垃圾渗滤液场外硝化－原位反硝化脱氮协同填埋场温室气体减排

垃圾卫生填埋是国内外城市垃圾的主要处置方法。垃圾渗滤液是渗入填埋场垃圾的降水混合垃圾降解过程中产生的物质而形成的混合物，是垃圾填埋场向环境排放的主要污染物。渗滤液由于其所含高浓度有机和无机污染物，且其中很多物质有生物毒性或难生物降解，难于治理。特别是到填埋晚期，渗滤液中高浓度的氨氮更是增加了治理的难度。渗滤液场外硝化－原位反硝化是填埋场氮管理的新途径。本文利用从环境中筛选出优势硝化功能菌对渗滤液中的高浓度氨氮进行生物硝化，经硝化后的渗滤液回灌至以垃圾柱模拟的生物反应器填埋场，在填埋场内实现原位反硝化。 上述目标通过以下两部分来实现： 第一部分：渗滤液场外硝化。首先从污水厂的硝化污泥中富集并筛选出硝化功能菌，在模拟氨氮废水中优化。将驯化的硝化功能菌接种于连续式完全混合反应器（CSTR）进行高氨氮渗滤液硝化研究。在200余天的连续运行中，反应器硝化和有机物去除效果良好。在最大氨氮负荷和有机物负荷分别为0.65 g N l-1 d-1 和3.84 g COD l-1 d-1时，氨氮和COD去除率分别高于99%和57%。实验过程中发现，游离氨（FA）和溶解氧（DO）浓度对反应器中亚硝酸盐的积累影响很大。 第二部分：渗滤液原位反硝化。本文利用一个垃圾填充柱模拟生物反应器填埋场，研究了硝化渗滤液回灌对垃圾降解的影响，和回灌的硝化渗滤液中TON（总氧化态氮）对填埋场生物反应器产甲烷作用的影响。最后利用变性梯度凝胶电泳（DGGE）分析了硝化渗滤液回灌对垃圾填埋场菌群结构的影响。结果表明：回灌的TON被完全还原，反硝化为主要反应，最大TON负荷为28.6 mg N kg-1 TS d-1。当垃圾柱TON负荷大于11.4 mg N kg-1 TS d-1时，出现了产甲烷抑制，抑制作用随TON负荷的增加而加强。在此过程中，反硝化逐渐代替产甲烷作用成为填埋场内垃圾降解的主要反应，且更多产生的是清洁的氮气，而非温室气体甲烷。直到实验结束时，回灌硝化渗滤液的垃圾柱的甲烷产量仅相当于对照的2.5%，并且回灌的硝化渗滤液还加速了填埋场垃圾的降解与稳定。通过DGGE进行菌群结构分析发现，由于TON对填埋场的长期作用，反硝化菌增多而产甲烷菌减少。 Landfill still remains the chief method for MSW management around the world. Leachate is a mixture of rainfall permeating through landfill and organic and inorganic matters generated during decomposition of the wastes in the landfills, characterized as highly complicated and refractory wastewater. Ex-situ nitrification and sequential in-situ denitrification represents a novel approach to nitrogen management at landfills. In the present paper, nitrification was carried out in a continuous stirred tank reactor (CSTR) inoculated with nitrifying bacteria which were isolated from municipal WWTP of Chengdu city. The nitrified leachate from CSTR was recirculated to a lab-scale municipal solid waste (MSW) column where in-situ denitrification took place. The above object was achived through two parts as following: First, ex-situ nitification of leachate. After acclimated in simulated wastewater for 3 month, nitrifying bacteria isolated from WWTP nitrifying sludge were added to the CSTR for nitrification. The results over 200 days showed that the maximum nitrogen loading rate (NLR) and the maximum organic loading rate (OLR) was 0.65 g N l-1 d-1 and 3.84 g COD l-1 d-1, respectively. The ammonia and COD removal was over 99% and 57%, respectively. Moreover, the effects of free ammonia (FA) and dissolved oxygen (DO) on nitrification were investigated. Second, in-situ denitrification was studied in a municipal solid waste (MSW) column. Variation of nitrified leachate and its effects on the decomposition of municipal solid waste (MSW) were studied in a lab-scale MSW column to which nitrified leachate was recirculated. Additionally, DGGE was employed to investigate the microbial community of both MSW columns. The results suggested: complete reduction of total oxidized nitrogen (TON) was obtained with maximum TON load of 28.6 mg N kg-1 TS d-1 and denitrification was the main reaction responsible. Methanogenesis inhibition was observed while TON load was over 11.4 mg N kg-1 TS d-1 and the inhibition was enhanced with the increase of TON load. Denitrification gradually took over methanogenesis to become the main reaction responsible for decomposition of MSW while nitrogen gas, a clean byproduct, was generated instead. Till the end of the experiment, the average weekly methane production in the denitrification column was as low as 2.5% of that of the control, and the rate of decompition and stability of MSW was accelerated by the recirculation of the nitrified leachate.Owing to long term exposure of nitrified leachate to landfill, denitrifying bacteria increased and methanogen decreased.

Activated carbons chemically modified by concentrated H2SO4 for the adsorption of the pollutants from wastewater and the dibenzothiophene from fuel oils

The surface properties, porosities, and adsorption capacities of activated carbons (AC) are modified by the oxidation treatment using concentrated H2SO4 at temperatures 150-270 degreesC. The modified AC was characterized by N-2 adsorption, base titration, FTIR, and the adsorption of iodine, chlorophenol, methylene blue, and dibenzothiophene. The treatment of AC with concentrated H2SO4 at 250 degreesC greatly increases the mesoporous volume from 0.243 mL/g to 0.452 mL/g, specific surface areas from 393 m(2)/g to 745 m(2)/g, and acidic surface oxygen complexes from 0.071 meq/g to 1.986 meq/g as compared with the unmodified AC. The base titration results indicate that the amount of acidic surface oxygen groups on the modified AC increases with increasing the treatment temperatures and carboxyls and phenols are the most abundant carbon-oxygen functional groups. The carboxyl groups, COO- species, and hydroxyl groups are detected mainly for the sample treated at 250 degreesC. The mesoporous properties of the AC modified by concentrated H2SO4 were further tested by the adsorption of methylene blue and dibenzothiophene. The AC modified by concentrated H2SO4 at 250 degreesC has much higher adsorption capacities for large molecules (e.g., methylene blue and dibenzothiophene) than the unmodified AC but less adsorption capacities for small molecules (e.g., iodine). The adsorption results from aqueous solutions have been interpreted using Freundlich adsorption models.

Development of a precolumn derivatization method for the determination of free amines in wastewater by high-performance liquid chromatography via fluorescent detection with 9-(2-hydroxyethyl)acridone

A simple, sensitive, and mild method for the determination of amino compounds based on a condensation reaction with fluorescence detection has been developed. 9-(2-Hydroxyethyl)acridone reacts with coupling agent N,N-carbonyldiimidazole at ambient temperature to form activated amide intermediate 9-(2-acridone)oxyethylcarbonylimidazole (AOCD). The amide intermediate (AOCD) preferably reacts with amino compounds under mild reactions in the presence of 4-(dimethylamino)pyridine (base catalyst) in acetonitrile to give the corresponding sensitively fluorescent derivatives with an excitation maximum lambda(ex) 404 mn and an emission maximum at lambda(em) 440 nm. The labeled derivatives exhibit high stability under reversed-phase conditions. The fluorescence intensities of derivatives in various solvents or at different temperatures were investigated. The method, in conjunction with a gradient elution, offers a baseline resolution of the common amine derivatives on a reversed-phase C-18 column. The LC separation for the derivatized amines shows good reproducibility with acetonitrile-water including 2.5% DMF as mobile phase. The relative standard deviations (n = 6) for each amine derivative are <4.5%. The detection limits (at a signal-to-noise ratio of 3) per injection were 0.16-12.8 ng/mL. Further research for the field of application, based on the AOCD amide intermediate as derivatization reagent, for the determination of free amines in real water samples is achieved.

Recovery of protein from discharged wastewater during the production of chitin

Studies were carried out to optimize the conditions for the recovery of protein. The results showed that pH of 6.00 for wastewater, the dosage of 1% chitosan solution in 1% acetic acid aqueous solution of 2.0 ml for 50 ml wastewater and 1% FeCl3 aqueous solution of 2 ml for 50 ml wastewater, the flocculation time of 4.0 h were the optimal conditions for the recovery of protein. The obtained protein sediment contained abundant amino acids, especially isoleucine, methione and lysine that are absent in other protein resource. (c) 2007 Elsevier Ltd. All rights reserved.

Biosorption and desorption of Cd2+ from wastewater by dehydrated shreds of Cladophora fascicularis

The adsorption and desorption of algae Cladophora fascicularis and their relation with initial Cd2+ concentration, initial pH, and co-existing ions were studied. Adsorption equilibrium and biosorption kinetics were established from batch experiments. The adsorption equilibrium was adequately described by the Langmuir isotherm, and biosorption kinetics was in pseudo-second order model. The experiment on co-existing ions showed that the biosorption capacity of biomass decreased with an increasing concentration of competing ions. Desorption experiments indicated that EDTA was efficient desorbent for recovery from Cd2+. With high capacities of metal biosorption and desorption, the biomass of Cladophora fascicularis is promising as a cost-effective biosorbent for the removal of Cd2+ from wastewater.

Sorption and desorption of lead (II) from wastewater by green algae Cladophora fascicularis

Biosorption is an effective method to remove heavy metals from wastewater. In this work, adsorption features of Cladophora fascicularis were investigated as a function of time, initial pH, initial Pb(II) concentrations, temperature and co-existing ions. Kinetics and equilibria were obtained from batch experiments. The biosorption kinetics followed the pseudo-second order model. Adsorption equilibria were well described by the Langmuir and Freundlich isotherm models. The maximum adsorption capacity was 198.5 mg/g at 298 K and pH 5.0. The adsorption processes were endothermic and the biosorption heat was 29.6 kJ/mol. Desorption experiments indicated that 0.01 mol/L Na(2)EDTA was an efficient desorbent for the recovery of Pb(II) from biomass. IR spectrum analysis suggested amido or hydroxy, C=O and C-O could combine intensively with Pb(II). (C) 2006 Elsevier B.V. All rights reserved.

Synthesis and evaluation of a thiourea-modified chitosan derivative applied for adsorption of Hg(II) from synthetic wastewater

In this work, a thiourea-modified chitosan derivative (TMCD) was synthesized through two steps, O-carboxymethylated first and then modified by a polymeric Schiff's base of thiourea/glutaraldehyde. The adsorption behavior of mercury (II) ions onto TMCD was investigated through batch method. The maximum adsorption capacity for Hg(II) was found to be 6.29 mmol/g at pH 5.0 and both kinetic and thermodynamic parameters of the adsorption process were obtained. The results indicated that adsorption process was spontaneous exothermic reaction and kinetically followed pseudo-second-order model. The adsorption experiments also demonstrated TMCD had high adsorption selectivity towards Hg(II) ions when coexisted with Cu(II), Zn(II), Cd(II) and Ca(II) in solution and it could be easily regenerated and efficiently reused. (C) 2010 Elsevier B.V. All rights reserved.

Determination of aliphatic amines from soil and wastewater of a paper mill by pre-column derivatization using HPLC and tandem mass spectrometry (HPLC-MS/MS)

A pre-column derivatization method for the sensitive determination of aliphatic amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by HPLC with fluorescence detection and APCI/NIS identification in positive-ion mode has been developed. The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by the 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent, BCEOC, that could easily and quickly label amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M + H](+) with APCI/MS in positive-ion mode. The collision induced dissociation of the protonated molecular ion formed characteristic fragment ions at m/z 264.1, m/z 246.0 and m/z 218.1, corresponding to the cleavages of CH2CH2O-CO, CH2CH2-OCO, and N-CH2CH2O bonds. Studies on derivatization conditions demonstrated that excellent derivatization yields close to 100% were observed with a 3 to 4-fold molar reagent excess in acetonitrile solvent, in the presence of borate buffer (pH 9.0) at 40 degrees C for 10 min. In addition, the detection responses for BCEOC derivatives were compared with those obtained with CEOC and FMOC as labeling reagents. The ratios I-BCEOC/I-CEOC and I-BCEOC/I-FMOC were, respectively, 1.40-2.76 and 1.36-2.92 for fluorescence responses (here, I was the relative fluorescence intensity). Separation of the amine derivatives had been optimized on an Eclipse XDB-C-8 column. Detection limits calculated from an 0.10 pmol injection, at a signal-to-noise ratio of 3, were 18.65-38.82 fmol (injection volume 10 mu L for fluorescence detection. The relative standard deviations for intraday determination (n = 6) of standard amine derivatives (50 pmol) were 0.0063-0.037% for retention times and 3.36-6.93% for peak areas. The mean intra-and inter-assay precision for all amines were <5.4% and 5.8%, respectively. The recoveries of amines ranged from 96 to 113%. Excellent linear responses were observed with correlation coefficients of >0.9994. The established method provided a simple and highly sensitive technique for the quantitative analysis of trace amounts of aliphatic amines from biological and natural environmental samples.

Proposta metodológica para estimar o potencial de expansão do sistema de integração lavoura-pecuária em nível municipal considerando a legislação ambiental: estudo de caso na microrregião de Bom Despacho, Minas Gerais.

2008

Sistema de suporte ao planejamento e levantamento agrícola municipal.

2006