Magnetic ion exchange treatment of stabilized landfill leachate

Stabilized landfill leachate is characterized by a high concentration of non-biodegradable organic matter, which is similar in chemistry to dissolved organic matter (DOM) in the natural aquatic environment. Magnetic ion exchange (MIEX) resin treatment is well-studied in drinking water for removal of DOM from natural waters. There are fewer studies evaluating MIEX treatment of waste waters, and there is no previous work evaluating MIEX treatment of landfill leachate. This work systematically evaluated MIEX treatment of stabilized landfill leachate and evaluated the results in the context of previous studies of MIEX treatment of natural and waste waters. Five leachates from four landfills were evaluated as a function of MIEX resin dose, mixing time, and regeneration efficiency. MIEX resin removed DOM from landfill leachate, even in the presence of a reported high background concentration of inorganic ions. MIEX resin that was exhausted with leachate DOM was effectively regenerated with a concentrated NaCl solution, and regenerated MIEX resin performed similarly to virgin resin. For a majority of the leachates, the removal trend for MIEX resin was color > UV-absorbing substances > dissolved organic carbon ≈ COD > total nitrogen. Finally, MIEX resin removed a wider range of DOM from leachate than coagulation. The most important contribution of this work is that MIEX treatment of leachate followed very similar trends as MIEX treatment of natural waters, which will allow previous MIEX data to be used to estimate the treatment efficiency of other waste waters.     

光催化氧化降解垃圾渗滤液中溶解性有机物

研究了UV-TiO2光催化氧化降解垃圾渗滤液过程中溶解性有机物(DOM)的变化特征。结果表明:在适宜条件下,UV-TiO2光催化氧化降解垃圾渗滤液的色度、COD和DOC的去除率分别可达97%、72%和60%;紫外光谱分析说明渗滤液DOM中包括多种含有共轭双键、羰基的大分子有机物及多环芳香类化合物,不同光催化处理液中DOM具有基本一致的结构单元和官能团;红外光谱分析说明渗滤液DOM中含有大量包括羟基、羧基、氨基和苯环的芳香族化合物,在光催化处理液中这几种官能团都能被有效降解;GC/MS分析结果表明,渗滤液DOM中含有72种有机污染物,醇类、羧酸和酮类分别为25、14和12种;在光催化72 h处理液中,有机物减少为44种;酯类和醇类较多,分别为12种和16种;酮类8种,羧酸没有检出。     

Dissolved organic matter with multi-peak fluorophores in landfill leachate

Dissolved organic matter (DOM) sampled from municipal landfill leachate of different ages with/without anoxic or aerobic treatment, was intensively fractionated via size exclusion chromatography (SEC) and hydrophobic resins, and was studied with fluorescence excitation and emission matrix (EEM). Six fluorophores with multiple EEM peaks (fluorophore A-F) were identified based on the collected EEM spectra and validated by bi-variate analysis, principal component analysis, and parallel factor analysis, as follows (excitation wavelength Ex and emission wavelength Em): (Ex 240, 310, 360 nm, Em 460 nm), (Ex 220, 280 nm, Em 340 nm), (Ex 220, 270 nm, Em 300 nm), (Ex 220, 280 nm, Em 360 nm), (Ex 230, 320 nm, Em 420 nm) and (Ex 220, 310 nm, Em 400 nm). The spectral characteristics of these fluorophores were discussed using fractional EEM and apparent molecular weight (AMW) data obtained via SEC analysis. The triple peak flurophore A was pointed at a hydrophobic acid or hydrophobic neutral compound with a pyrenyl functional group of AMW 2500-3500 Da, which displayed an excitation wavelength at 360 nm and a fluorescence intensity ratio of 6.70(+/-1.79):1.70(+/-0.41):1 (fluorescent intensities of Ex 240:Ex 310:Ex 360 nm at Ex 460 nm). This compound is observed to be refractory in landfilling or in anoxic/aerobic treatments, and is specific to this leachate contamination. This paper revealed that the coupling of SEC and EEM can be useful to track the fluorescent DOM fraction in landfill leachate.     

Effects of landfill leachate effluent and bisphenol A on glutathione and glutathione-related enzymes in the gills and digestive glands of the freshwater snail Bellamya purificata

Environmental contaminants with estrogenic activity have recently attracted attention due to their potential detrimental effects on the reproduction of human and wildlife. The aim of this study was to evaluate the use of endogenous glutathione and glutathione-related enzymes as biomarkers of exposure to landfill leachate effluent and bisphenol A (BPA) in the freshwater snail, Bellamya purificata. Following exposure to 1%, 5% and 10% landfill leachate effluent and 1, 10, 50 and 100mugl(-1) BPA for 0, 2, 7 and 15d, activities of glutathione S-transferase (GST), selenium-dependent glutathione peroxidase (SeGPx) and glutathione reductase (GR) and levels of total glutathione were measured in the gills and digestive glands of the snails. GST and total glutathione were the most sensitive parameters in both exposure scenarios. GST activities increased by about 80%, while total glutathione decreased to 70% and 80% in the gills and digestive glands, respectively. In contrast, SeGPx and GR activities remained at the same levels in all the treatment groups compared with those of controls. The results indicated that among glutathione and glutathione-related enzymes, GST activity and total glutathione level, which showed dose-dependent dynamics, could be used as biomarkers of aquatic ecosystems contaminated with landfill leachate.     

Attenuation of landfill leachate by UK Triassic sandstone aquifer materials: 2. Sorption and degradation of organic pollutants in laboratory columns

The sorption and degradation of dissolved organic matter (DOM) and 13 organic micropollutants (BTEX, aromatic hydrocarbons, chloro-aromatic and -aliphatic compounds, and pesticides) in acetogenic and methanogenic landfill leachate was studied in laboratory columns containing Triassic sandstone aquifer materials from the English Midlands. Solute sorption and degradation relationships were evaluated using a simple transport model. Relative to predictions, micropollutant sorption was decreased up to eightfold in acetogenic leachate, but increased up to sixfold in methanogenic leachate. This behaviour reflects a combination of interactions between the micropollutants, leachate DOM and aquifer mineral fraction. Sorption of DOM was not significant. Degradation of organic fractions occurred under Mn-reducing and SO₄-reducing conditions. Degradation of some micropollutants occurred exclusively under Mn-reducing conditions. DOM and benzene were not significantly degraded under the conditions and time span (up to 280 days) of the experiments. Most micropollutants were degraded immediately or after a lag phase (32–115 days). Micropollutant degradation rates varied considerably (half-lives of 8 to >2000 days) for the same compounds (e.g., TeCE) in different experiments, and for compounds (e.g., naphthalene, DCB and TeCA) within the same experiment. Degradation of many micropollutants was both simultaneous and sequential, and inhibited by the utilisation of different substrates. This mechanism, in combination with lag phases, controls micropollutant degradation potential in these systems more than the degradation rate. These aquifer materials have a potentially large capacity for in situ bioremediation of organic pollutants in landfill leachate and significant degradation may occur in the Mn-reducing zones of leachate plumes. However, degradation of organic pollutants in acetogenic leachate may be limited in aquifers with low pH buffering capacity and reducible Mn oxides. Contaminants in this leachate present a greater risk to groundwater resources in these aquifers than methanogenic leachate.     

城市生活垃圾填埋初期有机质演化规律研究

为阐明生活垃圾填埋初期有机质演化规律,于填埋场打井采集填埋1～3年3个不同时期垃圾样品,用水浸提制备水溶性有机物(DOM)。采用红外光谱、同步荧光光谱及紫外光谱,对浸提液中DOM的结构和演化特征进行了研究。结果显示,生活垃圾中含有脂肪类、蛋白类、糖类及木质素类物质,在填埋初期,有机质中的脂肪类、蛋白质类、糖类及木质素类物质均发生了降解,羧基、氨类及水溶性芳香结构物质减少,DOM分子量降低。研究结果表明,垃圾填埋初期有机质以降解为主。     

Biodegradation of organic matters from mixed unshredded municipal solid waste through air convection before landfilling

Landfilling is a dominant municipal solid waste (MSW) disposal method in most developing countries. In China, approximately 85% of the generated MSW is being disposed of in the landfills. The amount of MSW is growing rapidly with the rate of approximately 8-10% annually, which contains a high quantity of moisture and organic matters. The problems of leachate treatment and landfill gas (LFG) emissions are increasing gradually. Reducing the hazard before emplacement, pretreatment of MSW before landfilling has become very important for the conventional landfill. In this study, aerobic pretreatment of mixed MSW was used, and much attention has been given to the natural convection of air in the mixed and unshredded MSW for bioconversion of organic matter (OM). This study is an attempt to investigate aerobic pretreatment suitability for the mixed and unshredded MSW at Beijing. A pilot-scale aerobic pretreatment simulator (APS) was developed at Beishen Shu Landfill in Beijing. To work out the biodegradation of the OM in the APS, fresh and pretreated MSW samples were collected and analyzed for OM, moisture content, temperature, chemical oxygen demand, total organic carbon, carbon, nitrogen, hydrogen, lignocelluloses, and biochemical methane potential at various stages of the pretreatment. Furthermore, results of the fresh and pretreated MSW are compared. Significant reduction in the observed parameters of the pretreated waste samples is observed. This work demonstrates that pretreatment is significantly effective in reducing the landfill emissions that is leachate and LFG.     

回灌型准好氧填埋场脱氮特性及加速稳定化研究

采用2个模拟填埋生物反应器,1号柱渗滤液简单回灌,2号柱为渗滤液回灌准好氧联合运行方式,研究了渗滤液回灌准好氧生物反应器填埋场的脱氮特性及加速垃圾稳定化特性.研究结果表明:渗滤液回灌准好氧填埋场具有很强的脱氮能力,2号柱由厌氧运行方式改为准好氧条件下,渗滤液中的氨氮和凯式氮浓度分别由最大值的3 198 mg/L和3 345 mg/L降低到第160 d的73 mg/L和81 mg/L,去除率分别为97.7%和97.6%,pH快速升高到8.0左右,COD浓度快速降低.渗滤液中溶解性有机物(DOM)分级结果表明,2号柱HA和FA含量的增加明显快于1号柱.2号柱DOM的三维荧光光谱特性发生了较大变化,荧光基团从60 d结构简单的类蛋白物质转变为95 d结构复杂的类胡敏酸和富里酸物质,而l号柱渗滤液DOM荧光基团一直是结构简单的类蛋白物质.结果表明回灌准好氧生物反应器填埋场的稳定化速度远快于简单回灌的生物反应器填埋场.     

Investigating the effect of landfill leachates on the characteristics of dissolved organic matter in groundwater using excitation–emission matrix fluorescence spectra coupled with fluorescence regional integration and self-organizing map

For the purpose of investigating the effect of landfill leachate on the characteristics of organic matter in groundwater, groundwater samples were collected near and in a landfill site, and dissolved organic matter (DOM) was extracted from the groundwater samples and characterized by excitation–emission matrix (EEM) fluorescence spectra combined with fluorescence regional integration (FRI) and self-organizing map (SOM). The results showed that the groundwater DOM comprised humic-, fulvic-, and protein-like substances. The concentration of humic-like matter showed no obvious variation for all groundwater except the sample collected in the landfill site. Fulvic-like substance content decreased when the groundwater was polluted by landfill leachates. There were two kinds of protein-like matter in the groundwater. One kind was bound to humic-like substances, and its content did not change along with groundwater pollution. However, the other kind was present as “free” molecules or else bound in proteins, and its concentration increased significantly when the groundwater was polluted by landfill leachates. The FRI and SOM methods both can characterize the composition and evolution of DOM in the groundwater. However, the SOM analysis can identify whether protein-like moieties was bound to humic-like matter.     

Transformations of dissolved organic matter in a landfill leachate--a size exclusion chromatography/mass spectrometric approach

The aim of the present study was to search for qualitative changes in the landfill leachate DOM along a groundwater gradient. The study was focused on DOM characteristics of importance for its interaction with pollutants, such as molecular weight distribution and aromaticity. It was concluded that the leachate DOM underwent substantial qualitative changes along the investigated gradient at the Vejen landfill, Denmark. The molecular weight decreased, the polydispersity increased, and the aromaticity varied with the lowest values found in the middle of the gradient. The high aromaticity in the end of the gradient may explain the higher DOM binding capacity towards hydrophobic compounds seen earlier in these samples. The relative abundance of ions with mass to charge ratio (m/z) of 600-1200 seemed to be very stable along the gradient, indicating that the observed qualitative changes of the DOM is mostly attributed to changes in the m/z 100-600 range. The DOM seemed to become more similar to fulvic acids present in uncontaminated groundwater with respect to molecular weight and polydispersity along the gradient.     

垃圾渗滤液同时硝化反硝化处理中有机污染物去除效果

采用同时硝化反硝化对某垃圾填埋场渗滤液进行处理,并对有机物去除效果进行分析。实验结果表明,反应器对渗滤液中COD、氨氮、总氮和部分有机物具有较好的处理效果,COD、氨氮和总氮的平均去除率为82.34%、99.82%和65.31%。GC-MS分析总共检测出53种主要有机污染物,其中邻苯二甲酸二丁酯等29种有机物的去除率达100%,乙基苯等5种有机物的去除率高于90%,邻苯二甲酸二异辛酯等8种有机物的去除率介于60%和90%之间,此外还有4-苯基戊醇等5种有机物去除率低于60%。反应器内存在亚硝氮途径的脱氮反应形式。     

Treatment of landfill leachate by electrochemical oxidation and anaerobic process.

The removal performance of typical refractory organic compounds in landfill leachate was investigated during the electrochemical (EC) oxidation and anaerobic process combined treatment system in this paper. The results indicated that the treatment of landfill leachate by the combined system was highly effective. The toxicity of leachate was notably decreased after the electrochemical oxidation process and the biodegradability was improved. The concentration of the organic acid with low molecular weight in the leachate increased from 28% to 90% based on the biodegradability assays after the EC oxidation process. The anaerobic digestion could further remove the residual organic compounds. At a hydraulic retention time (HRT) of 16 hours and an organic loading rate (OLR) of 8 kg COD/m3 d, the concentration of COD, SS, ALK, VA, N-TKN, N-NH4+ and P-PO4(3)- [corrected] in UASB effluent were 532, 12, 6744, 400, 540, 455 and 11.6 mg/L, respectively, with approximately 90% removal efficiency of COD. The organic compounds in the landfill leachate revealed different degradation characteristics in the combined system. p-chloroaniline, bisphenol A, 6-methyl-2-phenyl-quinoline, dimethylnaphthaline and N'-(2-methyl-4-chlorophenyl)-N-cyclohexyformamidine, classified into the first group in this paper, were completely removed by the EC oxidation and did not reappear in the effluent of the UASB reactor. Phenylacetic acid, 3-methyl-indole and N-cyclohexyl-acetamide, called the second group, were completely removed, but reappeared in the UASB reactor. 4-methyl-phenol, 3,4-dihydroisoquinoline, 2(3H)-benzothiazolone, exo-2-hydroxycineole and benzothiazole, the third group, were degraded little in the EC oxidation process, but extensively removed by the anaerobic process. Benzoic acid, benzenepropanoic acid and 2-cyano-3,5-dimethyl-1-hydroxypyrrole, the fourth group, concentration obviously increased in the EC process, but was completely removed in the UASB reactor. The content of volatile fatty acids (VFAs) markedly increased from 0.68% in the leachate to 16.18% in the effluent from the electrochemical oxidation process (EC(effl)). In addition, the degradation rate of organic compounds from the landfill leachate was different in the EC oxidation and anaerobic process.     

垃圾填埋场渗滤液生物处理尾水的性质研究

采用多种先进测试分析仪器对不同月份的垃圾填埋场渗滤液生物处理尾水(简称渗滤液尾水)进行了全面的分析.结果表明,经生物处理后的渗滤液尾水难以进一步生物降解,仍然有很强的污染性,COD和NH3-N仍分别高达419～622、12.4～174.0 mg/L,未达到国家排放标准,且仍含有多种环境优先控制污染物.除有机物外,渗滤液尾水中还有部分无机类物质贡献COD,TN主要由无机氮构成.渗滤液生物处理的效果与温度关系密切,6、9月的处理效果明显好于3、12月.     

Estrogenic and dioxin-like potency in each step of a controlled landfill leachate treatment plant in Japan

The estrogenic activity (by E-screen bioassay), the concentrations of PCBs, PCDDs/PCDFs (and their resulting toxicity equivalents, TEQ) and several endocrine disrupting chemicals (EDCs: e.g., bisphenol A, nonylphenol, Butyl benzylpthalate (BBP), di-n-butylphthalate (DBP), 17alpha-ethynyl-estradiol or 4-octylphenol) have been analyzed from leachates of each step (before treatment, after biodegradation/sedimentation and after charcoal treatment) of a controlled landfill leachate treatment plant. The comparison of the effluent of the examined landfill leachate treatment plant with water from a nearby river in this study indicated no additional dioxin-like (e.g., TEQ: 0.027 compared to 1.01 pg TEQ/l; PCBs: 1.2 compared to 3.9 ng/l) or estrogenic impact (2.8 compared to 3.5 ng estradiol equivalents EE/l; analyzed by E-screen bioassay) from the leachate treatment plant into the surrounding water environment. The impact of dioxin-like compounds from uncleaned leachates into the final cleaned effluents could be sufficiently reduced by the leachate treatment plant for PCDDs (75%), PCDFs (62%), dioxin-like PCBs (97%), and the sum of TEQ (78%). The leachate treatment plant also achieved a reduction of the estrogenic activity as determined by E-screen (from 4.8 to 2.8 ng EE/l = 42%), by GC/MS for bisphenol A (>96% and nonylphenol (>98%) or by ELISA for estradiol (>80%). Additionally, for the validation of the E-screen, five known endocrine disrupting chemicals (EDCs: bisphenol A, BBP, DBP, 17 alpha-ethynyl-estradiol, 4-octylphenol) were analyzed. The EC50 values and estradiol equivalents factors (EEFs) for the five EDCs determined in this study were comparable to previously published data. The combined biological and chemical trace analysis data have provided valuable information on the relative contribution of natural, synthetic, and non-steroidal anthropogenic chemicals to the estrogenic and dioxin-like activity in leachates from a wastewater treatment plant, and water from a nearby river.     

Transformation of dissolved organic matter in a novel groundwater recharge system with reclaimed water

A novel process, enhanced direct injection-well recharge system (EnDir), can overcome the technical difficulties during the application of conventional surface spreading and has been developed to recharge groundwater with reclaimed water. In this study, removal and transformation of dissolved organic matter (DOM) in the system were investigated in laboratory-scale experiments. Results demonstrated that dissolved organic carbon and trihalomethane formation potential values could be reduced from 6.54 +/- 1.30 mg/L and 267.9 +/- 24.3 microg/L to 1.59 +/- 0.64 mg/L and 104.5 +/- 10.2 microg/L, respectively, as a result of DOM biodegradation in the aerobic short-term vadose soil treatment. Fluorescence spectra showed that aromatic protein-like substances and soluble microbial byproducts could be removed, to a great extent, in the soil system. Despite different removal efficiencies of DOM in different molecular weight fractions, the residual DOM was composed mainly of fulvic acid-like and humic acid-like substances, with molecular weights of 500 Da to 1 kDa.     

Removal potential of anti-estrogenic activity in secondary effluents by coagulation

Anti-estrogenic activity in wastewater is gaining increased attention because of its endocrine-disrupting function. In this study, the level and removal efficiency by coagulation of anti-estrogenic activity in secondary effluents of domestic wastewater treatment plants were studied. Anti-estrogenic activity was detected in secondary effluent samples at a tamoxifen (TAM) equivalent concentration level of 0.38–0.94 mg-TAM L⁻¹. Dissolved organic matters (DOM) with the molecular weight (MW) less than 3000 Da in hydrophobic acids (HOA) and hydrophobic neutrals (HON) fractions of the secondary effluent were the key fractions related to anti-estrogenic activity. Coagulation with FeCl₃ and polyaluminium chloride (PAC) can remove the anti-estrogenic activity of the secondary effluents, but the removal efficiency was limited. The removal efficiency using FeCl₃ coagulant was higher than that induced by PAC. Dissolved organic carbon was continuously removed with increased coagulant dose (0–120 mg L⁻¹ FeCl₃ or 0–60 mg L⁻¹ PAC). However, the removal of anti-estrogenic activity was not enhanced further when the coagulant concentration was beyond a critical value (30 mg L⁻¹ FeCl₃ or 10 mg L⁻¹ PAC). The highest removal of anti-estrogenic activity was about 36% by FeCl₃ and 20% by PAC. Size exclusion chromatography results indicated difficulty in removing DOM with MW less than 3000 Da in the secondary effluent during coagulation even at a high coagulant concentration, which led to low removal efficiency of anti-estrogenic activity.     

The biological treatment of landfill leachate using a simultaneous aerobic and anaerobic (SAA) bio-reactor system

A set of simultaneous aerobic and anaerobic (SAA) bio-reactor system was used for the removal of organic pollutants and ammonia in the landfill leachate generated from Datian Shan Landfill in Guangzhou, China. The influent concentrations of COD and NH(4)(+)-N were 1000-3300 and 80-230 mg L(-1), respectively. The average effluent concentrations of COD and NH(4)(+)-N were 131 and 7 mg L(-1), respectively. The concentrations of COD and NH(4)(+)-N had reached the Chinese second grade effluent standard (COD<300 mg L(-1), NH(4)(+)-N<25 mg L(-1)) for this kind of wastewater. Gas chromatogram-mass spectrum (GC/MS) analysis was used to measure the organic pollutants in the landfill leachate. About 87 organics were detected in this landfill leachate, and 16 of them belong to the list of environmental priority pollutants established by the US Environmental Protection Agency. About 31 of the 87 organic pollutants were completely removed by the SAA bio-reactor, the concentrations of further 14 organic pollutants were reduced by more than 80%, and the removal efficiencies of the other 25 organic pollutants were over 50%.     

生物反应器填埋的沉降加速效应

通过实验室填埋柱模拟实验,研究了生物反应器填埋操作方式对填埋层沉降的影响。结果表明：与传统卫生填埋方式相比,回灌经厌氧生物处理后渗滤液的生物反应器填埋方式能够加速填埋层的沉降,140 d内沉降提高比例达10%以上。我国填埋垃圾高含水率、高易腐有机物含量的特性,使得其填埋层的次沉降系数高于文献值。填埋垃圾有机物降解量及其引起的垃圾水分排出量与填埋层沉降有显著相关性,表明有机物降解是引起填埋层沉降的重要因素,也是造成生物反应器填埋与传统卫生填埋方式初期沉降差异的主要原因。     

垃圾渗滤液中的氨氮对微生物活性的抑制作用

研究了合成废水和垃圾滤渗滤中氨氮对活性污泥微生物活性的抑制作用。当合成废水的氨氮浓度从５０ｍｇ／Ｌ依次成倍递增至８００ｍｇ／Ｌ时,脱氢酶活性由１１．０４μｇＴＦ／ｍｇＭＬＳＳ下降至４．２２,此时ＣＯＤ的去除率相应由９５．１％降低到７９．１％。     

不同垃圾渗滤液组合处理工艺中DOM的变化特征

为了快速表征垃圾渗滤液处理过程中有机物的特性变化,分别采用紫外光谱和三维荧光光谱对2种垃圾渗滤液处理工艺不同单元溶解性有机物(DOM)的变化进行了系统分析。结果表明,二级RO和厌氧+好氧+MBR+NF+RO工艺对渗滤液COD和NH3-N的去除率分别为98.7%、99.0%和98.8%、98.6%。随着处理过程的进行,2个处理工艺中DOM的SUVA254、E253/E203分别由0.74、0.33和0.46、0.12下降至0.015、0.014和0.010、0.012,有机物的芳香性和不饱和性下降,脂肪链芳香烃化合物开始增加。不同处理阶段渗透液DOM三维荧光光谱表明,随着处理过程的进行,类富里酸和类蛋白物质的含量逐渐下降,芳构化程度开始降低。其中二级RO系统对渗滤液中类富里酸物质的去除效果较好,而厌氧-好氧-MBR-NF-RO工艺中,类酪氨酸物质主要通过微生物降解去除,NF和RO膜对类富里酸和类腐殖酸物质的截留效果较好。