垃圾焚烧飞灰中重金属的污染特性

以广西和重庆某生活垃圾焚烧厂的焚烧飞灰为研究对象,研究了飞灰中重金属的化学形态、不同粒径下飞灰中重金属含量及浸出毒性。结果表明:广西垃圾焚烧飞灰中含有5种重金属,且都是以残渣态为主要存在形态;重庆垃圾焚烧飞灰中Cr以残渣态为主要存在形态,Zn、Cu和Cd以醋酸可提取态为主要存在形态,具有较大的潜在毒性,毒性较强的Pb只以醋酸可提取态和可还原提取态两种形态存在,危险性非常高,Mn以可还原提取态为主要存在形态。两地飞灰中含量较高的重金属元素都表现出向小颗粒富集趋势。随飞灰颗粒粒径的减小,各重金属浸出量基本呈增加趋势。相比之下,重庆的垃圾焚烧飞灰中Zn、Cu、Pb和Cd的含量和浸出量都高于广西飞灰。广西飞灰中各粒级的飞灰中各元素浸出量均不超标,而重庆飞灰各粒级的飞灰中Zn、Pb和Cd的浸出量严重超标,表明重庆飞灰属于典型危险废物。     

北京地区生活垃圾焚烧飞灰理化和水洗特性分析

针对飞灰水洗预处理工艺控制难题,分析了北京地区3家生活垃圾焚烧厂飞灰的理化特性,并模拟国内首条生活垃圾焚烧飞灰工业化处置示范线进行了水洗实验研究。结果表明:朝阳飞灰Cl~-含量为18. 73%,其平均粒度最小;高安屯飞灰Cl~-含量最高,达到19. 40%,处理过程中每吨飞灰碳酸钠的消耗量最大,是朝阳飞灰的1. 4倍,是大工村飞灰的2. 9倍;大工村飞灰Cl~-含量为11. 71%,其CaO、SiO_2、Al_2O_3玻璃态含量最高,达到58. 31%,是水洗水泥窑资源化利用的优质配料。掌握北京地区典型垃圾焚烧厂飞灰的特性,可以指导飞灰水洗预处理工艺的灵活控制。     

内配燃料垃圾焚烧飞灰烧结无害化处理实验研究

研究了一种垃圾焚烧飞灰烧结无害化处理的工艺,该工艺是将飞灰与不同比例煤粉混合并添加助熔剂进行造粒烧结。通过对试样进行热流和热重测量,分析了飞灰试样在加热过程中热重变化的规律,并利用XRD、扫描电镜、氮吸附分析仪等仪器分析手段对烧结试样的物相、微观形态和孔隙特性等物理化学性质进行了研究。最后采用电感耦合等离子体发射光谱仪对烧结试样重金属浸出性进行了分析。实验结果为飞灰烧结炉的设计和内配燃料烧结工艺运行参数的制定提供了依据。     

混煤燃烧过程中温度对颗粒物生成特性影响的研究

利用沉降炉研究了混煤燃烧过程中温度对飞灰颗粒尤其是PM10及PM2.5生成特性的影响.试验煤种为不同灰熔点的平朔煤、大优煤及其混煤,燃烧温度分别为1100℃、1200℃、1300℃.采用Malvern MS2000粒度分析仪对收集的飞灰颗粒尺寸分布进行测定.试验结果表明,高灰熔点煤中掺入低灰熔点的煤能增大飞灰颗粒的粒径,减少PM10及PM2.5的排放;对同一煤样,随着温度的升高,飞灰颗粒中PM10及PM2.5所占比例相应减小.     

钢铁冶炼固废与垃圾焚烧飞灰共燃处置过程气相污染物生成特性

利用管式炉燃烧实验模拟水泥窑炉预分解与钢铁窑炉烧结过程,在900℃下开展钢铁尘泥、转炉灰、烧结灰、高炉布袋灰4种典型的钢铁冶炼固废与垃圾焚烧飞灰热利用及共燃过程气相污染物生成特性与排放控制的相关研究,其中,4种钢铁冶炼固废与垃圾焚烧飞灰分别以2∶8、3∶7、4∶6的质量比进行共燃。结果表明：钢铁尘泥、转炉灰、烧结灰、高炉布袋灰分别以20%、20%、30%和40%的比例与垃圾焚烧飞灰共燃,是抑制NO生成、挥发性重金属Pb、Zn挥发的最佳比例。4种钢铁冶炼固废中,转炉灰与垃圾焚烧飞灰共燃对NO生成的抑制效果最好,高炉布袋灰与垃圾焚烧飞灰共燃对Pb挥发的抑制效果最稳定,同时对Zn挥发的抑制效果最佳。该成果可为热处置过程中气体污染物的生成抑制和排放控制技术开发提供参考。     

高温自蔓延法固化处置生活垃圾焚烧飞灰

将高温自蔓延反应用于生活垃圾焚烧飞灰(以下简称飞灰)的无害化处置,探索了Mg-Fe_2O_3-飞灰反应体系中最大飞灰含量(质量分数,下同),评估了不同飞灰含量下的无害化效果,研究了自蔓延反应过程中飞灰中重金属元素的挥发行为,并通过XRD和SEM分析探讨了自蔓延反应固化飞灰中重金属的机制。研究结果表明,系统维持自蔓延的飞灰含量最大为65%;经高温自蔓延处置后,飞灰中Pb、Cd、Cu和Cr的毒性浸出浓度分别由21.51、0.19、0.18和0.58 mg/L降低到0.53、0.12、0.06和0.07 mg/L以下;Pb、Cd和Zn等重金属在自蔓延反应过程中大量挥发,飞灰含量40%时其挥发率分别高达92.24%、88.66%和87.77%,Cr和Cu主要以铬矿物和氧化亚铜的形式固化于产物中。XRD/SEM结果表明飞灰高温自蔓延反应产物以玻璃相为主体,体系中残留重金属与低熔点物质形成固液共存相并随着反应的推进迅速冷却形成密实的固熔体,通过化学固化和物理固封作用固定于玻璃体中。     

生活垃圾焚烧飞灰矿物学特性及重金属分布

生活垃圾焚烧飞灰的矿物学特性是飞灰中重金属赋存环境的直观反映,与重金属在处置环境中的释放和迁移行为密切相关.为掌握重金属在生活垃圾焚烧飞灰中的分布规律,结合X射线衍射、扫描电镜等常规矿物学研究工具及矿物解离分析系统对飞灰的矿物学宏观属性和微观属性进行全面测试.结果表明,飞灰是由矿物相和非矿物相组成,两者之间紧密连生,主要矿物相包括氯盐和方解石、氢氧钙石等多种含钙矿物.重金属元素在飞灰中主要以3种形式存在:均匀分布在无定形的非矿物组分中,以同晶置换赋存在方解石等矿物中以及吸附在特殊矿物如石英、赤铁矿等表面.难挥发性重金属Cu和Cr绝大部分分布在非矿物相中;半挥发性重金属Zn和Cd各有43.92%和60.61%的含量分布在矿物相中,其中,方解石对Cd、赤铁矿对Cr及硅酸盐对Zn存在较强的富集作用.     

生活垃圾焚烧飞灰生物脱氯机制研究

垃圾焚烧飞灰中的高氯含量是限制其在水泥工业中资源化利用的重要因素,如何实现垃圾焚烧飞灰的有效脱氯是飞灰应用于水泥工业亟需解决的关键技术问题.在对我国7个典型垃圾焚烧厂飞灰组成及特征分析的基础上,开发了飞灰与污泥共处置脱氯工艺,结果表明,我国典型生活垃圾焚烧厂飞灰氯含量达4.6%~12.7%;不同地区焚烧飞灰中氯含量差异性比较明显,主要原因是不同地区垃圾组成不同,其中工业垃圾是飞灰中不可溶氯的主要来源之一;对比水洗前后飞灰同步辐射X射线衍射分析结果,飞灰中可溶氯主要以KCl、NaCl、CaClOH形态存在,不可溶氯主要以AlOCl形态存在;飞灰与污泥按质量比8:2混合,并共处置150d后,飞灰氯含量由14%降低至0.03%,满足我国《通用硅酸盐水泥》(GB175-2007)标准所规定的水泥氯含量不高于0.06%的要求;飞灰与污泥共处置发酵产酸使得混合体系pH值降低,促进飞灰中不可溶氯盐向可溶性氯盐转化是飞灰生物脱氯的主要机制.     

利用城市垃圾焚烧飞灰制备微晶玻璃的研究

利用上海御桥垃圾焚烧厂的焚烧飞灰为主要原料,通过添加SiO2、Al2O3、NaOH组分在实验室研制成功了以硅灰石(wollastonite)为主晶相的微晶玻璃.该体系微晶玻璃制备的最佳工艺条件为:熔融温度1500℃、熔融时间1 h,核化温度为920℃,核化时间1.5 h,晶化温度为1150～1180℃,晶化时间为2 h.研究结果表明,硅灰石为主晶相的微晶玻璃对Pb、Cr和Cd重金属具有很强的稳定束缚能力.     

粉煤灰固化处理生活垃圾焚烧飞灰效果研究

为了减少生活垃圾焚烧飞灰中重金属等污染物对环境的危害,以粉煤灰和脱硫石膏为原料对生活垃圾焚烧飞灰中重金属进行安全处理。采用机械力化学法探究了脱硫石膏与垃圾焚烧飞灰掺加比、(脱硫石膏+垃圾焚烧飞灰)与粉煤灰掺加比、球磨频率、球磨时间和养护温度参数对固化体性能的影响。并通过XRD和FTIR手段对垃圾焚烧飞灰中重金属的固化机制进行了研究。研究结果表明,采用机械力化学法能够显著提升粉煤灰的活性,并使制备出的固化体具有较高的抗压强度。当脱硫石膏与垃圾焚烧飞灰掺加比为1∶4,(脱硫石膏+垃圾焚烧飞灰)与粉煤灰为2∶3,球磨频率30 Hz,球磨时间2 h,养护温度60℃时,固化体28 d抗压强度达到22.3 MPa,并采用AAS测得固化体浸出液中Cd和Zn重金属的浸出量分别仅为0.015 mg/L和0.008 mg/L,均远低于GB 5085.3-2007规定限值。XRD和FTIR表征结果表明,固化体水化过程中生成了水化硅酸钙(C—S—H)和钙矾石(AFt)并分别主要以物理包裹和化学吸附的形式实现了垃圾焚烧飞灰中重金属的稳定化。     

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.     

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.     

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.     

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.     

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.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.