Biogeochemistry and isotope geochemistry of a landfill leachate plume

The biogeochemical processes were identified which improved the leachate composition in the flow direction of a landfill leachate plume (Banisveld, The Netherlands). Groundwater observation wells were placed at specific locations after delineating the leachate plume using geophysical tests to map subsurface conductivity. Redox processes were determined using the distribution of solid and soluble redox species, hydrogen concentrations, concentration of dissolved gases (N(2), Ar, and CH(4)), and stable isotopes (delta15N-NO(3), delta34S-SO(4), delta13C-CH(4), delta2H-CH(4), and delta13C of dissolved organic and inorganic carbon (DOC and DIC, respectively)). The combined application of these techniques improved the redox interpretation considerably. Dissolved organic carbon (DOC) decreased downstream in association with increasing delta13C-DOC values confirming the occurrence of degradation. Degradation of DOC was coupled to iron reduction inside the plume, while denitrification could be an important redox process at the top fringe of the plume. Stable carbon and hydrogen isotope signatures of methane indicated that methane was formed inside the landfill and not in the plume. Total gas pressure exceeded hydrostatic pressure in the plume, and methane seems subject to degassing. Quantitative proof for DOC degradation under iron-reducing conditions could only be obtained if the geochemical processes cation exchange and precipitation of carbonate minerals (siderite and calcite) were considered and incorporated in an inverse geochemical model of the plume. Simulation of delta13C-DIC confirmed that precipitation of carbonate minerals happened.     

Reactive transport modelling of biogeochemical processes and carbon isotope geochemistry inside a landfill leachate plume

The biogeochemical processes governing leachate attenuation inside a landfill leachate plume (Banisveld, the Netherlands) were revealed and quantified using the 1D reactive transport model PHREEQC-2. Biodegradation of dissolved organic carbon (DOC) was simulated assuming first-order oxidation of two DOC fractions with different reactivity, and was coupled to reductive dissolution of iron oxide. The following secondary geochemical processes were required in the model to match observations: kinetic precipitation of calcite and siderite, cation exchange, proton buffering and degassing. Rate constants for DOC oxidation and carbonate mineral precipitation were determined, and other model parameters were optimized using the nonlinear optimization program PEST by means of matching hydrochemical observations closely (pH, DIC, DOC, Na, K, Ca, Mg, NH4, Fe(II), SO4, Cl, CH4, saturation index of calcite and siderite). The modelling demonstrated the relevance and impact of various secondary geochemical processes on leachate plume evolution. Concomitant precipitation of siderite masked the act of iron reduction. Cation exchange resulted in release of Fe(II) from the pristine anaerobic aquifer to the leachate. Degassing, triggered by elevated CO2 pressures caused by carbonate precipitation and proton buffering at the front of the plume, explained the observed downstream decrease in methane concentration. Simulation of the carbon isotope geochemistry independently supported the proposed reaction network.     

Enzymatic treatment of sanitary landfill leachate

The objective of this investigation was to study the effectiveness of applying enzymes (bioaugmentation) for enhancement of biological treatability of leachates generated in a typical municipal solid waste sanitary landfill. The basic purpose of enzyme use is to enforce the biodecomposition of organic constituents, as well as to reduce nitrogen content. A laboratory-scale sequencing batch (bio)reactor (SBR) was used for the examination of enzymatic application. The effect of different operation strategies on the efficiency of this biological treatment process was studied to optimize performance, especially for the removal of nitrogen compounds and of biodegradable organic matter. It was found that the enzymatic process was able to remove organic matter effectively (expressed as BOD5 and COD) and nitrogen content, color and turbidity.     

Treatment and detoxification of a sanitary landfill leachate

The leachate from an old sanitary landfill (Gramacho Metropolitan Landfill, Rio de Janeiro) was characterized and submitted to coagulation and flocculation treatment followed by ozonation and ammonia stripping. The performance of the treatment was assessed by monitoring the removal of organic matter (COD and TOC), ammonium nitrogen and metals. Detoxification was assessed by determining acute toxicity, using the following organisms: Vibrio fisheri, Daphnia similis, Artemia salina and Brachydanio rerio. Membrane fractionation was employed to infer the range of molecular masses of the pollutants found in the effluent, as well as the toxicity associated to these fractions. Of the techniques under investigation, coagulation and flocculation followed by ammonia stripping were the most effective for toxicity and ammonium nitrogen removal. Membrane fractionation was effective for COD removal; however, acute toxicity was almost the same in all the fractionated samples. Ozonation was moderately effective for COD removal, but significant toxicity removal was only attained when high ozone doses were used.     

Natural attenuation of xenobiotic organic compounds in a landfill leachate plume (Vejen,Denmark)

Demonstration of natural attenuation of xenobiotic organic compounds (XOCs) in landfill leachate plumes is a difficult task and still an emerging discipline within groundwater remediation. One of the early studies was made at the Vejen Landfill in Denmark in the late 1980s, which suggested that natural attenuation of XOCs took place under strongly anaerobic conditions within the first 150 m of the leachate plume. This paper reports on a revisit to the same plume 10 years later. Within the strongly anaerobic part of the plume, 49 groundwater samples were characterized with respect to redox-sensitive species and XOCs. The analytical procedures have been developed further and more compounds and lower detection limits were observed this time. In addition, the samples were screened for degradation intermediates and for toxicity. The plume showed fairly stationary features over the 10-year period except that the XOC level as well as the level of chloride and nonvolatile organic carbon (NVOC) in the plume had decreased somewhat. Most of the compounds studied were subject to degradation in addition to dilution. Exceptions were benzene, the herbicide Mecoprop (MCPP), and NVOC. In the early study, NVOC seemed to degrade in the first part of the plume, but this was no longer the case. Benzyl succinic acid (BSA) was for the first time identified in a leachate plume as a direct indicator, and as the only intermediate of toluene degradation. Toxicity measurements on solid phase-extracted (SPE) samples revealed that toxic compounds not analytically identified were still present in the plume, suggesting that toxicity measurements could be helpful in assessing natural attenuation in leachate plumes.     

利用水泥处理垃圾渗滤液生物处理出水的研究

利用水泥的表面吸附和水化反应性质处理垃圾渗滤液生物处理出水可以取得很好的效果,COD的去除率可达69.5%.处理效果与水灰比、反应时间密切相关,低水灰比和较长反应时间对COD的去除更为有利.对处理前后水样的COD和TOC分析表明,水泥对非TOC贡献的COD有很强的去除效果.     

Fate of organic contaminants in the redox zones of a landfill leachate pollution plume (Vejen, Denmark)

Samples from 75 sample locations in a landfill leachate pollution plume reveal a significant disappearance of specific organic compounds (SOC's) within the first 100 m of the plume. Only the herbicide Mecoprop® (MCPP) migrates further. Since sorption and dilution cannot account for the decreasing concentrations, degradation is considered to be the governing process. Non-volatile organic carbon shows a corresponding fate probably acting as a substrate for the microbial processes. The first 20 m of the plume are methanogenic/sulfidogenic, judged on the chemistry of the groundwater, followed by a significant ferrogenic zone exhibiting a substantial capacity to degrade the SOC's. The presence of intermediary products (here an oxidized camphor compound) supports the concept of degradation within the ferrogenic zone. This investigation draws the attention to the significant natural attenuation of organic contaminants and to the so far neglected ferrogenic zone in controlling the fate of organic contaminants in leachate plumes.     

某生活垃圾卫生填埋场渗滤液的梯度分离与表征

目前,渗滤液中污染物的粒度分布及其在渗滤液污染控制中的作用日益受到关注。通过系列微滤膜(1.2μm及0.45μm)对某生活垃圾卫生填埋场渗滤液各处理单元的渗滤液进行梯度分离,发现悬浮物对COD、浊度的影响较大;COD主要在胶体态和可溶解态间分配,不同渗滤液中的分配情况不同;磷主要与胶体、悬浮物以各种形式结合而存在;细胶粒和溶解态等小分子对TN的贡献大;不同粒度物质对pH的影响不明显;总残渣在可溶态组分中所占比例较大。膜微滤处理渗滤液可以有效的去除一部分物质,使COD、TP、TN、浊度、电导率都有不同程度的降低,pH逐渐升高,但对总N、残渣的去除效果不好。     

Concentrations of Synthetic organic chemicals in leachate from a municipal landfill

A study on the concentrations of synthetic organic chemicals in leachate from the municipal landfill of Lake Charles, Louisiana, was conducted from June 1987 through March 1989. The primary objective of this study was to provide information on the concentrations of synthetic organics in leachate from a typical municipal landfill. Leachate analyses yielded the presence of a variety of synthetic organic compounds at wide ranges in concentration. These compounds are potentially dangerous to human health.     

Biogeochemistry at a wetland sediment–alluvial aquifer interface in a landfill leachate plume

The biogeochemistry at the interface between sediments in a seasonally ponded wetland (slough) and an alluvial aquifer contaminated with landfill leachate was investigated to evaluate factors that can effect natural attenuation of landfill leachate contaminants in areas of groundwater/surface-water interaction. The biogeochemistry at the wetland-alluvial aquifer interface differed greatly between dry and wet conditions. During dry conditions (low water table), vertically upward discharge was focused at the center of the slough from the fringe of a landfill-derived ammonium plume in the underlying aquifer, resulting in transport of relatively low concentrations of ammonium to the slough sediments with dilution and dispersion as the primary attenuation mechanism. In contrast, during wet conditions (high water table), leachate-contaminated groundwater discharged upward near the upgradient slough bank, where ammonium concentrations in the aquifer where high. Relatively high concentrations of ammonium and other leachate constituents also were transported laterally through the slough porewater to the downgradient bank in wet conditions. Concentrations of the leachate-associated constituents chloride, ammonium, non-volatile dissolved organic carbon, alkalinity, and ferrous iron more than doubled in the slough porewater on the upgradient bank during wet conditions. Chloride, non-volatile dissolved organic carbon (DOC), and bicarbonate acted conservatively during lateral transport in the aquifer and slough porewater, whereas ammonium and potassium were strongly attenuated. Nitrogen isotope variations in ammonium and the distribution of ammonium compared to other cations indicated that sorption was the primary attenuation mechanism for ammonium during lateral transport in the aquifer and the slough porewater. Ammonium attenuation was less efficient, however, in the slough porewater than in the aquifer and possibly occurred by a different sorption mechanism. A stoichiometrically balanced increase in magnesium concentration with decreasing ammonium and potassium concentrations indicated that cation exchange was the sorption mechanism in the slough porewater. Only a partial mass balance could be determined for cations exchanged for ammonium and potassium in the aquifer, indicating that some irreversible sorption may be occurring.Although wetlands commonly are expected to decrease fluxes of contaminants in riparian environments, enhanced attenuation of the leachate contaminants in the slough sediment porewater compared to the aquifer was not observed in this study. The lack of enhanced attenuation can be attributed to the fact that the anoxic plume, comprised largely of recalcitrant DOC and reduced inorganic constituents, interacted with anoxic slough sediments and porewaters, rather than encountering a change in redox conditions that could cause transformation reactions. Nevertheless, the attenuation processes in the narrow zone of groundwater/surface-water interaction were effective in reducing ammonium concentrations by a factor of about 3 during lateral transport across the slough and by a factor of 2 to 10 before release to the surface water. Slough porewater geochemistry also indicated that the slough could be a source of sulfate in dry conditions, potentially providing a terminal electron acceptor for natural attenuation of organic compounds in the leachate plume.     

Dissolved organic matter and estrogenic potential of landfill leachate

The estrogenic potentials of leachate samples collected at Laogang Sanitary Landfill in Shanghai, China were measured together with the associated dissolved organic matter (DOM) in leachate samples. Over 99% of the DOM in fresh leachate was removed upon 3-7 years of landfill, leaving only DOM with strong fluorescent activity. Anoxic or aerobic treatment of landfill leachate can further degrade DOM of MW<300 Da and transform those with fluorescent activity of MW>10(5) Da to those of 2000-10(5) Da. Neither landfilling nor storage in anoxic pond effectively removed estrogenic potential of leachate. Fractionation test revealed that residual organic matters of MW 3000-14000 Da and of <600 Da with high UV254 contributed most of the estrogenic activities in leachate. Aerobic SBR treatment considerably reduced the estrogenic potential of these organic matters in leachate.     

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.     

Geology and sediment geochemistry of a landfill leachate contaminated aquifer (Grindsted, Denmark)

A landfill leachate affected aquifer was investigated with respect to the geology and sediment geochemistry (solid organic carbon, cation exchange capacity, oxidation capacity, reduced iron and sulfur species) involving 185 sediment samples taken along a 305-m-long and 10–12-m-deep transect downgradient from the landfill. The geology showed two distinct sand layers (upper Quaternary, Weichselian and a lower Tertiary, Miocene) sandwiching thin layers of silt/clay deposits, peat and brown coal. The organic carbon content (TOC) and the cation exchange capacity (CEC) of the sandy sediments were low (TOC, 100–300 μg C (g DW)⁻¹ ; CEC, 0.1–0.5 meq per 100 g DW) and correlated fairly well with the geology. Processes in the contaminant plume caused depletion of oxidation capacity and precipitation of reduced iron and sulfur species. However, some of these parameters were also affected by the geology, e.g. the oxidation capacity (OXC) was significantly higher in the Quaternary layer (OXC, 14–35 μeq g DW⁻¹) than in the Tertiary sand layer (OXC, <5 μeq g DW⁻¹). The intermediate layers (silt/clay and brown coal) have significantly higher values of most of the parameters investigated. This work demonstrates the need for a small scale geological model and a detailed mapping of the geochemistry of the sediments in order to distinguish impacts caused by the contaminant plumes from natural variations in the aquifer geochemistry.     

Comparison of two biological treatment processes using attached-growth biomass for sanitary landfill leachate treatment

The objective of this investigation was to compare two biological systems using attached-growth biomass, for treatment of leachates generated in a typical municipal solid waste sanitary landfill. A moving-bed biofilm process, which is a relatively new type of biological treatment system, has been examined. It is based on the use of small, free-floating polymeric (polyurethane) elements, while biomass is being grown and attached as biofilm on the surface of these porous carriers. A granular activated carbon (GAC) moving-bed biofilm process was also tested. This method combines both physico-chemical and biological removal mechanisms for the removal of pollutants. The presence of GAC offers a suitable porous media, which is able to adsorb both organic matter and ammonia, as well as to provide an appropriate surface onto which biomass can be attached and grown. A laboratory-scale sequencing batch reactor (SBR) was used for the examination of both carriers. The effects of different operation strategies on the efficiency of these biological treatment processes were studied in order to optimize their performance, especially for the removal of nitrogen compounds and of biodegradable organic matter. It has been found that these processes were able to remove nitrogen content almost completely and simultaneously, the removal of organic matter (expressed as BOD5 and COD), color and turbidity were sufficiently achieved.     

太阳光Fenton法处理垃圾渗滤液中有机污染物

研究利用太阳光Fenton法处理垃圾渗滤液。根据太阳光辐射强度随时间的变化规律,选择重庆7、8月份的晴天,在中午12：00到下午14：00时进行试验,研究太阳光辐射时间、pH值、Fenton试剂用量对垃圾渗滤液COD去除率的影响。研究结果表明：太阳光Fenton法对垃圾渗滤液的COD有较好的去除效果,COD去除率达86.2%。太阳光Fenton法处理垃圾渗滤液的优化条件是：日光辐射时间为120 min,pH值为2.5,Fe²⁺浓度为5 mmol/L,H₂O₂浓度为570 mmol/L。同时,论文还对太阳光Fenton法处理垃圾渗滤液的动力学进行分析。研究结果显示：太阳光Fenton法处理垃圾渗滤液,其表观动力学方程为-dC/dt=2.6×10^-8×P^1.92×F^1.79×E^1.67。     

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。     

Identification of a reactive degradation zone at a landfill leachate plume fringe using high resolution sampling and incubation techniques

Vertical small-scale variation in phenoxy acid herbicide degradation across a landfill leachate plume fringe was studied using laboratory degradation experiments. Sediment cores (subdivided into 5 cm segments) were collected in the aquifer and the sediment and porewater were used for microcosm experiments (50 experiments) and for determination of solid organic carbon, solid-water partitioning coefficients, specific phenoxy acid degraders and porewater chemistry. Results from a multi-level sampler installed next to the cores provided information on the plume position and oxygen concentration in the groundwater. Oxygen concentration was controlled individually in each microcosm to mimic the conditions at their corresponding depths. A highly increased degradation potential existed at the narrow plume fringe (37.7 to 38.6 masl), governed by the presence of phenoxy acids and oxygen. This resulted in the proliferation of a microbial population of specific phenoxy acid degraders, which further enhanced the degradation potential for phenoxy acids at the fringe. The results illustrate the importance of fringe degradation processes in contaminant plumes. Furthermore, they highlight the relevance of using high-resolution sampling techniques as well as controlled microcosm experiments in the assessment of the natural attenuation capacity of contaminant plumes in groundwater.     

Fenton法降解垃圾渗滤液中的溶解性有机质

垃圾渗滤液是一种高浓度难降解废水,含有大量有毒物质和溶解性有机质（dissolved organic matter, DOM）,可生化性差。Fenton试剂（Fe2++H2O2）能产生活性极强的羟基自由基（·OH）,能快速氧化渗滤液中DOM和微量有机物质。本研究采用Fenton法处理垃圾渗滤液,结果表明,在优化的处理条件下,渗滤液COD和TOC去除率分别为65%和42%,其中混凝作用去除的COD和TOC分别为20%和21%。进一步通过紫外可见光谱扫描、SUVA254、E3/E4等指标评价,发现Fenton法可以有效降低渗滤液中的DOM含量,大分子有机物的含量明显减少,而分子量小的有机物含量相对增加,反应体系中溶解性有机物分子量随着反应的进行而降低,腐殖化程度降低。利用GC-MS定性出渗滤液原液中47种有机物,该类有机物在Fenton反应后上清液中未再检出,但5种物质（邻苯二甲酸二（2-乙基己）酯、植酮、角鲨烯、麥角甾烷醇和二氢胆固醇）在沉淀的铁泥中检出。研究发现不同pH值、H2O2和Fe2+浓度条件下,残留的COD与DOM、TOC和UV254存在显著的相关关系（R2> 0.9）。本研究结果为改进垃圾渗滤液处理工艺和探索DOM在Fenton过程中的降解行为提供科学依据。     

水化深度处理渗滤液尾水中的有机物

利用水泥的水化过程易受有机物影响的特点,采用硅酸盐水泥深度处理了垃圾渗滤液膜生物反应器(MBR)工艺出水,考察了不同因素,如投加量、初始pH、反应时间及振荡速率等对于渗滤液尾水中有机物的去除效果以及最佳工艺条件,并分析了渗滤液尾水中有机物的去除机理。结果表明,水化过程对渗滤液尾水中的有机物去除性能良好,且对不同有机物具有一定的选择性,尤其对具有近紫外区(200～400 nm)吸收峰特征的有机物去除效果更佳,同时发现,当投加量为50 g/L、pH=8.3(原渗滤液pH)、反应时间为24 h和振荡速度为200 r/min时,去除效果最佳,其COD、TOC和UV254的平均去除率分别达到55.6%、62.1%和68.8%。