飞灰中二英热脱附行为的研究

研究了垃圾焚烧产生的飞灰中二噁英在隔绝空气受热条件下的热脱附行为及规律.通过气相和固体残留中二噁英的含量分析,推测了二噁英在不同温度条件下可能发生的几种化学反应和物理变化,同时研究了17种有毒二噁英的热脱附效率和飞灰的最佳热脱附条件.PCDD/Fs在200℃和300℃下平均脱附率分别为96.2%和95.5%,而400℃下的平均脱附率高达99.7%.结果表明,在300℃加热条件下,飞灰中的PCDD/Fs主要发生脱氯降解反应.在400℃下,飞灰中发生大量的前体合成反应,使PCDD/Fs含量显著增加.     

水泥窑协同处置生活垃圾焚烧飞灰过程中二噁英的迁移和降解特性

为了解生活垃圾焚烧飞灰中的二噁英在水泥脱氯预处理过程中的迁移特性以及在水泥窑内的热降解特性,依托北京市琉璃河水泥有限公司的生活垃圾焚烧飞灰水泥窑协同处置示范线,开展了生活垃圾焚烧飞灰的水洗脱氯预处理和水洗后飞灰向水泥窑投加的工程试验研究.结果表明:烘干烟气中和水泥窑窑尾烟气中二噁英排放浓度低于GB 30485—2013《水泥窑协同处置固体废物污染控制标准》中所规定的标准限值(以I-TEQ计)为0.1 ng/m~3,结晶氯盐中二噁英含量(以I-TEQ计)仅为2.8 ng/kg;以每h进入水洗罐的原飞灰中所含二噁英量为100%计,经过水洗处理后,99.97%的二噁英仍留在脱氯飞灰中,仅有0.08%和0.14%的二噁英分别通过烘干废气和结晶盐排出;以每h投入水泥窑窑尾烟室的飞灰所含二噁英为100%计,仅有0.82%、0.13%和0.002%的二噁英分别随窑灰、熟料、烟气排出,飞灰中的二噁英在水泥窑内的消减率达到了99%以上,实现了较为彻底的降解.     

关于医疗垃圾飞灰中二噁英在惰性气氛下的低温热脱附研究

以医疗垃圾焚烧炉布袋除尘器前管道内飞灰(BG)及布袋除尘器后飞灰(AG)为对象,研究不同温度及时间段下其在管式炉中的热脱附特性.结果表明,在低温氮气气氛下,热脱附作用较为明显,2种飞灰中的二噁英都有了不同程度的脱除,其中布袋前飞灰中二噁英的脱除率为82.9%～99.9%之间,毒性当量脱除率为77.3%～99.8%,布袋后飞灰中二噁英的脱除率为66.8%～99.8%之间,毒性当量脱除率为43.5%～99.6%.检测收集到的实验尾气,发现了二噁英的存在,且在300～350℃这个温度段生成量最多,且生成的有毒二噁英同系物中以OCDD为主.通过比较发现,当温度为400℃,加热时间为45 min时2种飞灰中的二噁英脱除效率最高.鉴于惰性气氛下的热脱附对处理飞灰中的二噁英具有较好的作用,可将其大规模应用于实际工程中.     

硫氨磷基阻滞剂对飞灰特性的影响及对二噁英的阻滞效果

阻滞剂技术由于操作简单、成本低和效率高等优点,被广泛应用于实际生活垃圾焚烧炉,逐渐成为控制二噁英生成的重要技术之一。选取某台典型循环流化床生活垃圾焚烧炉为研究对象,通过高精度给料设备向余热锅炉两侧喷射硫氨磷基阻滞剂,研究阻滞剂对飞灰物化特性影响及其对二噁英的阻滞效果。结果表明:硫氨磷基阻滞剂对飞灰中的PCDD/Fs有很好的阻滞效果,喷射阻滞剂后飞灰中PCDD/Fs毒性当量从2.31 ng I-TEQ/g降至0.23 ng I-TEQ/g,阻滞率达到90.0%;阻滞剂主要通过减少氯源、改变飞灰粒径及表面特性等实现飞灰中二噁英的高效阻滞。此外,阻滞剂对飞灰中部分重金属有一定的固化作用,其中对Pb固化效果最好,达到49.02%。该成果可为后续硫氨磷基阻滞剂的工业化应用提供技术支撑。     

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。     

医疗废物焚烧飞灰二噁英的热处理研究

比较了医疗废物焚烧飞灰在温度200～450℃,流动氮气和静态空气气氛中二噁英气固相行为变化.在流动氮气条件下,固相二噁英随温度升高逐渐增加,350℃下飞灰二噁英浓度升至最高,毒性当量浓度和总浓度分别增加了46.0%和26.0%,随后随着温度升高,二噁英含量逐渐降低,450℃条件下浓度减少至最低,分别减少了86.8%和80.5%.在静态空气下,固相二噁英随温度至250℃条件下,飞灰二噁英浓度升至最高,毒性当量浓度和总浓度分别增加了20.7%和28.7%,随着温度进一步升高,二噁英含量逐渐降低,450℃条件下浓度减至最低,分别减少了99.5%和99.5%.气相只有少量二噁英产生,仅占总产生量的0.11%～2.16%.本实验研究飞灰的最佳热处置条件为:静态空气条件下,450℃处置1 h.本研究中,分解反应在PCDDs与PCDFs的降解过程起到主要作用,而脱氯与脱附仅为次要作用.     

水洗-球磨法降解飞灰中二噁英的研究

从珠三角地区2家典型垃圾焚烧厂采集飞灰,通过分析飞灰中金属及二噁英异构体的组成和分布特性,提出了水洗球磨法处理飞灰的新工艺.结果表明,飞灰中细颗粒物所占的比重大,80%以上的颗粒集中在2~100μm粒径之间,二噁英主要集中的粒径范围是30~53μm.飞灰中的二噁英包括多氯二苯并呋喃类(PCDFs)和多氯二苯并对二噁英类(PCDDs)两大类,二噁英的17种主要异构体中含量最大的是OCDD,毒性当量浓度最大的物质为2,3,4,7,8-Pe CDF.水洗后钾盐钠盐大量溶出,而二噁英是水难溶性物质,水洗后98%以上仍在固相中.使用球磨法降解飞灰水洗渣中的二噁英可以实现较好的降解率,特别是当使用双金属球磨法时,降解率可以达到93.20%.球磨过程中PCDDs类物质优先降解,且PCDFs类物质可能会转化成PCDDs类物质.当球磨反应进行到20 h时,球磨时间过长造成了二噁英的二次生成.     

生活垃圾焚烧飞灰二噁英控制技术研究进展

生活垃圾焚烧飞灰含有二噁英等有机物和Cr、Hg等重金属,是高度危险的固体废物,已成为二噁英污染的主要来源之一。针对飞灰中二噁英的不同解毒技术研究现状,系统阐述了近年来不同技术的原理、研究现状及发展趋势等,指出具有较大工业化应用前景的是水泥窑协同处置和低温热解技术。水泥窑协同处置技术可实现二噁英高效降解,且无二次污染物产生,局限性是该技术需要依托熟料生产线,飞灰水洗预处理投资运行成本相对较高;低温热解技术可高效实现飞灰中二噁英的脱除,局限性是存在二噁英从固相转移至气相,通常集成其他气相二噁英降解技术,如催化氧化等技术,可实现气相二噁英的高效降解,能耗及投资成本相对较低。并对飞灰中二噁英未来的降解技术和发展方向进行了展望,旨在为飞灰二噁英解毒技术的实用研究提供理论研究基础。     

添加剂对垃圾焚烧飞灰熔融过程二不断噁英分解的影响

为了研究添加剂对垃圾飞灰熔融处理过程中二噁英分解特性的影响，选择碱性氧化物CaO和液体陶瓷(LC)2种添加剂，改变温度、气氛和熔融时间研究2种添加剂对二噁英分解率的影响．研究表明CaO对二噁英分解影响随气氛不同而改变，氧化气氛下，加入CaO使二噁英的分解率略微降低，而在还原气氛下则会使二噁英分解率升高．液体陶瓷添加剂对熔融过程二噁英分解有显著影响．1400℃时，随着LC添加比例由0增加到10％，二噁英分解率则从99．997％升高到100％．同时加入10％的LC可以使二噁英的完全分解温度由无添加剂时的1460℃降低至1100℃．     

稳定化飞灰填埋处置环境中二噁英溶出影响因素研究综述

垃圾焚烧飞灰是一种富集二噁英类污染物的危险废物。随着我国垃圾填埋场从原生垃圾填埋向焚烧残渣(主要为稳定化飞灰)填埋转型,稳定化飞灰中的二噁英溶出将是未来填埋场渗滤液污染的重要来源之一,溶出过程受填埋环境中DOM(DOC、DHM、HA等)、pH值、表面活性剂、非有机溶剂和微生物作用等多种因素的共同影响。目前对填埋稳定化飞灰中二噁英的溶出风险问题尚缺乏全面认识。综述了国内外关于垃圾焚烧飞灰中二噁英的典型含量和分布特征,重点总结了稳定化飞灰填埋处置环境中影响二噁英溶出的主要因素及影响规律,分析了二噁英的溶出风险性。指出应从飞灰中二噁英产生的源头、过程以及最终处置等方面加强对二噁英的减量化,并开展关于共填埋处置环境或多因素交互影响条件下二噁英溶出和转化机制以及风险评估方法学的研究。     

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.     

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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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.     

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.     

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.     

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.