LANDFILL LEACHATE TREATMENT : REVIEW AND OPPORTUNITIES

S. Renoua, J-G. Givaudana, S. Poulaina, F. Dirassouyanb, P. Moulinc,*

a

Laboratoire de Transfert de Contamination Dcontamination, Commissariat lEnergie Atomique de Cadarache, 13108 St Paul-les-Durance Cedex, France
b

Groupe Pizzorno Environnement, 109, Rue Jean Aicard, 83300 Draguignan, France

Laboratoire en Procds Propres et Environnement (UMR 6181), Universit Paul Czanne, Europle de lArbois, BP 80, Batment Laennec, Hall C, 13545 Aix-en-Provence Cedex 4, France

* Corresponding author : Dr. P. Moulin Tel.: +33-4-4290-8505; fax: +33-4-4290-8515 Email: philippe.moulin@univ.u-3mrs.fr

Abstract

In most countries, sanitary landfilling is nowadays the most common way to eliminate Municipal Solid Wastes (MSW). In spite of many advantages, generation of heavily polluted leachates, presenting significant variations in both volumetric flow and chemical composition, constitutes a major drawback. Year after year, the recognition of landfill leachate impact on environment have forced authorities to fix more and more stringent requirements for pollution control. This paper is the state of art review of landfill leachate treatability and of available treatment process performances. Advantages and drawbacks of the various treatments are discussed under the items : (a) leachate transfer, (b) biodegradation, (c) chemical and physical methods and (d) membrane processes. Several tables permit to review and summarize each treatment efficiency depending on operating conditions. Finally,

considering the hardening of the standards of rejection, conventional landfill leachate treatment plants appear under-dimensioned or do not allow to reach the specifications required by the legislator. So that, new technologies or conventional ones improvements have been developed and tried to be financially attractive. Today, the use of membrane technologies, more especially Reverse Osmosis (RO), either as a main step in a landfill leachate treatment chain or as single post-treatment step has shown to be an indispensable means of achieving purification.

Keywords : landfill leachate, wastewater treatment, review.

1. Introduction

Increasingly affluent lifestyles, continuing industrial and commercial growth in many countries around the world in the past decade has been accompanied by rapid increases in both the municipal and industrial solid waste production. Municipal Solid Waste (MSW) generation continues to grow both in per capita and overall terms. For example, in 1997, waste production in Rio de Janeiro, Brazil, was 8042 ton.day-1 compared to 6200 ton.day-1 in 1994, despite the fact that population growth during that period was practically zero. Waste production increased by 3% and 4.5 % per year between 1992 and 1996 respectively in Norway and in the USA. During the latter part of the 1990s, annual waste production ranged from 300-800 kg per person in the more developed countries to less than 200 kg in other countries (United Nations Center for Human Settlements, 2001). In 2002, French population produced 24 million of MSW, namely 391 kg per person (ADEME, 2002). The sanitary landfill method for the ultimate disposal of solid waste material continues to be widely accepted and used due to its economic advantages. Comparative studies of the various possible means of eliminating solid urban waste (landfilling, incineration, composting, etc.) have shown that the cheapest, in term of exploitation and capital costs, is landfilling. In 2002, 52% of waste production in France was landfilled into regulated centers (ADEME, 2002). Besides its economic advantages, landfilling minimizes environmental insults and others inconveniences, and allows waste to decompose under controlled conditions until its eventual transformation into relatively inert, stabilized material. So, the worldwide trend is for controlled sanitary landfilling as the preferred means of disposing of both solid urban refuse and a large proportion of solid industrial waste. It concerns both industrialized cities (11500 ton.day-1 of MSW in Mexico city) and rural areas (about 40000 tonnes per year in the Kyletalesha landfill site, Ireland). Also, recent estimates indicates that 52, 90 and 95% of urban wastes are disposed of at landfill sites respectively in Korea (Cho et al, 2002), Poland (Piatkiewicz, 2001) and Tawan. However, the release from a sanitary landfill consist mainly of leachate

which has became the subject of recent interest as a strongly polluted wastewater and biogas, that is a resource which can be utilized for energy production (Di Palma et al., 2002). Their now expensive scientific literature on the collection, storage and suitable treatment of its highly contaminated leachates (Fig. 1), threatening surface and ground waters. Fig. 1 summarizes the evolution of main published research, concerning landfill leachate treatment, reported in the world's journal and patent literature since 1973 (data extracted from Chemical Abstracts) Leachates are defined as the aqueous effluent generated as a consequence of rainwater percolation through wastes, biochemical processes in wastes cells and the inherent water content of wastes themselves. Leachates may contain large amounts of organic matter (biodegradable, but also refractory to biodegradation), where humic-type constituents consist an important group, as well as ammonia-nitrogen, heavy metals, chlorinated organic and inorganic salts. The removal of organic material based on Chemical Oxygen Demand (COD), Biological Oxygen Demand (BOD) and ammonium from leachate is the usual prerequisite before discharging the leachates into natural waters. Toxicity analysis carried out using various test organisms (Vibrio fisheri, Daphnia similes, Artemia salina, Brachydanio rerio) have confirmed the potential dangers of landfill leachates (Pirbazari et al., 1996; Clment et al., 1997 ; Sisinno et al., 2000 ; Marttinen et al., 2002, Silva et al., 2004) and the necessity to treat it so as to meet the standards for discharge in receiving waters. According to this fact, governments apply enhanced regulation for non-biodegradable organic matter and for nitrogenous compounds. In 1997, French authorities have fixed more stringent

requirements concerning discharge into surface waters (Table 1). Fortunately, the remarkable growth in economics and living standard has accelerated the development of water and wastewater purification technologies. To sum up, MSW management constitutes today a major environmental, economical and social problem worldwide, mainly because the waste volume is growing faster than the worlds population. Moreover, as stricter environmental requirements are continuously imposed regarding ground and surface waters, the treatment of landfill leachate becomes a major environmental concern. This review, 4

therefore, focuses on the state of art in landfill leachate treatment and provides a comparative evaluation of various treatment processes. New treatment alternatives and conventional technology improvements are highlighted and examinated.

2. Leachate characteristics

The two factors characterizing a liquid effluent are the volumetric flow rate and the composition which in the case of leachate are related. Fig. 2 illustrates water cycle in a landfill. Leachate flow rate (E) is closely linked to precipitation (P), surface run-off (Rin, Rext), and infiltration (I) or intrusion of groundwater percolating through the landfill. Landfilling technique (waterproof covers, liner requirements such as clay, geotextiles and/or plastics) remains primordial to control the quantity of water entering the tip and so, to reduce the threat pollution (Lema et al., 1988). The climate has also a great influence on leachate production because it affects the input of precipitation (P) and losses through evaporation (EV). Finally, leachates production depends on the nature of the waste itself, namely its water content and its degree of compaction into the tip. The production is generally greater whenever the waste is less compacted, since compaction reduces the filtration rate (Lema et al., 1988). There are many factors affecting the quality of such leachates, i.e., seasonal weather variation, waste type and composition (depending on the standard of living of the surrounding population, structure of the tip). In particular, the composition of landfill leachates varies greatly depending on the age of the landfill (Baig et al., 1999). Fig. 3 proposes anaerobic degradation scheme for the organic material in a sanitary landfill. In young landfills, containing large amounts of biodegradable organic matter, a rapid anaerobic fermentation takes place, resulting in Volatile Fatty Acids (VFA) as the main fermentation products (Welander et al., 1997). Acid fermentation is enhanced by a high moisture content or water content in the solid waste (Wang et al., 2003). This early phase of a landfills lifetime is called the acidogenic phase, and leads to the release of large quantities of free VFA, as much as 95% of the organic content (Harsem, 1983). As a landfill matures, the methanogenic phase occurs. 5

Methanogenic microorganisms develop in the waste, and the VFA are converted to biogas (CH4, CO2). The organic fraction in the leachate becomes dominated by refractory (non-biodegradable) compounds such as humic substances (Chian and DeWalle, 1976). The characteristics of the landfill leachate can usually be represented by the basic parameters COD, BOD, the ratio BOD/COD, pH, Suspended Solids (SS), Ammonium nitrogen (NH3-N), Total Kjeldahl Nitrogen (TKN) and heavy metals. The leachate composition from different sanitary landfills, as reported in the literature, show a wide variation. Tables 2 and 3 summarize the ranges of leachate composition. These data show that the age of the landfill and thus the degree of solid waste stabilization has a significant effect on water characteristics. Values of COD vary from 70900 mg.L-1 with leachate sample obtained from the Thessaloniki Greater Area (Greece) to 100 mg.L-1 with sample from an more than 10-year old landfill near Marseille (France). With few exception, the pH of leachates lie in the range 5.8 to 8.5, which is due to the biological activity inside the tip. It is also important to notice that the majority of TKN is ammoniacal-N, which can range from 0.2 to 13000 mg.L-1 of N. The ratio of BOD/COD, from 0.70 to 0.04, decrease rapidely with the aging of the landfills (Chian and DeWalle, 1976). This is due to the release of the large recalcitrant organic molecules from the solid wastes. Consequently, old landfill leachate is characterized by its low ratio of BOD/COD and fairly high NH3N. Although leachate composition may vary widely within the successive aerobic, acetogenic, methanogenic, stabilization stages of the waste evolution, three types of leachates have been defined according to landfill age (Table 4). The existing relation between the age of the landfill and the organic matter composition may provide a useful criteria to choose a suited treatment process. Review of leachate treatment processes and its performance is now presented.

3. Leachate treatment

Technologies used for leachate treatment can be classified into four major groups: (a) leachate transfer : recycling, lagooning and combined treatment with domestic sewage, (b) biodegradation: aerobic and anaerobic processes, (c) chemical and physical methods: chemical oxidation, adsorption, chemical precipitation, coagulation/flocculation, sedimentation/flotation and air stripping and (d) membrane filtration : microfiltration, ultrafiltration, nanofiltration and reverse osmosis. Each of the aforementioned alternatives presents its own advantages and disadvantages. The combination of biological and physicalchemical processes is being considered as the most appropriate technology for manipulation and management of high strength effluents. The integrated chemical physicalbiological processes (whatever the order) ameliorates the drawbacks of individual processes contributing to a higher efficacy of the overall treatment. Additionally, the changing nature and composition of leachates depending on age, season, climatic conditions, etc., implies that specific treatments of wide application must be proposed. As a consequence, the methodology adopted to face these effluents must be flexible and adaptable to relatively different inputs.

3.1. Leachate transfer 3.1.1. Combined treatment with domestic sewage

Few years ago, a common solution was to treat the leachate together with municipal sewage in the municipal sewage treatment plant. It was preferred for its easy maintenance and low operating costs (Ahn et al., 2002). However, this option has been increasingly questioned due to the presence in the leachate of organic inhibitory compounds with low biodegradability and heavy metals that may reduce treatment efficiency and increase the effluent concentrations (Ceen and Aktas, 2004). An argument in favour of this alternative treatment is that nitrogen (brought by leachate) and phosphorus (brought by sewage) dont need to be added at the plant. Among the few studies published, authors tried to optimize the volumetric ratio of leachate in the total wastewater. Combined treatment was investigated by Diamadopoulos et al. (1997) using a Sequencing Batch Reactor (SBR) consisting of filling, anoxic, oxic 7

and settling phases. When the ratio of sewage to leachate was 9/1, nearly 95% BOD and 50% nitrogen removals were obtained at the end of the daily cycles. COD and NH4+-N reduction decreased with increasing landfill leachate/domestic wastewater ratio (Ceen and Aktas, 2001). Moreover, the effluent quality may be improved with Powdered Activated Carbon (PAC) addition, particularly if the leachate input exceeds 10%. Other researchers (Table 5) studied the co-treatment of leachate and sewage (Lema et al., 1988 ; Booth et al., 1996 ; Ceen and Cakiroglu, 2001) and showed similar results.

3.1.2 Recycling

Recycling leachate back through the tip has been largely used in the past decade because it was one of the least expensive options available (Lema et al., 1988). Recently, authors showed benefits of this technique. Bae et al. (1998) reported that leachate recirculation increased the moisture content in a controlled reactor system and provided the distribution of nutrients and enzymes between methanogens and solid/liquids. Significant lowering in methane production and COD was observed when the recirculated leachate volume was 30% of the initial waste bed volume (Chugh et al., 1998). Also, Rodriguez et al. (2004) reported a 63-70% COD lowering in an anaerobic pilot plant with recirculation. The leachate recycle not only improves the leachate quality, but also shortens the time required for stabilization from several decades to 23 years (Reinhart and Al-Yousfi, 1996). Although positive effects have been reported on solid waste degradation, limited data are available (Table 6) concerning the recirculation rate impact on treatment efficiency in controlled anaerobic digesters (OKeefe et al., 2000 ; Sponza et al., 2004 ; Rodriguez et al., 2004). High recirculation rates may adversely affect anaerobic degradation of solid wastes. For instance, Ledakowicz and Kaczorek (2004) observed that leachate recirculation can lead to the inhibition of methanogenesis as it may cause high concentrations of organic acids (pH<5) which are toxic for the methanogens. Furthermore, if the volume of leachate recirculated is very high, problems such as saturation, ponding and acidic conditions may occur (Chan et al., 2002 ; San and Onay, 2001). 8

3.1.3 Lagooning

Lagoons have generally been viewed as an effective and low-cost method for removing pathogens, organic and inorganic matters. Their low operation and maintenance costs have made them a popular choice for wastewater treatment, particularly in developing countries since there is a little need for specialised skills to run the system (Maynard et al., 1999). Wide variations in the standard performance of lagoon systems have been reviewed in the literature (Table 7). Maehlum (1995) used on-site anaerobicaerobic lagoons and constructed wetlands for biological treatment of landfill leachate. Overall N, P and Fe removals obtained in this system were above 70% for diluted leachate. Orupold et al. (2000) studied the feasibility of lagooning to treat phenolic compounds as well as organic matter. Abatement of 55-64% of COD and 80-88% of phenol was achieved. High productivity plant, large adsorptive surfaces on sediments, plants and roots, aerobicanaerobic interfaces, and varied active microbial populations (Maehlum, 1995), make lagooning adapted to landfill leachate or wastewater treatment. However, as stricter requirements are imposed, lagooning may not be a completely satisfactory treatment option for leachate in spite of its lower costs (Zaloum and Abbott, 1997). In particular, authors claimed that the temperature dependence of lagooning is a significant limitation because it mainly affects microbial activity.

3.2 Physical/Chemical Treatment

Physical and chemical processes include reduction of suspended solids, colloidal particles, floating matters, color, and toxic compounds by either flotation, coagulation/flocculation, adsorption, chemical oxidation and air stripping.

3.2.1 Flotation 9

For many years, flotation has been extensively used and focused on the decrease of colloids, ions, macromolecules, microorganisms and fibers (Rubio et al., 2002). However, until to date, very few studies have been devoted to the application of flotation for the treatment of landfill leachate. Recently, Zouboulis et al. (2003) investigated the use of flotation in column, as a post-treatment step for removing residual humic acids (non-biodegradable compounds) from simulated landfill leachates. Under optimised conditions, almost 60% humic acids removal has been reached.

3.2.2 Coagulation-Flocculation

Coagulation and flocculation may be used successfully in treating stabilized and old landfill leachates (Kang and Hwang, 2000 ; Monje-Ramirez and Orta de Velasquez, 2004 ; Silva et al., 2004). It is widely used as a pre-treatment (Zamora et al., 2000 ; Amokrane et al., 1997 ; Tatsi et al., 2003), prior to biological or reverse osmosis step, or as a final polishing treatment step in order to remove nonbiodegradable organic matter. Aluminum sulfate, ferrous sulfate, ferric chloride and ferric chloro-sulfate were commonly used as coagulants (Ehrig, 1984; Amokrane et al., 1997). The application of bioflocculant, in comparison with traditional inorganics coagulants has been recently investigated by Zouboulis et al. (2004), for the lowering of humic acids. It revealed as a viable alternative since 20 mg.L-1 bioflocculant dosage was sufficient in providing more than 85% humic acid removal. Several studies have been reported on the examination of coagulationflocculation for the treatment of landfill leachates, aiming at process optimization, i.e. selection of the most appropriate coagulant (Tatsi et al., 2003), identification of optimum experimental conditions and assessment of pH effect (Amokrane et al., 1997 ; Rivas et al., 2004). Synthesis of recent works, presented in Table 8, clearly reveal that iron salts are more efficient than aluminum ones, resulting in sufficient chemical oxygen demand (COD) reductions (up to 50%), whereas the corresponding values in case of aluminium or lime addition were moderate (between 10 and 40%). Nevertheless, combination of coagulants 10

(Loizidou et al., 1992) or addition of flocculants together with coagulants may enhance the floc-settling rate (Amokrane et al., 1997) and so the process performance (COD abatement up to 50%). However, this treatment presents some disadvantages : consistent sludge volume is produced and an increase on the concentration of aluminum or iron, in the liquid phase, may be observed (Silva et al., 2004).

3.2.3 Chemical precipitation

In the case of leachate treatment, chemical precipitation is widely used as pre-treatment in order to remove high strength of ammonium nitrogen (NH4+-N). In a study, Li et al. (1999) confirmed that the performance of a conventional activated sludge process could be significantly affected by the inhibition of microbial activity by NH4+-N. The COD removal declined from 95 to 79%, when the NH4+-N concentration in wastewater increased from 50 to 800 mg.L-1. So, many works have been initiated to investigate the feasibility of selectively precipitating NH4+-N (Table 9). Li et al. (1999, 2001) precipitated ammonium ions as Magnesium Ammonium Phosphate (MAP) with the addition of MgCl2.6H2O and Na2HPO4.12H2O with a Mg/NH4/PO4 ratio of 1/1/1 at a pH of 8.59. Ammonium concentration was reduced from 5600 to 110 mg.L-1 within 15 min by this method. Yangin et al. (2002) and Altinbas et al. (2002) studied MAP precipitation after anaerobic pre-treatment of domestic wastewater and landfill leachate mixture. Maximum ammonia lowering was obtained as 66% at a pH of 9.3 at the stochiometric ratio whereas ammonia lowering reached to 86% at the same pH above the stochiometric ratio. In MAP precipitation at the stochiometric ratio and above the stochiometric ratio, ammonia concentration, in the Upflow Anaerobic Sludge Blanket (UASB) reactor, was reduced to 31 mg.L-1 and 13 mg.L-1, respectively. Recently, struvite precipitation (Mg:NH4:PO4=1:1:1) was applied to anaerobically pretreated effluents for ammonia removal (Ozturk et al., 2003). Ammonium nitrogen depletion were observed as 85, 72 and 20% at pH of 9.2, 12 and 10-11, respectively.

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3.2.4 Adsorption

The adsorption of pollutants onto Activated Carbon in columns (Fettig et al., 1996 ; Imai et al., 1998 ; Morawe et al., 1995) or in powder form (Welander and Henrysson, 1998 ; Zamora et al., 2000 ; Kargi and Pamikoglu, 2003, 2004) provides better reduction in COD levels than the chemicals methods, whatever the initial organic matter concentration (Table 10). The main drawback is the need for frequent regeneration of columns or an equivalently high consumption of Powdered Activated Carbon (PAC). Adsorption by activated carbon has been used along with biological treatment for effective treatment of landfill leachate (Morawe et al., 1995; Ceen et al., 2001, 2003, 2004). Non-biodegradable organics, inert COD and the color may be reduced to acceptable levels for biologically treated landfill leachate. Rodriguez et al. (2004) studied PAC and different resins efficiency in the reduction of nonbiodegradable organic matter from landfill leachate. Activated carbon presented the highest adsorption capacities with 85 % COD decrease and a residual COD of 200 mg.L-1. Recently, simultaneous adsorption and biological treatment has been tested. For instance, pretreated leachate (coagulation-flocculation and air stripping of ammonia) was subjected to biological treatment in an aeration tank operated in repeated fed-batch mode in the presence of adsorbent (PAC and powdered zeolite) (Kargi and Pamukoglu, 2004). Nearly 87% and 77% COD removals were achieved with PAC and zeolite concentrations of 2 g.L-1, respectively. Other adsorbent media have been studied. Heavey (2003) used a pre-treated peat as the treatment medium. Almost 100% removal of both BOD and ammonia, and 69% removal of COD were achieved. Moreover, treatment rates of 36 g BOD.m-2.d-1 and 11g ammonia.m-2.d-1, similar with those obtained by high cost aerobic lagoons systems, were noticed. In 1988, McLellan and Rock already concluded that filtration through peat can be used only as a pre-treatment process to reduce metal concentrations prior to a conventional treatment. Finally, limestone has been proven effective in removing metals from wastewaters. Aziz et al. (2004) indicated that 90% of Fe could be removed from semi-aerobic landfill leachate by limestone filter, based on retention time of 57.8 min and surface loading of 12.2 m3/m-2.d-1. 12

3.2.5 Chemical oxidation

Chemical oxidation is a widely studied method for the treatment of effluents containing refractory compounds such as landfill leachate. Growing interest has been recently focused on Advanced Oxidation Processes (AOP). Most of them, except simple ozonation (O3), use a combination of strong oxidants, e.g. O3 and H2O2, irradiation, e.g. ultraviolet (UV), ultrasound (US) or electron beam (EB), and catalysts, e.g. transition metal ions or photocatalyst. Table 11 lists typical AOP systems currently reported in the literature. All these processes have been recently reviewed by Wang et al. (2003). Authors confirmed that AOP, adapted to old or well-stabilized leachate, are applied to : - oxidize organics substances to their highest stable oxidation states being carbon dioxide and water (i.e. to reach complete mineralization), - improve the biodegradability of recalcitrant organic pollutants up to a value compatible with subsequent economical biological treatment.

Performances of each process can be evaluated thanks to key parameters (COD, BOD, BOD/COD, oxidant dose) summarized in Tables 12 and 13 Although many of the previous researches using ozonation have demonstrated the effectiveness in eliminating COD (reduction is about 50% to 70% in most cases) (Bigot et al., 1994; Kim et al., 1997; Steensen, 1997; Haapea et al., 2002), most of them only used this process as tertiary treatment prior to discharge in the environment. Sometimes the treatment efficiency on stabilized leachates has been moderate (Silva et al., 2004). After 1h of ozonation (1.3-1.5 gO3/gCOD degraded), only 30% COD depletion was observed by Rivas et al. (2003).COD lowering can be greatly enhanced combining oxidants (H2O2/O3) (Table 12) or adding an irradiation system (H2O2/UV) (Table 13). Wable et al. (1993), Bigot et al. (1994) and Schulte et al. (1995) reported organic matter removal efficiency as high as 90% for the O3/H2O2 process. Concerning the H2O2/UV process, the BOD5/COD ratio has been increased significantly from 0.1 to 0.45 by Qureshi et al. (2002). 13

Also, Steensen (1997) reported 85-90% of COD reduction with a biologically pre-treated leachate. Fenton and photo-Fenton processes allow COD decrease efficiency of, respectively, 45-75% and 7078%. In term of biodegradability improvement, BOD/COD ratios close to 0.5 after oxidation have been reported in recent works using Fenton process (Kim et al., 1997 ; Lopez et al., 2004). Finally, a few papers reported photocatalytic treatment (Bekblet et al., 1996 ; Cho et al., 2002 ; Wang et al., 2002 ; Wiszniowski et al., 2004) or electron-beam radiation treatment (Bae et al., 1999) of organic components from landfill leachates even at laboratory scale. These technologies have been applied to treat or degrade principally humic substances. However, common drawbacks of AOP is the high demand of electrical energy for devices such as ozonizers, UV lamps, ultrasounds, which results in rather high treatment costs (Lopez et al., 2004). Also, for complete degradation (mineralization) of the pollutants to occur, high oxidant doses would be required, rendering the process economically expensive. Silva et al. (2004) applied high ozone doses (until 3.0 g.L-1) to attain significant toxicity decrease. Furthermore, some intermediate oxidation products can actually raise the toxicity of the leachate. Among these processes and according to Lopez et al. (2004), Fentons process seems to be the best compromise because the process is technologically simple, there is no mass transfer limitation (homogeneous nature) and both iron and hydrogen peroxide are cheap and non-toxic.

3.2.6 Air stripping

Nowadays, the most common method for eliminating a high concentration of NH4+-N involved in wastewater treatment technologies is air stripping. High levels of ammonium nitrogen are usually found in landfill leachates, and stripping can be successful for eliminating this pollutant, which can increase wastewater toxicity (Marttinen et al., 2002). If this method is to be efficient, high pH values must be used and the contaminated gas phase must be treated with either H2SO4 or HCl. In Table 14, performances which such a process can be evaluated in term of ammonia-nitrogen removal efficiency. 14

Marttinen et al. (2002) reported a 89% ammonia reduction at pH=11 and 20C within 24h retention time. High rates of ammonia removal have been achieved by Cheung et al. (1997) in spite of high initial ammonia concentration (0.5-0.7 gN.L-1). Their results showed that 93% of 309368 mg.L-1 ammonianitrogen were removed in free stripping tanks with one day retention time. In recent works, 85 and 99.5% of ammonia reduction has been respectively attained by Ozturk et al. (2003) and Silva et al. (2004). The main drawback of this method concerns calcium carbonate scaling of the stripping tower, when lime is used for pH adjustment (Li et al., 1999).

3.3 Biological treatment

Biodegradation is carried out by microorganisms, which can degrade organics compounds to carbon dioxide and sludge under aerobic conditions and to biogas (a mixture comprising chiefly CO2 and CH4) under anaerobic conditions (Lema et al., 1988). Biological processes have been shown to be very effective in removing organic and nitrogenous matter from immature leachates when the BOD/COD ratio has a high value (> 0.5). With time, the major presence of refractory compounds tends to limit processs effectiveness.

3.3.1 Aerobic treatment

An aerobic treatment should allow a partial abatement of biodegradable organic pollutants and should also achieve the ammonium nitrogen nitrification. Aerobic biological processes based on suspended-growth biomass, such as aerated lagoons, conventional activated sludge processes and sequencing batch reactors (SBR), have been widely studied and adopted (Knox, 1985 ; Hosomi et al., 1989 ; Bae et al., 1999 ; Lin and Chang, 2000 ; Li and Zhao, 2001). Attached-growth systems have recently attracted major interest : the Moving-Bed Biofilm Reactor (MBBR) and biofilters. The

15

combination of membrane separation technology and aerobic bioreactors, most commonly called membrane bioreactor, has also led to a new focus on leachate treatment.

3.3.1.1 Suspended-growth biomass processes

Activated sludge process. It is expensively applied for the treatment of domestic wastewater or for the co-treatment of leachate and sewage. However, this method has been shown in the more recent decades to be inadequate for handling landfill leachate treatment (Lin et al., 2000). Even if processes were proved to be effective for the removal of organic carbon, nutrients and ammoniac content, too much disadvantages tend to focus on others technologies : - inadequate sludge settleability and the need for longer aeration times (Loukidou and Zouboulis, 2001), - high energy demand and excess sludge production (Hoilijoki et al., 2000), - microbial inhibition due to high ammonium-nitrogen strength (Lema et al., 1988)

Consequently, only few works are recently available concerning landfill leachate treatment by activated sludge method (Table 15). Hoilijoki et al. (2000) investigated nitrification of anaerobically pre-treated municipal landfill leachate in lab-scale activated sludge reactor, at different temperatures (510C) and with the addition of plastic carrier material. Aerobic post-treatment produced effluent with 150500 mgCOD.L-1, less than 7 mgBOD.L-1 and on an average, less than 13 mgNH4+-N.L-1. Addition of PAC to activated sludge reactors enhanced nitrification efficiency on biological treatment of landfill leachate (Aktas and Ceen, 2001).

Sequencing Batch Reactor. This system is ideally suited to nitrification-denitrification processes since it provides an operation regime compatible with concurrent organic carbon oxidation and nitrification (Diamadopoulos et al., 1997). Process characteristics, summarized by Diamadopoulos et al. (1997) and 16

Dollerer and Wilderer (1996), resulted in a wide application for landfill leachate treatment (Irvine et al., 1984 ; Hosomi et al, 1989 ; Zaloum and Abbott, 1997 ; Lin and Chang, 2000 ; Uygur and Kargi, 2004 ). Many authors have reported COD removals up to 75% (Table 15). Also, 99% NH4+-N removal has been observed by Lo (1997) during the aerobic treatment of domestic leachates in a SBR with a 20-40 days residence time.The greater process flexibility of SBR is particularly important when considering landfill leachate treatment, which have a high degree of variability in quality and quantity (Kennedy and Lentz, 2000).

Membrane Bioreactor. The combination of membrane separation technology and bioreactors has led to a new focus on wastewater treatment. It contributes to very compact systems working with a high biomass concentration and achieving a low sludge production with an excellent effluent quality. Membrane bioreactors have been widely applied at full scale on industrial wastewater treatment and some plants have been adapted to leachate treatment (Dijk and Roncken, 1997). However, few research studies are related to landfill leachate purification by membrane bioreactors (Table 16). Pirbazari et al. (1996) used a hybrid technology known as the ultrafiltration-biologically active carbon (UF-BAC) process that amalgamates adsorption, biodegradation and membrane filtration. The process efficiencies were in the range of 95-98% in terms of TOC reduction, and exceeded 97% for specific organic pollutants. Contrary to conventional systems, organisms such as nitrifiers or organisms which are able to degrade slowly biodegradable substances are not washed out of the system and no loss of process activity occurs.

3.3.1.2 Attached-growth biomass systems

Due to main problems of sludge bulking or inadequate separability (Dollerer and Wilderer, 1996) in conventional aerobic systems, a number of innovative aerobic processes, called attachedgrowth biomass systems, using biofilms, have been recently developed. These systems present the 17

advantage of not suffering from loss of active biomass. Also nitrification is less affected by low temperatures (Knox, 1985) than in suspended-growth systems, and by inhibition due to high nitrogen content.

Trickling Filters. This method has been investigated for the biological nitrogen lowering from municipal landfill leachate. Biofilters remain an interesting and attractive option for nitrification due to low-cost filter media (Jokela et al., 2002). Typical efficiencies of biofilters, encountered in literature, are presented in Table 15. In a recent work, above 90% nitrification of leachate was achieved in laboratory and on-site pilot aerobic crushed brick filters with loading rates between 100 and 130 mgNH4+-N.L-1.d-1 at 25C and 50 mgNH4+-N.L-1.d-1 even at temperatures as low as 5-10C, respectively (Jokela et al., 2002). In the last decade, maximum ammonia rejection of 97 and 75 % in a trickling filter were respectively claimed by Knox (1985) and Martienssen and Schops (1997).

Moving-Bed Biofilm Reactor (MBBR) (or Suspended-Carrier Biofilm Reactor (SCBR) or Fluidized Bed Reactor). MBBR process is based on the use of suspended porous polymeric carriers, kept in continuous movement in the aeration tank, while the active biomass grows as a biofilm on the surfaces of them. Mains advantages of this method compared to conventional suspended growth processes seems to be : higher biomass concentrations, no long sludge-settling periods, lower sensitivity to toxic compounds (Loukidou and Zouboulis, 2001) and both organic and high ammonia removals in a single process (Horan et al., 1997). For instance, Welander et al. (1998) reported nearly 90% nitrogen removal while the COD was around 20%. In case of treating high strength ammonia leachate, no inhibition of nitrification is encountered (Welander et al., 1997). Moreover, the use of Granular Activated Carbon (GAC) as porous material offers an appropiate surface to adsorb organic matter and optimised conditions for enhanced biodegradation (Horan et al., 1997). Thus, a steady-state equilibrium is established between adsorption and biodegradation (Iwami et al., 1992). Imai et al (1993, 1995, 1998) developed an efficient biological activated carbon fluidized bed 18

process. Nearly, 70% refractory organics were removed by coupling biological treatment and adsorption process (Imai et al., 1998). After optimising the reactor operating regime, Horan et al. (1997) and Loukidou and Zouboulis (2001) proved possible to reach 85-90% ammonia reduction and 60-81% COD reduction.

3.3.2 Anaerobic treatment

An anaerobic digestion treatment of leachates allows to end the process initiated in the tip, being thus particularly suitable for dealing with high strength organic effluents, such as leachate streams from young tips (Pokhrel and Viraraghavan, 2004). Contrary to aerobic processes, anaerobic digestion conserves energy and produces very few solids, but suffers from low reaction rates (Berrueta and Castrillon, 1992). Moreover, it is possible to use the CH4 produced to warm the digester, that usually works at 35C and, under favourable conditions, for external purposes. In Table 17, performances of conventional anaerobic suspended-growth digester are reported. Typical values of 80-90% and nearly 55% COD removals were reached in anaerobic lab-scale tank at 35C and ambient temperature, respectively (Bull et al., 1983 ; Sung-Sung et al., 1997 ; Lin, 1991). Some studies also revealed good performances of anaerobic sequencing batch reactors. These systems are able to achieve solid capture and organic lowering in one vessel, eliminating the need for a clarifier. Recently, nutrient reduction from pre-treated leachate was carried out using a lab-scale SBR by Uygur and Kargi (2004). Sequential anaerobic-aerobic operations resulted in COD, NH4+-N and PO43--P removal of 62%, 31% and 19%, respectively, at the end of cycle time (21h). Also, in the initial period of the landfill, sufficient organic abatement in the anaerobic reactor through methanogenesis and denitrification, can enhance better nitrification in the following aerobic reactor. Therefore, anaerobic-aerobic system is recommended to bring down simultaneously organic and nitrogen matter (Welander et al., 1998 ; Shiskowski and Mavinic, 1998 ; Martienssen et al., 1997 ). For instance, Kettunen and Rintala (1995) showed that COD

19

removal was 35% in the anaerobic stage while in the combined process the COD and BOD7 removals were up to 75% and 99%. In last decades, the performance improvement of the existing anaerobic process was believed to be a promising option and so, high rate reactors have been designed in order to reduce long digestion time (Lin et al., 2000). Except the conventional anaerobic suspended-growth reactor, UASB and fluidized bed reactors are the main processes encountered in the literature (Table 17). They offer lower operating costs (Agdag and Sponza, 2004) and should permit to achieve the denitrification process more quickly (Garcia et al., 1996). The main disadvantages of such a treatment include sensitivity to environmental changes and toxic substances (Sung Sung et al., 1997).

Up-flow anaerobic sludge blanket (UASB) reactor. UASB process is a modern anaerobic treatment that can have high treatment efficiency and a short hydraulic retention time (Lin et al., 2000). UASB reactors, when they are submitted to high volumetric organic loading rate values (Garcia et al., 1996), have exhibited higher performances compared to other kinds of anaerobic reactors. The process temperatures reported have generally been 20-35C for anaerobic treatment with UASB reactors. In these conditions, the average performance of COD decrease efficiency (Table 17) was always higher than 70% at ambient temperature (20-23C) and 80% at 35C. Up to 92% COD decreases were obtained by Kennedy and Lentz (2000) at low and intermediate organic loading rates (between 6 and 19.7 gCOD.L-1.d-1). Only a few studies have been conducted at temperatures between 11-23C (Mendez et al., 1989 ; Garcia et al., 1996 ; Kettunen et al, 1996, 1998) although leachates may be cooler than that, especially in cold countries. Kettunen and Rintala (1998) showed that leachate can be treated on-site UASB reactor at low temperature. A pilot-scale reactor was used to study municipal landfill leachate treatment (COD 1.53.2 g.L-1) at 1323C. COD (6575%) and BOD7 (up to 95%) removals were achieved at organic loading rates of 24 kg COD.m-3.d-1. Garcia et al. (1996) concluded that COD rejection efficiency was not effected by temperature between 15 and 35C. These promising results

20

show that high-rate treatment at low temperature may minimise the need for heating the leachate prior to treatment, which may thus provide an interesting cost-effective option (Kettunen et al., 1996).

Anaerobic filter. The anaerobic filter is a high rate system that gathers the advantages of other anaerobic systems minimizing the disadvantages. In an up-flow anaerobic filter, biomass is retained as biofilms on support material, such as plastic rings (Nedwell and Reynolds, 1996). Henry et al. (1987) demonstrated that anaerobic filter could reduce the COD by 90%, at loading rates varying from 1.26 to 1.45 kg.COD.m-3.d-1, and this for different ages of landfill. Total biogas production ranged between 400 and 500 L.gas.kg-1COD destroyed and methane content between 75 and 85%.

Hybrid bed filter. It consists on an up-flow sludge blanket at the bottom and an anaerobic filter on top. This device acts as a gas-solid separator and enhances solids retention without causing channelling or short-circuiting (Timur and Ozturk, 1997). Enhanced performances of such a process results from maximization of the biomass concentration in the reactor. Nedwell and Reynold (1996) reported steady state COD removal efficiencies of 81-97% under methanogenic digestion, depending upon organic loading rate. One drawback of hybrid reactor, as well as anaerobic filter, is the added cost of the support media.

Fluidized bed reactor. Suidan et al. (1993) and Imai et al. (1993, 1995, 1998) reported studies on carbon-assisted fluidized beds. The combined biodegradation and adsorption process provide a means for removing a variety of organic compounds (Suidan et al., 1993). Imai et al. (1993) found that the biological activated carbon fluidized bed process was much more effective for treating old landfill leachate than the conventional one such as activated sludge and fixed film processes. The anaerobic treatability of this process is given in Table 17.

3.4 Membrane 21

Since inorganic contaminants are mostly not appropriate for treatment by conventional biological treatments, new regulations tend to prohibit the discharge of such complex wastes to municipal sewers. Even by combining biological and classical physical processes, only partial destruction of contaminants will be achieved. Non-biodegradable organic fraction cannot be destroyed, so will remain in the water discharge and will cause problems of long time accumulation in the future (Peters, 1998). Therefore, in the last 20 years, more effective methods based on membrane technology has emerged as a viable treatment alternative to comply and pending water quality regulations : microfiltration (MF), ultrafiltration (UF), nanofiltration (NF) and reverse osmosis (RO). In the literature, a preponderance has been shown for RO, but the choice is rather guided by the quality of the desired permeate and the landfill management.

3.4.1 Microfiltration (MF)

MF remains interesting each time that an effective method is required to eliminate colloids and the suspended matter like, for instance, in pre-treatment for another membrane (UF, NF or RO) or in partnership with chemical treatments. But, it cannot be used alone. Only Piatkiewicz (2001), in a polish study, reported the use of MF as prefiltration stage. No significant retention rate (COD reduction between 25-35%) was achieved (Table 18).

3.4.2 Ultrafiltration (UF)

UF is effective to eliminate the macromolecules and the particles, but it is strongly dependant on the type of material constituting the membrane. UF may be used as a tool to fractionate organic matter and so to evaluate the preponderant molecular mass of organic pollutants in a given leachate. Also, tests with membrane permeates may give information about recalcitrance and toxicity of the permeated 22

fractions.Except Tabet et al. (2002), UF was eliminated as a primary means for treating landfill leachate due to drastic existing regulations. These authors used membranes close to nanofiltration, leachate had a low organic matter content and local water standards were not so strict. However, Syzdek and Ahlert (1984) suggested that UF might prove to be effective as a pre-treatment process for reverse osmosis (RO). UF can be used to remove the larger molecular weight components of leachate that tend to foul reverse osmosis membranes. Table 19 summarizes studies including an UF step. The elimination of polluting substances is never complete (COD between 10 and 75%) More recently, UF has been applied to biological post-treatment of landfill leachate (Bohdziewicz et al., 2001). Several hybrid processes such as activated sludge-ultrafiltration-chemical oxidation and activated sludge-ultrafiltration-reverse osmosis have been tested. Authors demonstrated that 50% of the organic matter could be separated by the UF step alone. Finally, UF membranes have been successfully used in full scale membrane bioreactor plants (Dijk and Roncken, 1997). High treatment levels for landfill leachate have been achieved in such a process.

3.4.3 Nanofiltration (NF)

NF technology offers a versatile approach to meet multiple water quality objectives, such as control of organic, inorganic, and microbial contaminants. NF studied membranes are usually made of polymeric films with a molecular cut-off between 200 and 2000 Da. The high rejection rate for sulphate ions and for dissolved organic matter (Table 20) together with very low rejection for chloride and sodium reduces the volume of concentrate (Peters, 1998). Few studies mention the use of NF to treat landfill leachates (Rautenbach and Mellis, 1994 ; Linde and Jonsson, 1995 ; Trbouet et al, 1998, 1999, 2001 ; Marttinen et al, 2002). Nearly 60-70% COD and 50% ammonia were removed by NF, whatever membrane material and geometry (flat, tubular, or spiral wounded), with an average velocity of 3 m.s-1 and a transmembrane pressure between 6 and 30 bars. Physical methods were used in combination with 23

nanofiltration and it was found satisfactory for removal of refractory COD from the leachate used. COD removal was 70-80% (Trbouet et al., 2001). However, successful application of membrane technology requires efficient control of membrane fouling. A wide spectrum of constituents may contribute to membrane fouling in leachates nanofiltration : dissolved organic and inorganic substances, colloidal and suspended particles (Trbouet et al., 2001). In particular, natural organic matter fouling has recently gained interest (Hong and Elimelech, 1997 ; Braghetta et al., 1998).

3.4.4 Reverse Osmosis (RO)

RO seems to be one of the most promising and efficient methods among the new processes for landfill leachate treatment. In the past, several studies, performed both at lab and industrial scale, have already demonstrated RO performances on the separation of pollutants from landfill leachate (Linde et al., 1995; Bilstad and Madland, 1992). Values of the rejection coefficient referred to COD parameter and heavy metal concentrations higher than 98 and 99%, respectively, were reported. Tubular and spiral wounded modules were the first medium used in the early RO systems for the purification of landfill leachate starting in 1984. An innovative technology was introduced to this market in 1988 : the disctube-module (DT-module) developed by Pall-Exekia. Thanks to open channel module, systems can be cleaned with high efficiency with regard to scaling, fouling and especially biofouling (Peters, 1996). In 1998, Peters reported that more than 80% of the total capacity installed for leachate purification by RO use a DT-module (Germany, the Netherlands, Switzerland, North America). Recent works confirmed the feasibility of using RO technologies for municipal leachate disposal whatever the organic content (Chianese et al., 1999 ; Di Palma et al, 2002 ; Ozturk et al., 2003). Table 21 proves the ability of modern high-rejection RO membranes to retain both organic and inorganic contaminants dissolved in water at rejection rates up to 80% in the worst case. However, in the case of

24

industrial landfill leachate the contemporaneous presence of both high concentration of organic compounds, ammonia and heavy metals strongly affects treatment performances (Di Palma et al., 2002).

5. Discussion/Conclusion

Optimal leachate treatment, in order to fully reduce the negative impact on the environment, is todays challenge. But, the complexity of the leachate composition makes it very difficult to formulate general recommendations. Variations in leachates, in particular their variation both over time and from site to site, means that the most appropriate treatment should be simple, universal and adaptable. The various methods presented in the previous sections offer each advantages and disadvantages with respect to certain facets of the problem. Suitable treatment strategy depends on major criteria : - the initial leachate quality. Table 22 summarizes the effectiveness of treatment process according to key leachate characteristics : COD, BOD/COD and age of the fill. The knowledge of these specific parameters may help to select suitable treatment processes for the lowering of organic matter present in leachate. - the final requirements given by local discharge water standards. Year after year, the recognition of landfill leachate impact on environment have forced authorities to fix more and more stringent requirements for pollution control. Even by combining biological and physico/chemical processes, only partial destruction of contaminants will be achieved. Due to the so called hard COD, new regulations will not be reached. In recent years, membrane filtration has emerged as a viable treatment alternative to comply with existing and pending water quality regulations.

Today, as stricter environmental requirements are continuously imposed, conventional treatment plants, such as biological treatments, appear under-dimensioned or do not allow to reach the 25

specifications required by the legislator. Moreover, considering the hardening of landfill regulations, controls and management, processes must be more and more efficient. According to this fact, force is to note that, in this paper (which appears the most exhaustive possible), the majority of studies focus on new technologies developments or conventional ones improvements. Among them, membrane technologies, either as a main step in a landfill leachate treatment chain (RO, nanofiltration) or in combination with a biological treatment (Membrane bioreactor) have been proved to be the more efficient, adaptable and indispensable means of both : - achieving full purification (rejection rates of 98-99% for RO), - solving the growing problem of water pollution. In Fig. 4 concerning leachate treatments distribution, french case clearly reflects the worldwide trend, namely a marked increase of pressure-driven membrane processes in comparison with biological treatment plants. Nevertheless, whatever the technology adopted, residues production still remains a major hurdle, since it is usually unusable and has to be discharged or further treated. Physico/chemical sludges, biological sludges and filtration concentrates produced during leachate purification constitutes a capital environmental concern. The transport to an incineration plant equipped for the burning of liquid hazardous waste remains the preferred option (in spite of many controversies) but leads to high treatment costs. Others possibilities are slowly gaining importance: - the solidification of residues with different materials, like fly ash or sludges from wastewater treatment plants, and disposal on the landfill itself, - controlled reinjection of the concentrate into changing areas of the landfill. However, this option may adversely affect anaerobic degradation of solid wastes. Lastly, sanitary landfilling enhancement remains inevitable, and so, some aspects need to be further investigated :

26

- techniques to prevent or control membrane fouling must be improved (suitable pre-treatment choice, modifications affecting surface membrane roughness or hydrophilicity/hydrophobicity, cleaning of membrane surface), - methods for treating or disposing the treatment residues must be developed or improved with respect to ecological and economical requirements, biogas capture must be promoted , because it permits interesting exploitation cost reductions.

References 27

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Appendix NOMENCLATURE AOP Advanced Oxidation Processes AS Activated Sludge BOD Biological Oxygen Demand COD Chemical Oxygen Demand DOC Dissolved Organic Carbon GAC Granular Activated Carbon HRT Hydraulic Retention Time MAP Magnesium Ammonium Phosphate 38

MBBR MSW PAC RO SBR SCBR SRT SS TKN TOC UASB VFA

Moving-Bed Biofilm Reactor Municipal Solid Waste Powdered Activated Carbon Reverse Osmosis Sequencing Batch Reactor Suspended-Carrier Biofilm Reactor Sludge Retention Time Suspended Solids Total Kjeldahl Nitrogen Total Organic Carbon Upflow Anaerobic Sludge Blanket Volatil Fatty Acids

Table 1 : Revised French regulation criteria (selected), in 1997.

Item COD TOC Total (TSS) BOD5 Volumetric Criterion after revision classification <100 kg.d-1 >100 kg.d-1 Solids <15 kg.d-1 >15 kg.d-1 <30 kg.d-1 >30 kg.d-1 300 mg.L-1 125 mg.L-1 70 mg.L-1 100 mg.L-1 35 mg.L-1 100 mg.L-1 30 mg.L-1

Suspended

39

Total Nitrogen

>50 kg.d-1

30 mg.L-1

40

Table 2 : Leachate composition (COD, BOD, BOD/COD, pH, SS, TKN, NH3-N).
Age Y Y Y Y Y Y Y Y Y Y Y Y Y Y MA MA MA MA MA MA MA MA MA MA MA O O O O O O O O O O COD BOD 13800 9660 1870 90 15700 4200 17000 7300 13000 5000 50000 22000 China, Mainland 1900-3180 3700-8890 Greece 70900 26800 Italy 19900 4000 Italy 10540 2300 South Korea 24400 10800 Turkey 16200-20000 10800-11000 35000-50000 21000-25000 Turkey 35000-50000 21000-25000 Turkey 10750-18420 6380-9660 Canada 3210-9190 China 5800 430 China, Hong Kong 7439 1436 Germany 3180 1060 Germany 4000 800 Greece 5350 1050 Italy 5050 1270 Italy 3840 1200 Poland 1180 331 Taiwan 6500 500 Turkey 9500 Brazil 3460 150 Estonia 2170 800 Finland 556 62 Finland 340-920 84 France 500 7.1 France 100 3 France 1930 Malaysia 1533-2580 48-105 South Korea 1409 62 Turkey 10000 Y = Young ; MA=Medium Age ; O = Old All values except pH and BOD/COD are in mg.L-1 Landfill site Canada Canada China, Hong Kong China, Hong Kong BOD/COD 0.70 0.05 0.27 0.43 0.38 0.44 0.36-0.51 0.38 0.20 0.22 0.44 0.55-0.67 0.5-0.6 0.5-0.6 0.52-0.59 0.07 0.19 0.33 0.20 0.20 0.25 0.31 0.28 0.08 0.04 0.37 0.11 0.09-0.25 0.01 0.03 0.03-0.04 0.04 pH 5.8 6.58 7.7 7.0-8.3 6.8-9.1 7.8-9.0 7.4-8.5 6.2 8 8.2 7.3 7.3-7.8 5.6-7.0 5.6-7.0 7.7-8.2 6.9-9.0 7.6 8.22 7.9 8.38 8 8 8.1 8.15 8.2 11.5 7.1-7.6 7.5 7.7 7 7.5-9.4 8.57 8.6 SS >5000 2000 2000 950 1666 2400 2630-3930 1013-1540 784 480 130 13-1480 159-233 404 1600 TKN 212 75 3200 11000 13000 3400 1766 2370 1135 1100 1670 1450 192 540 5-960 141 1680 NH3-N 42 10 2260 3000 11000 13000 630-1800 3100 3917 5210 1682 1120-2500 2020 2020 1946-2002 884 800 940 1330 743 5500 1270 800 159 330-560 430 0.2 295 1522 1590 Reference Henry et al., 1987 Lau et al., 2001 Lo, 1996 Wang and Shen, 2000 Tatsi et al., 2003 Di Palma et al., 2002 Lopez et al., 2004 Im et al., 2001 Timur and Ozturk, 1999 Ozturk et al., 2003 Ceen and Aktas, 2004 Kennedy and Lentz, 2000 Wang et al., 2002 Li and Zhao, 2001 Baumgarten and Seyfried, 1996 Dijk and Roncken, 1997 Tatsi et al., 2003 Frascari et al., 2004 Chianese et al., 1999 Bohdziewicz et al., 2001 Wu et al., 2004 Kargi and Pamukoglu, 2000, 2003 Silva et al., 2004 Orupold et al., 2000 Hoilijoki et al., 2000 Marttinen et al., 2002 Trbouet et al., 1999 Tabet et al., 2002 Gourdon et al., 1989 Aziz et al., 2004 Cho et al., 2002 Uygur and Kargi, 2004

41

Table 3 : Heavy metals composition in landfill leachate.

Age Y MA MA MA MA O O O O Landfill site Fe Mn Ba Italy 2.7 0.04 Canada 1.28-4.90 0.028-1.541 0.006-0.164 Hong Kong 3.811 0.182 South Korea 76 16.4 Spain 7.45 0.17 Brazil 5.5 0.2 France 26 0.13 0.15 Malaysia 4.1-19.5 15.5 South Korea 0.298 Y = Young ; MA=Medium Age ; O = Old All values are in mg.L-1 Cu 0.12 0.78 0.26 0.08 0.005-0.04 0.031 Al <0.02-0.92 <1 2 Si 3.72-10.48 <5 Reference Lopez et al., 2004 Kennedy and Lentz, 2000 Li and Zhao, 2001 Im et al., 2001 Rivas et al., 2003 Silva et al., 2004 Tabet et al., 2002 Aziz et al., 2004 Cho et al., 2002

42

Table 4 : Landfill leachate classification vs. Age (Chian and Dewalle, 1976).
Age (years) pH COD (mg.L-1) BOD5/COD Organic compounds Heavy metals Biodegradability Recent <5 6.5 >10000 >0.3 80% Volatile fat acids (VFA) Low-medium Important Intermediate 5-10 6.5-7.5 4000-10000 0.1-0.3 5-30% VFA + humic and fulvic acids Medium Old >10 >7.5 <4000 <0.1 Humic and fulvic acids Low Low

43

Table 5 : Combined treatment with domestic sewage.

Feeding COD (g.L ) 1090 10750 2431-37024 10750-18420
-1

BOD/COD pH 0.4 0.59 0.2-0.4 0.55 -

From

Operational conditions Kind of Volume of reactor reactor (L) SBR AS AS AS -

Performance Reference Volumetric T (C) HRT (d) removal (%) ratio (%) 20 1 1.3 1-10 0.11 (1:9) 6.7-13.3 5-20 5-25 95 BOD 60-90 COD 16-88 COD Diamadopoulos et al., 1997 Ceen and Aktas, 2001 Ceen and Cakiroglu, 2001 Ceen and Aktas, 2004

landfill leachate + municipal sewage 8.2 landfill 7.3-7.9 landfill landfill leachate + 7.7-8.2 municipal sewage

2 2 22 3.6 (aeration tank) 2.5 (settling tank)

44

Table 6 : Landfill leachate recycling.

Feeding COD (g.L ) 80000 47000-52000 716-1765 2560-5108
-1

pH 5.5-6.5 7.58-7.60 8.00-8.43

From Pilot plant Pilot plant Pilot plant Landfill

Operational conditions Volume of T Recirculation Rate reactor (L) (C) (L.d-1) 707 36 70 35 9-21 40 40

Performance removal (%) 98 COD 63-70 COD Reference Rodriguez et al., 2000 Sponza and Agdag, 2004 Rodriguez et al., 2004

45

Table 7 : Lagooning performance.

Feeding COD (g.L-1) 5518 Operational conditions Kind of lagoon Size Aerated lagoon 1000 m3 (1) Anaerobic pond (2) Aerated lagoon (3) Constructed wetlands (4) Free water surface (1) Primary lagoon (2) Aerated Wetlands (3) Final surge lagoon (1) Aerated lagoon (2) Polishing lagoon (laboratory-scale) Non-aerated lagoon (1) 400 m3 (2) 4000 m3 (3) 400 m (4) 2000 m Performance Reference removal (%) 97 COD Robinson and Grantham, 1988 60-95 COD Maehlum, 1995

BOD/COD 0.7 -

pH 5.8 -

From landfill landfill

T (C) -

HRT (d) >10 40

1182

0.26

landfill

(1) 113400 m3 (2) 4528 m3 (1) 17 L (2) 9.7 L 9960 m 19

20

89 COD

Martin and Johnson, 1995

765-3090

0.43-0.53

8.7-12.5

landfill

(1) 16-22 (2) 9.1-12.6 32

55-64 COD

Orupold et al., 2000

5050

0.25

8.38

landfill

22.8

40 COD

Frascari et al., 2004

46

Table 8 : Treatment effectiveness of landfill leachate with the use of coagulation/flocculation.

COD 4000-8810 4100 6000-8200 330 (Biologically treated) 282-417 TOC 782-1585 15700 1200-1500 5350 5000 7400-8800 3460 750 BOD/COD 10850 BOD 1500 BOD 0.15 0.05 0.11-0.17 0.02 0.07-0.15 0.27 0.04 0.2 <0.01 0.05-0.06 0.04 0.08 pH 6.55 8.3 8.2 7.5 From landfill landfill landfill landfill landfill landfill Coagulant Ca(OH)2 Ca(OH)2 Ca(OH)2 + Fe2(SO4)3 FeCl3 or Al2(SO4)3 Ca(OH)2 + Al2(SO4)3 FeCl3 + Al2(SO4)3 FeCl3 Al2(SO4)3 + FeCl3 Fe2(SO4)3 Al2(SO4)3 + FeCl3 FeCl3 FeCl3 + Al2(SO4)3 Fe2(SO4)3 + Al2O3 FeCl3 Al2(SO4)3 Bioflocculant (Rhizomonas) Concentration range 0.3-0.6 g.L-1 6 kg.m-3 0.5-4.0 + 0-0.2 g.L-1 0.01-0.07 M 1.5 + 1.0 kg.m-3 0.1-1.0 g.L-1 0.8-1.0 g.L-1 0.150 g.L-1 of Al + 0.05 g.L-1 0.3 g.L-1 of Fe 0.738 + 1.136 g.L-1 0.2-1.2 g.L-1 1.0-5.0 g.L-1 1.8-3.0 + 1.0-2.0 g.L-1 0.01 M 0.7 g.L-1 0.01-0.02 g.L-1 Removal (%) 8.2-23.5 COD 57 COD 39 COD 40-50 COD 42 COD 53 COD 38-48 TOC 20-35 COD 70 COD 55-70 Colour 39 COD 75 COD 67 COD 40-90 COD 10-25 COD 85 Humic acid 40 COD Reference Thornton and Blanc, 1973 Keenan et al., 1984 Loizidou et al., 1992 Amokrane et al., 1997 Papadopoulos et al., 1998 Welander et al., 1998 Yoon et al., 1998 Lema et al., 1988 Wang and Shen, 2000 Zamora et al., 2000 Yoo et al., 2001 Tatsi et al., 2003 Monje-Ramirez et Orta De Velasquez, 2004 Rivas et al., 2003 Silva et al., 2004 Zouboulis et al., 2004

aerated lagoon 7.6-8.2 landfill 7.7 landfill landfill 6.8-7.5 landfill 7.9 landfill landfill 8.5-9.0 landfill 8.2-8.5 landfill 7.5 landfill

47

Table 9 : Treatment effectiveness of landfill leachate with the use of chemical precipitation.
COD 1585 (Young leachate) 7511 65-1047 35000-50000 BOD/CO D 0.07 0.19 0.5-0.6 pH 8.2 8.22 From landfill landfill Precipitant Ca(OH)2 (1 g.L-1) MgCl2.6(H2O) + Na2HPO4.12(H2O) (Mg:NH4:PO4 = 1:1:1) MgCl2.6(H2O) + Na2HPO4.12(H2O) (Mg:NH4:PO4 = 1:1:1) Struvite (Mg:NH4:PO4 = 1:1:1) Removal (%) Reference 27 COD 40 COD 98 N-NH4+ 98 N-NH4+ 50 COD Baig et al., 1999 Li et al., 1999 Li and Zhao, 2001 Ozturk et al., 2003

7.79-8.52 landfill 5.6-7.0 landfill

48

Table 10 : Treatment effectiveness of landfill leachate with the use of adsorption.

COD 879-940 (biologically pretreated) 640 108 800-2000 625 9500 1533-2580 10750-18420 7000 716-1765 BOD/COD pH 0.03 7.5 0.06 0.04-0.07 0.3 0.03-0.04 0.55 8 7.9 7 7.5-9.4 7.7-8.2 From landfill landfill landfill landfill Adsorbent Granular activated carbon (columns) Granular activated carbon (columns) Powdered activated carbon Activated carbon (concentration range 210 g.L-1) Powdered activated carbon (2 g.L-1) Peat Powdered activated carbon (0-2 g.L-1) CaCO3 (particule size range 2-4 mm) Powdered activated carbon (concentration range 0.1-3.5 g.L-1) Powdered activated carbon (0-2 g.L-1) Granular activated carbon and resins removal (%) 91 COD 96 TOC 55-70 colour 69 COD 38 COD 90 COD 90 COD Reference Morawe et al., 1995 Fettig et al., 1996 Imai et al., 1998 Welander and Henrysson, 1998 Zamora et al., 2000 Heavey, 2003 Kargi and Pamukoglu, 2003 Aziz et al., 2004 Ceen and Aktas, 2004 Kargi and Pamukoglu, 2004

landfill landfill landfill landfill landfill leachate + municipal sewage 7 synthetic wastewater 7.58-7.60 Pilot plant

85 non-biodegradable Rodriguez et al., 2004 COD (GAC) 59 non-biodegradable COD (resin)

49

Table 11 : List of typical AOP systems (Huang et al., 1993).

Homogeneous System with irradiation O3/ultraviolet (UV) H2O2/UV electron beam ultrasound (US) H2O2/US UV/US H2O2/Fe2+/UV(photo-Fentons) without irradiation O3/H2O2 O3/OHH2O2/Fe2+ (Fentons) Heterogeneous Systems with irradiation TiO2/O2/UV TiO2/H2O2/UV without irradiation electro-Fenton

50

Table 12 : O3, O3/H2O2 and O3/UV treatments of leachates (updated from Wang et al., 2003).
COD removal (%) 44 62 50 50 25 71 67 80 33 35 23-32 66 30 67 >50 56 30 15 2.5-48 BOD/COD after treatment 0.4 140 mg.L-1 BOD5 0.35 0.15 0.11 0.21 0.25 0.32 0.25 0.5 -

COD (mg.L-1) Ozonation 1610 2300 2300 2300 740 4000 640 460 1050 500 300-1200 151 330 1585 518 895 3500 480 14600 2300-4970 6500 3460

BOD (mg.L-1) 210 210 210 240 230 205 DOC 30 <10 5 <8 111 43 25 25 2920 290-850 500 150

pH

O3/COD (g/g) 1.3 1.5 0.5 1 0.53 1.28-1.92 1.8 1.7 0.11 3 3.5 1.7 1.7 1.11 0.7 0.5 3.1 1.3-1.5 1.2 g.L-1 (O3 dose) 0.1-3 g.L-1 (O3 dose)

H2O2/O3 (g/g)

UV (W)

Reference

8 3 8 8.5 8.5 7 7.0-8.0 8.1 7.5 8.2 8.3 8.2 8.2 7.7 7.8 7.90-9.02 8.1 8.3

Huang et al., 1993 Bigot et al., 1993

Hausler et al., 1995 Sandya et al., 1995 Fettig et al., 1996 Barratt et al., 1997 Karrer et al., 1997 Steensen, 1997 Imai et al., 1998 Welander et al., 1998 Baig et al., 1999 Baig and Liechti, 2001 Geenens et al., 2001 Derco et al., 2002 Haapea et al., 2002 Qureshi et al., 2002 Rivas et al., 2004 Wu et al., 2004 Silva et al., 2004

O3/H2O2 2000 600 2000 895 1360 480 O3/UV 1280 1280 2300 430 TOC 26000 26000

160 43 <5 25

8.4 8 8 8.2 8.4 7.7

95 92 92 97 70 28 93 40

0.13 0.14 0.32 0.13

3.5 3.3 1.5 2.5 g.L-1 (O3 dose) 0.76 1.5 0.05-0.5

0.4 0.4 0.3 1 0.5 0.3 0.25-1

Wable et al., 1993 Bigot et al., 1994 Schulte et al., 1995

Geenens et al., 1999 Haapea et al., 2002

100 100 210 2920 2920

2 2 8 7.8 7.8

54 47 50 51 TOC 63 61

0.32 0.35

1 0.1 g.L-1 (O3 dose) 3.5 4.7

100 500 15 300 1500 1500

Ince, 1998 Bigot et al., 1994 Wenzel et al., 1999 Qureshi et al., 2002

51

Table 13 : H2O2/UV, H2O2/Fe2+ and H2O2/Fe2+/UV in leachates treatment (updated from Wang et al., 2003).
BOD/COD after treatment 0.37 0.4 0.45 Fe2+ (mg.L-1)

COD (mg.L-1) H2O2/UV 760 760 1000-1200 1000-1000 1280 1280 430 TOC 26000 26000 26000 H2O2/Fe2+ 1050-2020 1200 1150 2000 330 282-417 TOC 1500 Old leachate 1800 1800 1500 1500 10540

BOD pH (mg.L-1) <10 <10 100 100 2920 2920 2920 3 3.0-4.0 3.0-4.0 2 2 3 3 3

COD removal (%) 22 99 90 85 57 59 42 TOC 79 91 96

UV (W)

H2O2 (g.L-1) 3.4 3.4 0.5 0.5 5.19 13 26

Reference

150 150 15 150 100 500 300 1500 1500 1500

Schulte, 1995 Steensen, 1997 Ince, 1998 Wenzel et al., 1999 Qureshi et al., 2002

50-270 3-5 87 <8 30 225 225 75 75 2300

3 4 3 3.5 7.5 3 3 3.5 3 4.5 6 8.5 8.2

50 60 63 70 69 72 49-76 TOC 55 75 52 45 70 14 60

0.15 0.58 0.3 0.22 0.27 0.5

1.6 0.2 2.44 1.5 10 mL.L-1 1 2.2 1.65 1 1.5 1.2 0.2 0.2 1

600-800 56 120 20 1250 645 1000 2000 1500 300 300 830

Schulte et al., 1995 Gau and Chang, 1996 Bae et al., 1997 Kim et al., 1997 Kim and Huh, 1997 Welander et al., 1998 Yoon et al., 1998

Kang and Hwang, 2000 Zamora et al., 2000 Kim et al., 2001

Lau et al., 2001 Lopez et al., 2004

H2O2/Fe2+/UV 1150 3-5 1150 440 -

3 3.2 2.7

70 70 78

500-1000 1.15 UVA 1.15 UVA 0.44

56 72 30

Kim et al., 1997 Kim and Vogelpohl, 1998

52

Table 14 : Treatment effectiveness of landfill leachate with the use of air stripping
From landfill landfill synthetic wastewater landfill landfill NH4+-N (mg.L-1) 556-705 74-220 1270 1025 800 Time of stripping (h) 24 24 0.75 17 120 NH4+-N removal (%) 76-93 89 45 85 99.5 Reference Cheung et al., 1997 Marttinen et al., 2002 Kargi and Pamukoglu, 2003 Ozturk et al., 2003 Silva et al., 2004

53

Table 15 : Different aerobic reactors performance.

Feeding COD (g.L )
-1

BOD/COD

pH 7 5.95 8 12-13 6.8-7.4 8 7.5 7.3 8.22 -

From landfill landfill landfill coke-plant landfill landfill landfill landfill landfill landfill landfill UASB reactor pretreatment landfill landfill Municipal solid waste

Operational conditions Volume of HRT T (C) reactor (L) (days) >4 20 470 6700 5.9 65000 m 0.5 5 30 3.35 40 2 9 20-25 5-10 21 25 24 25 25 20 5-10 23 35 10 (SRT) 1.5 6.25 2.75 0.5-2 3.4 h 3 10 1 4.5

Performance removal (%) 51.3 TOC >92 COD 96 COD 46-64 COD 59 COD 75 COD 97 COD 87.5 N-NH4+ 69 COD 50 COD 80-90 COD 78-98 COD 85-89 COD Reference

Activated sludge reactor 4000 (BOD) 5000 0.6 1000-4000 1537 2000-4600 0.41-0.59 3176 0.33 2900 0.66 5000-6000 2560 200-1200 (NH4+) 3130 270-1000 24400 7439 5400-20000 0.56 -

Bull et al., 1983 Robinson and Maris, 1983 Rautenbach and Mellis, 1994 Yi et al., 1994 Kettunen and Rintala, 1995 Baumgarten and Seyfried, 1996 Kettunen et al., 1996 Bae et al., 1997 Martienssen and Schops, 1997 Shiskoswski and Mavinic, 1998 Bae et al., 1999 Hoilijoki et al., 2000 Im et al., 2001 Li and Zhao, 2001 Agdag and Sponza, 2004

Sequencing batch reactor 5295 0.49 2560 0.07 2110 1183 15000 9500 7000 5750 0.4-0.5 -

9.1 8.6 6.9 8 7.5 7 7 8.6

landfill landfill anaerobic lagoon pretreatment landfill landfill landfill synthetic wastewater landfill

10-20 32 45 8 18.8 18.8 5

25 20 40-50 20 25 25

0.5 20-40 3.2 1 1.25 1.25 -

62 DOC 48-69 COD >99 NH4+ 91 COD 6.7 COD 75 COD 74 COD 75 COD 62 COD

Dollerer and Wilderer, 1996 Lo, 1996 Zaloum and Abbott, 1997 Bohdziewicz et al., 2001 Zouboulis et al., 2001 Kargi and Pamikoglu, 2003 Kargi and Pamukoglu, 2004 Uygur and Kargi, 2004

54

Table 15 (following)
Feeding COD (g.L )
-1

BOD/COD

pH 12-13 9 8 8 >7.5 7.7

From landfill landfill landfill landfill landfill landfill landfill (preozonation)

Operational conditions Volume of HRT T (C) reactor (L) (days) 1 1.5 0.22-0.6 4.5 5000 8 2 21 20 5-22 20 17 1 2-5 4 20-24 -

Performance removal (%) 75 COD 60 COD 20-30 COD 42-57 DOC 20 COD 81 COD 85 NH3 60-80 TOC Reference

Moving-bed biofilm reactor 2000-3000 0.41-0.59 1740-4850 0.05-0.1 800-1300 0.1 108 0.06 800-2000 5000 480 0.2 0.05

Kettunen and Rintala, 1995 Horan et al., 1997 Welander et al., 1997 Imai et al., 1998 Welander and Henrysson, 1998 Loukidou and Zouboulis, 2001 Haapea et al., 2002

Trickling filter 850-1350 0.1-0.2 2560 230-510 0.04-0.08

8.0-8.5 landfill 8 landfill 6.5-7 landfill

16500 141 9.4

1.7-19.7 25 5-25

0.6-4.5 2.1-9.6

87 BOD 90 NH4+

Gourdon et al., 1989 Martienssen and Schops, 1997 Jokela et al., 2002

55

Table 16 : Membrane bioreactor effectiveness for the treatment of landfill leachates.

Feeding COD (g.L ) 4000 2750-3105 2740-3200 -1

Operational conditions BOD/COD pH 0,2 0.48 0.51 6.5-7.5 From landfill landfill landfill Volume of T (C) reactor (m3) industrial scale 180 stirred tank / biologically active 15 28-30 carbon process Kind of reactor pilot research HRT (d) 3-4 -

Performance COD removal (%) >90 95-98 TOC 90

Reference Wherle Werk, 1995 Pirbazari et al., 1996 Dijk and Roncken, 1997

56

Table 17 : Different anaerobic reactors performance.

Feeding COD (g.L ) Digester 4000 (BOD) 37000-66660 1000-4000 1537 2560 5100-8300 200-1200 (NH4+) 800-2000
-1

BOD/COD pH 0.4-0.6 0.43-0.50 7 8 8 7.6-9.3 7.5 -

From landfill landfill landfill coke-plant landfill landfill landfill landfill

Operational conditions Volume of T (C) HRT (d) reactor (L) >4 2 6 155 3300 30 1.25 900 20-25 24 35 25 15.5-35 20 17 86 30 1-20 0.75 2-10 1.72 h 0.72

Performance removal (%) 96 BOD 53 COD 92.5 COD 95.7 COD 56-70 COD 20 COD Reference

Bull et al., 1983 Lin, 1991 Rautenbach and Mellis, 1994 Yi et al., 1994 Martienssen and Schops, 1997 Sung Sung et al., 1997 Shiskowski and Mavinic, 1998 Welander and Henrysson, 1998

Anaerobic sequencing batch reactor 546-5770 (TOC) 0.53 7.3-7.8 15000 7.5 5750 8.6

landfill landfill (stabilized leachate) landfill

2 8 5

35 40-50 25

10-1.5 -

73.9 TOC 75 COD 62 COD

Timur and Ozturk, 1997 Zouboulis et al., 2001 Uygur and Kargi, 2004

Up-flow anaerobic sludge blanket reactor 6649-15425 7.6-8.7 landfill 10000-64000 61-7.8 landfill 3000-4300 0.65-0.67 6.8-7.4 landfill 1500-3200 0.61-0.71 6.5-7.0 landfill 30000 landfill 3800-15900 0.54-0.67 7.3-7.8 landfill 3210-9190 6.9-9.0 landfill 9264-12050 7.2 anaerobic digestion plant sludge + septage + leachate 24400 7.3 landfill 35000-50000 0.5-0.6 5.6-7.0 landfill 5400-20000 municipal solid waste

3.5 0.38 40 4.6 2 6.2 13.5 20 2.5

15-35 11-24 13-23 30 35 35 35 36 37-42

2.4 0.6-0.1 0.4-1.4 0.96-1.30 0.75 10-1.5 0.5-1 1.5-10 1.25

88 COD 82 COD 45-71 COD 65-75 COD 82 COD 83 COD 77-91 COD 58 COD 80-90 COD 96-98 COD

Garcia et al., 1996 Kettunen et al., 1996 Kettunen and Rintala, 1998 Borzacconi et al., 1999 Timur and Ozturk, 1999 Kennedy and Lentz, 2000 Lin and Chang, 2000 Im et al., 2001 Ozturk et al., 2003 Agdag and Sponza, 2004

57

Table 17 (following)
Feeding COD (g.L ) Anaerobic filter 14000 3750 5000-6000 Hybrid bed filter 2000-3000 1800 19600-42000 1250-4490 (TOC)
-1

BOD/COD 0.7 0.3 -

PH

From

Operational conditions Volume of T (C) HRT (days) reactor (L) 3 4 21-25 35 2-4 0.5-1 -

Performance removal (%) 68-95 COD 60-95 COD 87.5 NH4+ Reference

5.8 young landfill 6.35-6.58 old landfill landfill

Henry et al., 1987 Bae et al., 1997

0.41-0.59 0.53 0.53

12-13 6.8-7.4 6.5-7.5 7.3-7.8

landfill landfill landfill landfill

2.5 0.56 22 3.35

21 11 30 35

62 1.4 2.5-5 5.1-0.9

75 COD 56 COD 81-97 COD 65.3 TOC

Kettunen and Rintala, 1995 Kettunen et al., 1996 Nedwell and Reynolds, 1996 Timur and Ozturk, 1997

Fluidized bed reactor 108 0.06 1100-3800 -

8 -

landfill landfill

4.5 7.9

20 35

42-57 DOC 82 COD

Imai et al., 1998 Suidan et al., 1993

58

Table 18 : Treatment effectiveness of landfill leachate with the use of Microfiltration.

Operating conditions Material / Geometry Polypropylene / Tubular (Membrana GmbH / Accurel) Cut-off 0.2 m Surface (m) 0.11 T (C) 20 velocity P (bar) (m.s-1) 4.1-4.3 Feeding From landfill COD (g.L ) 2300
-1

Performance pH 7.5 Flux COD removal (%) 25-35 (retention rate) Reference Piatkiewicz, 2001

59

Table 19 : Treatment effectiveness of landfill leachate with the use of Ultrafiltration.

Operating conditions Material / Geometry Substituted olefin, aromatic, polymer, polyelectrolyte complex, cellulose acetate (Amicon) Cellulosic / Tubular (Memtek Corp.) PVC / Flat Polysulfone / Tubular Polysulfone / Tubular (Membrana GmbH / UltraPES) Cut-off 0.5-300 kDa dp = 0.2 m 20-55 kDa 300 kDa 50-80 kDa Surface velocity T (C) (m) (m.s-1) 0.0065 0.0155 0.025 0.15 Feeding P (bar) From 20-22 p.s.i. 3 landfill landfill landfill landfill COD (g.L-1) 14000-17000 (TOC) 8300-9500 1660 1700 pH 7.0 7.0 8.6 Performance COD Flux removal -1 -2 (L.h .m ) (%) 30-180 95-98 50 5-10

Reference Syzdek and Ahlert, 1984 Pirbazari et al., 1996 Bohdziewicz et al., 2001 Piatkiewicz, 2001

20-45 25 20 2.5 4.1-4.3

60

Table 20 : Treatment effectiveness of landfill leachate with the use of Nanofiltration.

Operating conditions Material / Geometry Spiral wound (Desal) Organic / Tubular (PCI Membrane Systems.) Polyacrilonitrile / Flat (Koch-Weizmann) Polysulfone / Flat (KochWeizmann) Cut-off 50% NaCl 1ppm 450 Da 450 Da Surface (m) 0.04 0.007 0.007 0.125 0.049 25 3 20 landfill 500 7.5 velocity T (C) (m.s-1) 25 25 2.8 1-5 P (bar) 8.5 15-30 0-15 Feeding From landfill landfill landfill COD (g.L-1) pH Performance Flux COD removal Reference -1 -2 (L.h .m ) (%) 7-12 55-75 18 52 57 80 60 0.0045 25 3 6-8 landfill 200-600 7.3-7.9 97.5-99 55-60 TOC 60 75 65 74 80 52-66 Marttinen et al., 2002 Trbouet et al., 1999 Rautenbach and Mellis, 1994 Linde and Jonsson, 1995 Trbouet et al., 1998, 2001

142 TOC 550-2295 7.4-7.8

Oxide de Zirconium / 1000 Da Tubular (Koch-Weizmann) Polyacrilonitrile / Tubular (Koch-Weizmann) Polysulfone / Tubular (Koch-Weizmann) Polymer / Flat sheet (Desal) 450 Da 450 Da 200-300 Da

61

Table 21 : Treatment effectiveness of landfill leachate with the use of Reverse Osmosis.
Operating conditions Material / Geometry Composite / Tubular (PCI Membrane Systems.) Tubular / Spiral wound Surface (m) 0.013 T (C) 20 25 P (bar) 40 40 Feeding From landfill landfill (Biological pretreatment) landfill landfill landfill landfill (MBR pre-treatment) landfill (Evaporation pre-treatment) landfill COD (g.L ) 335-925 1 301
-1

pH -

Performance Reference Flux removal (%) -1 -2 (L.h .m ) 3-48 >98 COD Linde et al., 1995 30 99 COD Baumgarten and Seyfried, 1996 Chianese et al., 1999 Bohdziewicz et al., 2001 Piatkiewicz, 2001 Ahn et al., 2002 Di Palma et al., 2002

Spiral wound Cellulose acetate / Flat (Osmonics) Spiral wound Polyamide / Spiral wound (Filmtec) Polyamide (Desal)

0.0155 6.7 0.0044

28 25 20 -

20-53 27.6 60

0-1.749 846 1820 211-856 200.5

6 8.8 5.6-6.6 8

20.7-29

96-98 COD 93 COD 97 COD 86-90 COD

Polyamide / DT-Module (Pall)

7.6 7.6 7.9 2

15.5-31.8 9-70.5 30 3-11 26-174 25 55

4.8-7.0 5.0-5.9 8

Spiral wound

landfill

1700 3000

47.2-102.8 L/h/module 50-105.8 L/h/module 32 58

50-85 COD 80-90 COD 99 COD 89 COD

Ushikoshi et al., 2002

Ozturk et al., 2003

62

Table 22 : Effectiveness of treatment vs. leachate characteristics.

Character of leachate Young Medium Old Good Good Good Fair Fair Fair Poor Poor Poor Average Removal (%) BOD COD TKN

Process Transfer Combined treatment with domestic sewage Recycling Lagooning Physico/Chemical Coagulation/Flocculation Chemical precipitation Adsorption Oxidation Stripping Biological Aerobic processes Anaerobic processes Membrane Bioreactor Membrane filtration Ultrafiltration Nanofiltration Reverse Osmosis

SS

Turbidity

Residues

Depending on domestic water treatment plant >90 80 60-80 40-95 >80 30-40 30-40

excess biomass sludge

Poor Poor Poor Poor Poor

Fair Fair Fair Fair Fair

Fair Poor Good Fair Fair

>80 -

40-60 <30 70-90 30-90 <30

<30 <30 >80

>80 30-40 -

>80 >80 50-70 >80 30-40

sludge sludge residual O3 air-NH3 mixture

Good Good Good

Fair Fair Fair

Poor Poor Fair

>80 >80 >80

60-90 60-80 >85

>80 >80 >80

60-80 60-80 >99

40-60

excess biomass excess biomass excess biomass

Poor-Fair Good Good

Good Good

Good Good

80 >90

50 60-80 >90

60-80 60-80 >90

>99 >99 >99

>99 >99 >99

concentrate concentrate concentrate

63

100 90 80 70 60 50 40 30 20 10 0 1973 1978 1983 1988 1993 1998 2003 Year

Fig. 1 : Evolution of published works concerning landfill leachate treatment since 1973 (source : Chemical Abstracts).

Number of published works in the literature

64

Collection drain Rext Precipitation P

Evaporation
EV

Rint

Rext

Fitted tip Infiltration I

Exploited tip

Effluent E

Fig. 2 : Water cycle in a sanitary landfill (Billard, Techniques de lIngnieur).

65

100 % COD

Organic matter
Hydrolysis 66 %
Amino acids, sugars

34 %
Fatt y acids sugars

Fermentation

Acidogenesis
I ntermediary products : propianate, butyrate

Anaerobic Oxidation

46 %

20 % Acetogenesis

34 %

Acetotroph Hydrogenotroph 30 % 70 % Methanogenesis

100 % COD
Fig. 3 : COD banlance of the organic fraction in a sanitary landfill (Lema et al., 1988).

66

46 62

18 10 9 21 13 23

2000 Transfer + others Membrane

2002 Physico-chemical Biological

Fig. 4 : Landfill leachate treatment distribution, in France (source : ADEME, 2002).

67