草酸、壳聚糖与CaO联合调理对污泥脱水性能的影响

为提高剩余污泥脱水性能,本文采用单因素实验确定草酸、壳聚糖和CaO各因素的影响水平范围,基于响应曲面优化法建立了污泥滤饼含水率预测模型,通过粒子群算法计算污泥滤饼含水率预测模型,优化草酸、壳聚糖与CaO联合调理污泥脱水的最佳配比,并分析了污泥调理过程中胞外聚合物（EPS）的变化特性,深入解析了污泥脱水的关键机制.结果表明,草酸、壳聚糖与CaO联合调理污泥能明显提高污泥脱水性能,调理后的污泥滤饼含水率为64.017%,最佳投加量分别为0.377,0.029,0.040g/g;模型拟合度良好（R²=0.9651）,方差分析表明草酸对于污泥滤饼含水率的影响为主要因素;草酸投加量与溶解型EPS（SL-EPS）呈显著正相关关系,而与紧密型EPS（TB-EPS）呈显著负相关关系.该研究成果可为剩余污泥脱水性能的提高提供技术与方法参考.     

NC-PC锚定微量Fe活化PMS降解水中2,4-二氯苯氧乙酸

采用分步热分解法制备了NC-PC（三维多孔碳材料）锚定的微量Fe基催化剂,用于活化过一硫酸盐（PMS）氧化降解水中2,4-二氯苯氧乙酸（2,4-D）.采用透射电子显微镜（TEM）、高精度比表面积仪（BET）、X射线光电子能谱分析（XPS）和电感耦合等离子体发射光谱分析（ICP）对催化剂进行表征.考察了不同金属、制备方法、催化剂投加量、PMS投加量、初始pH值以及水中不同阴离子（Cl^-、NO₃^-、HCO₃^-）对2,4-D降解的影响.结果表明,通过热分解法合成的Fe-NC-PC对2,4-D具有更好的降解效果,当2,4-D初始浓度为0.1mmol/L,初始pH=3.4,催化剂投加量0.15g/L,PMS浓度0.7mmol/L时,反应20min内2,4-D的去除率可达91%.随着催化剂投加量、PMS投加量的提高,2,4-D的降解效果提高;随着初始pH值的提高,2,4-D的降解效率逐渐降低;水中不同阴离子（Cl^-、NO₃^-、HCO₃^-）和腐殖酸（HA）对2,4-D的降解有轻微的抑制作用.通过自由基淬灭实验、EPR测试以及XPS分析了反应的主要活性物种和反应机理,发现材料制备过程中形成的Fe-N_x是主要的反应活性位,能够有效的活化PMS降解水中2,4-D,¹O₂在2,4-D的降解过程中起到主要作用.     

生物淋滤中硫粉对污泥EPS组分和脱水性的影响

为探讨生物淋滤过程中污泥的脱水性能及其与胞外聚合物（EPS）中蛋白质（PN）、多糖（PS）的关系,以硫粉（S⁰）作为底物,设计了不同S⁰投量（0,2,4,6,8g/L）+10%接种物的实验组进行10d淋滤实验.结果表明：溶解态PN、PS含量和污泥比阻（SRF）在淋滤0~2d降低,之后呈上升趋势,结合态PN、PS含量在淋滤0~8d呈下降趋势,之后略微上升,且S⁰投加量越大,上述变化趋势越明显.统计结果发现,SRF与溶解态PN、PS有显著的正相关性（R=0.861、0.875,P<0.01）.说明不同S⁰投加量导致溶解态PN、PS含量变化从而影响了污泥脱水性能,其中溶解态PS的变化对污泥脱水性能作用更大.S⁰投量为8g/L、淋滤时间为2d时,污泥脱水效果最佳,S⁰投量为2g/L、淋滤时间6d效果次之,SRF分别比原污泥降低58%和54%,又由于后者重金属去除率高于前者,推荐S⁰ 2g/L,温度30℃,淋滤时间6d,pH值降至2.66为最适工艺条件.     

超声-生物沥浸-氧化钙联合超高压压滤系统实现市政污泥深度脱水及其泥饼的毒性评估

本研究采用超声-生物沥浸-氧化钙调理联合超高压压滤系统对市政污泥进行深度脱水试验,探讨了其调理过程对污泥脱水效率的影响,并对调理后的脱水污泥的重金属含量及植物毒性进行评估.结果表明,经超声-生物沥浸-氧化钙调理后,比阻（SRF）去除率和结合水去除率分别达到90.12%和72.21%.经预调理联合超高压压滤系统处理后,泥饼含水率降低至49.94%,泥饼中Cr 、Cu、Cd、 Zn、As 和Pb的去除率分别为42.41%、36.50%、30.92%、27.97%、25.94%、22.11%,白菜发芽指数大于80%.通过分析污泥理化性质及滤液有机物含量,阐明该联合技术的作用机理.首先,超声预处理后,污泥结构被破坏,造成污泥粒径d_0.5减小、zeta电位上升,污泥中多糖和蛋白质被释放,从而改善脱水性能,促进污泥中重金属释放,植物毒性降低;经超声-生物沥浸调理后,污泥粒径d_0.5进一步减小、zeta电位趋近于中性,滤液中酪氨酸/色氨酸类氨基酸类有机物和酪氨酸/色氨酸类蛋白有机物被降解且疏水性的腐殖酸和富里酸类有机物含量升高,污泥脱水性能进一步提高,泥饼重金属含量进一步下降,但植物毒性反而加强;最后添加氧化钙后,污泥颗粒被重新絮凝,形成刚性骨架,增加了污泥的可压缩性能,在高压压滤过程释放出更多有机物,最终实现了污泥深度脱水,重金属总量减少,植物毒性显著降低.此外,经济分析表明该联合工艺具有一定潜在推广应用价值.     

不同无机盐对市政厌氧污泥脱水性能的影响

为实现市政厌氧污泥高效深度脱水与无害化、资源化利用,本研究选用三种无机盐调理市政厌氧污泥,主要考察其对厌氧污泥脱水性能与胞外聚合物的影响。结果表明:FeCl3和Al Cl3均能显著改善厌氧污泥的脱水性能,当投加量为60mg/g (无机盐与干污泥质量比)时,FeCl3和Al Cl3处理后污泥TTF较初始厌氧污泥分别缩短81. 03%和80. 00%,而PAC改善效果不明显。进一步实验发现,经不同浓度无机盐调理后污泥含水率与污泥比阻均有不同程度下降,其中FeCl3和Al Cl3调理后污泥改善程度最显著,无机盐浓度越高,污泥含水率和污泥比阻越低;经FeCl3和Al Cl3调理后污泥中多糖和蛋白质含量较高,当FeCl3投加量为40mg/g (无机盐与干污泥质量比)时,其多糖和蛋白质含量达到最高;当Al Cl3投加量为20mg/g (无机盐与干污泥质量比)和40mg/g (无机盐与干污泥质量比)时,其多糖和蛋白质含量分别达到最高。     

缺氧酸化联合零价铁-过氧化氢改善污泥脱水性能的研究

为探讨缺氧酸化联合零价铁(ZVI)-过氧化氢(H_2O_2)调理对污泥脱水性能的影响,本文通过单因素试验,以污泥比阻(SRF)作为参考指标,系统考察了调理条件对污泥脱水性能的影响.同时,在试验的最佳调理条件下,分析了污泥各层胞外聚合物(EPS)有机物质量浓度及荧光光谱强度以阐明该联合作用机理.结果表明,当初始pH为2,ZVI投加量为280 mg·g~(-1)(以干污泥量(DS)计,下同),缺氧时间为4 h,H_2O_2投加量为30 mg·g~(-1)(以DS计,下同),类芬顿反应时间为10 min时,SRF降低了90.39%,处理效果较单独类芬顿处理提升了1倍.机理探究试验表明,在缺氧条件下,酸化处理可加速污泥的水解,溶解得到更多的二价铁离子,促使EPS结构发生改变;ZVI-H_2O_2调理可有效地氧化部分EPS,使得紧密结合胞外聚合物(TB-EPS)破解转化至松散结合胞外聚合物(LB-EPS)和上清液胞外聚合物(SB-EPS).EPS分析结果表明,蛋白质的减少能有效提高污泥脱水性能,腐殖酸和富里酸类有机物的产生能提高污泥疏水性能.此外,ZVI的再次利用效率高,重复利用仍能使SRF降低率达到82.04%.因此,缺氧酸化联合ZVI-H_2O_2处理能实现污泥的水解、氧化和絮凝过程,达到改善污泥脱水性能的目的.     

Cl-/PMS体系降解甲氧苄啶的效能与机理

采用氯离子（Cl^－）作为阴离子活化剂,活化单过硫酸氢钾（PMS）氧化降解甲氧苄啶（TMP）.研究了Cl^－/PMS体系降解TMP中起主要作用的活性物种,同时考察了Cl^－浓度、PMS投加量、初始pH值对降解效果的影响,并研根据中间产物推断了TMP降解路径.实验结果表明,Cl^－/PMS体系中的主要活性物种是Cl^－和PMS直接反应生成的活性氯.降解过程符合拟一级反应动力学模型（R²>0.99）;随着Cl^－浓度和PMS投加量增加,反应速率常数k_obs增大;初始pH范围在5.0~9.0范围内,随着pH值的增大,TMP的去除率先减小后增大;TMP主要经历了氯取代和羟基取代过程,其核心结构上没有实质性的分解.     

调理剂Fenton/CaO对深度脱水市政污泥燃烧特性的影响

采用超高压板框压滤法进行污泥脱水,制备了3种Fenton/Ca O调理的深度脱水污泥.同时,利用热重分析仪(TG/DTG)研究了Fenton/Ca O投加量和升温速率对深度脱水市政污泥燃烧特性的影响,获得其燃烧特性指数,并建立了燃烧动力学方程.研究表明,Fenton/Ca O调理污泥燃烧过程中有3个失重阶段:水分的析出、挥发分的析出与燃烧、部分挥发分与固定碳的燃尽.与原泥(S1)对比研究可知,调理污泥S2(调理剂折算量Fe2+/H2O2/Ca2+=30/30/70 mg·g-1DS)、S3(调理剂折算量Fe2+/H2O2/Ca2+=50/30/100 mg·g-1DS)的燃尽指数Cb较小,S4(调理剂折算量Fe2+/H2O2/Ca2+=70/30/120 mg·g-1DS)的燃尽指数Cb较大,说明调理剂投加较多时(S4)有利于污泥的燃尽.而3种调理污泥的挥发分释放特性指数D分别增大为原泥的1.10、1.97、1.73倍,可燃性指数C及综合燃烧特性指数S分别降低为原泥的78%~95%、52%~75%,说明增加调理剂用量提升了污泥的初期燃尽率,却降低了污泥的整体燃烧性能.调理污泥的对比研究可知,S3的燃烧特性指数(D、C、S)最大,说明适量的调理剂投加(S3)能在调理污泥中获得最佳的燃烧性能.利用Ozawz-Flynn-Wall法和Kissinger-Akahira-Sunose法计算得到原泥S1及调理污泥(S2、S3、S4)燃烧的质量平均表观活化能,发现调理后污泥的质量平均表观活化能Em1(阶段Ⅰ)下降,但Em2(阶段Ⅱ)提高,整体活化能Em下降;S3获得最低的Em.     

磁性壳聚糖改善污泥脱水性能的研究

采用天然壳聚糖为原料,戊二醛为交联剂,Fe₃O₄为磁核制备磁性壳聚糖,以改善污泥脱水性能.考察了磁性壳聚糖投加量、污泥pH值、调理时间对磁性壳聚糖改善污泥脱水性能的影响,探讨了磁性壳聚糖的作用机理,并通过响应面法研究了磁性壳聚糖和CPAM复配处理污泥对污泥脱水性能的影响.结果表明,保持污泥pH值为6.8时,经20mg/L的磁性壳聚糖调理30min后,污泥比阻（SRF）和含水率（MC）分别由原污泥的13.8×10¹²m/kg和98.7%降低至4.8×10¹²m/kg和75.5%,说明磁性壳聚糖明显改善了污泥脱水性能.响应面实验所拟合的响应值为污泥SRF的二次模型P（Prob>F）<0.05、R²=0.98>0.90,响应值为污泥MC的二次模型P（Prob>F）<0.05、R²=0.95>0.90,表明模型显著,且实验设定变量之间的相关性较好.根据响应值的分布情况,确定污泥脱水的最佳条件为磁性壳聚糖18mg/L、CPAM26mg/L、调理时间27min,相应SRF和MC分别为3.3×10¹²m/kg和59.5%,污泥脱水效果较单独采用磁性壳聚糖或CPAM时得到了明显的提高.     

不同调理剂对厌氧石化污泥脱水性能的影响研究

以厌氧消化后的石化污泥为研究对象,研究聚合硫酸亚铁(PFS)、聚丙烯酰胺(PAM)、聚合氯化铝(PAC)、Fenton试剂对厌氧石化污泥脱水性能的影响,再对调理后的厌氧污泥通过板框压滤机压滤脱水,考察其脱水难易程度。研究结果表明:相比无机絮凝剂PFS、PAC和有机絮凝剂PAM,Fenton试剂(七水合硫酸亚铁加到15,20,25 g/L时,H_2O_2溶液投加量为5 m L/L)的调理效果较好,调理后污泥的毛细吸水时间分别降低至36.82,18.3,27.28 s,污泥比阻分别降低至4.22×1011,1.23×1011,2.45×1011cm/g;采用FPS、PAC、PAM、Fenton(H_2O_2溶液投加量为5 m L/L,Fe SO4·7H2O加到15,20,25 g/L时)调理后的污泥,经过板框脱水后的泥饼含水率分别为68.65%、64.19%、67.21%、57.46%、55.83%、59.36%。由此可见,最优的厌氧石化污泥脱水调理剂为Fenton试剂(Fe SO4·7H2O、H_2O_2投加量分别为20 g/L、5 m L/L),该研究对厌氧石化污泥的高干脱水和减量化具有参考价值。     

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.