泥活性炭脱硫脱硝性能的影响,探讨壳聚糖改性提高污泥活性炭脱硫脱硝性能的机理.结果表明,壳聚糖颗粒物能够较为均匀地分布于污泥活性炭的表面,壳聚糖与污泥活性炭结合良好,孔径也明显减小.壳聚糖与污泥活性炭是通过化学键结合的.改性时间与改性温度均可改变污泥活性炭的BET比表面积和孔容,但改性温度对BET比表面积和孔容的影响更为显著.具有最优孔结构的样品A3的BET比表面积、总孔容及中孔容分别为168.76m·2g-1、0.084cm·3g-1及0.041cm·3g-1.与污泥活性炭相比,改性污泥活性炭的脱硫脱硝性能优于污泥活性炭,这是由于壳聚糖中含氮与含氧官能团,丰富了污泥活性炭表面脱硫脱硝活性基团的种类与数量,利于SO2与NO的吸附氧化;通过适当控制改性条件,也可显著地增加BET比表面积和中孔容,以提高SO2与NO气体的物理吸附,从而提高其脱硫脱硝性能.     

炭化温度对废旧布袋制备活性炭性能的影响及其表征

以水泥厂废旧除尘布袋为原料,KOH为活化剂制备了活性炭.利用热重分析法(TG-DTG)对废旧布袋热解过程进行分析;重点考察了不同炭化温度(400、450、500、550和600℃)对废旧布袋制备活性炭的产率及活性炭的碘吸附值和亚甲基蓝吸附值的影响;同时采用N2吸附等温线对最佳工艺条件制备的活性炭孔隙结构进行了表征.研究结果表明,500℃为最佳炭化温度.最佳炭化温度下制备的活性炭,碘吸附值、亚甲基蓝吸附值和产率分别为1350.72 mg·g-1、97.5 mg·g-1和20.16%.活性炭比表面积高达1228.51 m2·g-1,总孔容达0.7134 cm3·g-1,孔径分布以微孔居多,N2吸附等温线为I型.     

KOH活化法制备牛粪活性炭的研究

以牛粪为原料,采用KOH活化法制备活性炭,并考察了浸渍比、活化剂浓度、活化时间和活化温度等不同制备条件对牛粪活性炭样品性能的影响.实验结果表明,在浸渍比1∶4、KOH质量分数35%、活化时间60min、活化温度700℃条件下制备的活性炭性能最佳,制得的活性炭比表面积为979.8m2·g-1,碘吸附值可达796.37mg·g-1,亚甲基蓝吸附值可达150.30mg·g-1.最后,将制备的牛粪活性炭应用于对Cr(Ⅵ)的吸附,研究了最佳工艺条件下制备的活性炭吸附Cr(Ⅵ)的适宜条件.结果表明,在投加量为8g·L-1时、吸附时间90min、pH值为5和较低温度的适宜条件下,自制牛粪活性炭对Cr(Ⅵ)的吸附量最大.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

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.