LANDFILL LEACHATE TREATMENT USING FREE WATER SURFACE CONSTRUCTED WETLANDS SITI RABE’AH BINTI OTHMAN A project report submitted in partial fulfillment of the requirements for the award of the degree of Master of Engineering (Civil – Environmental Management) Faculty of Civil Engineering Universiti Teknologi Malaysia NOVEMBER, 2007 iii This work is dedicated to my parents Hj. Othman Hj. Kassim, Hjh. Laila Mariam Hj. Pudzil and my family members who love me and support me during my whole journey of education. Without you all who am I today! iv ACKNOWLEDGEMENT “In the name of God, the most gracious, the most compassionate” I would like to thank and express my appreciation for the support that I received throughout my studies from my supervisor, Assoc. Prof. Dr. Johan Sohaili and Pn. Normala Hashim and Cik Shamila Azman. They went above and beyond the call of my duty as members of my steering committee, and never failed to keep my eyes on the bottom line. I enjoyed doing my M.Eng study under their supervision. Also, during my stay at Universiti Teknologi Malaysia I have had the chance to meet and learn from many people. Among them there are three individuals that have been a great teacher and friend, and have contributed to my studies by discussing and commenting on different aspects of this work. Special thanks go to Dr. Fadhil Othman, Dr. Fadhil Md. Din, and Dr. Azmi Aris as well. Many friends and colleagues have contributed to my studies in many ways. The exceptional help, support and friendship that I received from Mohd. Izuddin, Mohd. Fahmi, Hafizi, Abd. Karim and Azhan. Finally, I wish to express my heartfelt thanks to all my environmental laboratories technicians, especially to Pak Usop, En. Ramlee Ismail, Pn. Rosmawati and En. Muzaffar for their timely support during my stay in the laboratories. “May Allah bless us with His Taufik and Hidayat. May we benefit from the knowledge He has given us. May we always be under His Protection and Guidance. May He forgive us for our sins, those we know and those we do not know. May He place us on the righteous path and steadfast our Imans. May He shower our one and true Prohphet Muhammad Alaihisalam and his family and followers, with eternal blessings. Amin amin, ya rabbal-alamin” v ABSTRAK Masa kini, pengurusan sisa pepejal dan rawatan airsisa merupakan masalah utama yang sedang kita hadapi. Jumlah sisa pepejal yang dihasilkan di seluruh dunia meningkat secara mendadak, begitu juga di Malaysia amnya. Walaupun terdapat pelbagai alternatif untuk mengurangkannya, atau untuk tujuan rawatan dan pelupusan. Tempat pelupusan sampah (landfill) masih kerap dipraktikkan di negara maju dan membangun. Walaubagaimanapun, kaedah landfill ini menyebabkan penghasilan air leleh (leachate). Air leleh (leachate) dari pusat pelupusan sampah adalah merupakan cecair yang menyusup dari sesuatu tapak pelupusan ke alam sekitar. Tanah bencah buatan (constructed wetlands) muncul sebagai salah satu kaedah rawatan alternatif yang berpotensi dengan menggunakan tumbuhan tenggelam (emergent plant) untuk menyingkirkan bahan cemar dari air leleh. Dalam kajian ini, tanah bencah buatan telah di bangunkan menggunakan tumbuhan Limnocharis flava untuk merawat air leleh dari tapak pelupusan. Kepekatan air leleh yang berbeza (50% dan 33%) telah dikaji di tanah bencah buatan tersebut untuk membandingkan keupayaan rawatan dari segi keupayaan penyingkiran bahan cemar dan keupayaan penyingkiran tanah bencah buatan apabila masa tahanan hidraulik (HRT) yang berlainan digunakan. Keputusan menunjukkan bahawa keupayaan penyingkiran tertinggi bagi HRT 3 hari telah diperolehi di Cell B dimana peratus penyingkiran NH3-N, PO43-, Mn, Fe, Turbidity, dan TSS adalah 83%, 88%, 91%, 92%, 100%, dan 98%. Bagi HRT 6 hari pula, penyingkiran tertinggi adalah NO3-N, PO43-, Turbidity dan TSS dimana peratusan adalah 98%, 98%, 100% dan 90% telah didapati di Cell B, selain itu, penyingkiran tertinggi bagi Cell A pula berlaku di HRT 6 hari dimana parameter yang diperolehi adalah NH3-N, COD, Mn, Fe, Tubidity dan TSS iaitu 93%, 91%, 90%, 94%, 100% dan 90%. Walaubagaimanapun, keputusan makmal menunjukkan bahawa keupayaan penyingkiran bagi HRT 3 hari dan 6 hari tidak menunjukkan perbezaan yang ketara. vi ABSTRACT Nowadays, solid waste management and wastewater treatment are the most important problems that we are facing. The amount of solid waste produced around the world is increasing at high rate as well as in Malaysia. Although there are different alternatives to reduce them or for their treatment and disposition, landfill is still the most common practice in developed and developing countries. However, the landfill method causes generation of leachate Landfill leachate refers to the liquid that seeps through a landfill site and enters the environment. Constructed wetlands emerged as one of the potential treatment alternative that employed emergent plants to remove pollutant from leachate. In this research, a constructed wetland was developed by using Limnocharis flava to treat the landfill leachate. Different leachate concentration (50% and 33%) was studied in the constructed wetland to compare the treatment efficiency in terms of pollutants removal in leachate and the efficiency of the system in different hydraulic retention time (HRT). The result shows a better removal efficiencies at HRT 3 days can be obtained in Cell B where the parameter are NH3-N, PO43-, Mn, Fe, Turbidity, and TSS (83%, 88%, 91%, 92%, 100%, and 98% removal). The highest removal at HRT 6 days are NO3-N, PO43-, Turbidity and TSS (98%, 98%, 100% and 90%) can be obtained in Cell B, while in Cell A the highest removal parameters are NH3-N, COD, Mn, Fe, Tubidity and TSS (93%, 91%, 90%, 94%, 100% and 90%). However, the highest removal of COD can be obtained at HRT 6 days in control unit of 94%. However, the laboratory result shows that the removal efficiencies for HRT 3 days and HRT 9 days have not much different. vii TABLE OF CONTENT CHAPTER 1 2 TITLE PAGE DECLARATION ii DEDICATION iii ACKNOWLEDGEMENT iv ABSTRAK v ABSTRACT vi TABLE OF CONTENTS vii LIST OF FIGURES x LIST OF PLATES xiii LIST OF TABLES xiv LIST OF SYMBOLS xvi LIST OF APPENDICES xvii INTRODUCTION 1 1.1 Reviews 1 1.2 Constructed Wetland and Landfill 2 1.3 Objectives of the Study 4 1.4 Scope of Study 5 1.5 Problem Statement 5 LITERATURE REVIEW 7 2.1 Introduction 7 2.2 What is Constructed Wetlands? 8 2.3 Types of Constructed Wetland 9 2.3.1 Free Water Surface Wetlands (FWS) 10 viii 2.3.2 Sub-Surface Flow Wetlands (SSF) 12 2.3.3 Hybrid Systems 17 2.4 Theory of Operation 18 2.5 Aquatic Macrophytes 19 2.6 Treatment Process Mechanisme 22 2.6.1 Biodegradable Organic Matter Removal 22 2.6.2 Metal Removal Mechanisms 26 2.6.3 Removal of Nitrogen 26 2.6.4 Removal of Phosphorus 29 2.7 3 2.6.5 Solids Removal 31 Landfill Leachate 31 2.7.1 Leachate Generation 32 2.7.2 Leachate Composition 33 2.8 Leachate Contol Strategies 36 2.9 Type of Landfill 37 RESEARCH METHODOLOGY 39 3.1 Introduction 39 3.2 Experimental Set Up and Operating Conditions of 41 Constructed Wetland 3.3 4 Experimental Analysis 44 3.3.1 Analysis of Leachate 44 RESULTS AND DISCUSSION 47 4.1 Introduction 47 4.2 Pollutant Removal In Leachate 48 4.3 Water Quality Analysis 51 4.3.1 Total Suspended Solid Removal 52 4.3.2 Turbidity Removal 54 Organic Matter Analysis 56 4.4.1 56 4.4 4.5 Biochemical Oxygen Demand Removal Chemical Water Quality Analysis 58 4.5.1 58 Ammonia Nitrogen Removal ix 5 4.5.2 Nitrate Nitrogen Removal 59 4.5.3 Phosphorus Removal 61 4.5.4 Manganese Removal 63 4.5.5 Iron Removal 65 4.6 Analysis of Variance 66 4.7 Conclusion 67 CONCLUSIONS 69 5.1 Introduction 69 5.2 Recommendations 70 5.3 Conclusions 71 REFERENCES 73 APPENDICES 84 x LIST OF FIGURES NO. TITLE PAGE Figure 2.1 Typical surface flow and subsurface flow constructed wetlands 9 Figure 2.2 Classification of constructed wetlands for wastewater treatment 10 (Vymazal, 2001) Figure 2.3 Free water surface flow (FWS) constructed wetland 12 Figure 2.4 The free water surface constructed wetlands in a foreign 12 country Figure 2.5 The subsurface constructed wetlands in a foreign country 13 Figure 2.6 Longitudinal constructed wetlands with horizontal SSF. Key: 15 1) Inflow of mechanically pretreated wastewater; 2) Distribution zone filled with large stone; 3) Impermeable liner; 4) Medium (Gravel, sand, crush stones); 5) Vegetation; 6) Outlet collector; 7) Collection zones filled with large stones; 8) Water level in the bed maintained with outlet structure; 9) outflow (Vymazal, 1997). Figure 2.7 Typical arrangement of a vertical flow (VF) reed bed system 16 Figure 2.8 Hybrid constructed wetlands for wastewater treatment (based 18 on Cooper, 1999) Figure 2.9 Floating aquatic weeds (a) water lettuce (Pista stratiotes); (b) 20 water lily (Nymphaeaceae) Figure 2.10 Emergent aquatic weeds (a) Cattails (Typha latifolia); (b) 21 common reeds (Phragmites australis) Figure 2.11 Aerobic condition (oxygen from water column if FWS systems and from atmosphere if SF systems) (Chongrak and Lim, 1998) 23 xi Figure 2.12 Aerobic condition (oxygen from plant roots) (Chongrak and 23 Lim, 1998) Figure 2.13 Simplified wetlands nitrogen cycle (Kadlec and Knight, 1996) 29 Figure 2.14 Phosphorus removal process in constructed wetlands 30 Figure 2.15 Typical layout of landfill 32 Figure 2.16 Classification of landfill structures (Chew, 2005) 38 Figure 3.1 The framework of study 40 Figure 3.2 Limnocharis flava (yellow burhead) 42 Figure 4.1 Percentage of removal for Cell A and B for total suspended 53 solids (TSS). The FWSCW system can reach until 100% removal for both cells. Figure 4.2 Concentration of TSS as a function of sampling day for Cell A, 54 B as well as control unit where the concentration at HRT 9 day reaches 0 mg/l. It was believed that all the particles are trapped in the media. Figure 4.3 Percentage removal for Cell A, B and control unit in different 54 HRT. The percentage removals are increasing steadily where the system can reach until 100% removal for those cells in FWSCW. Figure 4.4 The turbidity concentration with different HRT for Cell A, B 55 and control unit where the leachate concentration are decrease due to sedimentation and filtration that occur during the process. Figure 4.5 The percentage of removal of COD for Cell A, B and control 56 unit. The removals are increase steadily up to 94% removal in control unit. On the other hand, the removal of control unit higher than Cell A and B which was probably due to the presence of non-biodegradable organic compounds in the landfill leachate. Figure 4.6 The effluent quality for Cell A, B and control unit with different HRT. The highest COD removal occurs in Cell B at HRT 9 day with 95.0 mg/l. The effluent quality for HRT 3 day can be observed in Cell A with 93.0 mg/l. 57 xii Figure 4.7 The percentage of removal for NH3-N with different hydraulic 58 retention time (HRT). The highest removal can be obtained in Cell A at HRT 6 day. The lowest removal of NH3-N occurs in control unit with 26% at HRT 6 day. Figure 4.8 The percentage of removal for NO3-N with different hydraulic 60 retention time (HRT). The highest removal can be obtained in Cell B at HRT 6 day with removal 98%. The lowest removal of NO3-N occurs in control unit with 25% at HRT 9 day. Figure 4.9 The percentage removal of orthophosphate under different 62 HRT. The highest removal can be obtained in Cell B at HRT 6 day with removal 98%. The lowest removal of PO43- occurs in control unit with 23% at HRT 3 day. Figure 4.10 The percentage removal of manganese under different HRT. 64 The highest removal can be obtained in Cell B at HRT 3 day with removal 91%. The lowest removal of Mn occurs in control unit with 48% at HRT 9 day. Figure 4.11 The percentage removal of iron (Fe) under different HRT. The highest removal can be obtained in Cell A at HRT 6 days with removal 94%. The lowest removal of Mn occurs in control unit with 17% at HRT 3 days. 65 xiii LIST OF PLATES NO. TITLE PAGE Plate 3.1 Lab-scale constructed wetland 41 Plate 3.2 Dilution of landfill leachate before pour into the cells 43 Plate 3.3 Different concentration during the experiment 44 xiv LIST OF TABLES NO. TITLE Table 2.1 Some environmental requirements of the aquatic weeds PAGE 24 (adapted from Stephenson et. al., 1980; Reed et. al., 1988 and USEPA, 1988). Table 2.2 Summary of removal mechanisms in wetland for the 25 pollutant in wastewater (Adapted from Stowell et. al., 1981) Table 2.3 Nitrogen transformation in wetlands Table 2.4 Landfill leachate composition from three different sources 34 (Harrington et al., 1986) Table 2.5 Landfill Leachate Composition from new and mature 35 landfill (Tchobanoglous et. al., 1993). Table 2.6 Landfill Aged Influence on BOD5/COD Ratio and pH of 36 leachate (Henry, 1987 and Amokrane, 1997) Table 2.7 Classification of Landfill Structure (Pankratz, 2001) 37 Table 3.1 The characteristics of the Limnocharis flava 43 Table 4.1 Characteristics of landfill leachate used in FWSCW 48 experiments Table 4.2 Effluent concentration after treated by FWSCW for Cell A 49 Table 4.3 Effluent concentration after treated by FWSCW for Cell B 49 Table 4.4 Effluent concentration after treated by FWSCW for control 50 unit Table 4.5 Removal efficiencies in FWSCW at HRT 3 day 50 Table 4.6 Removal efficiencies in FWSCW at HRT 6 day 51 Table 4.7 Removal efficiencies in FWSCW at HRT 9 day 51 Table 4.8 Significant differences between control, Cell A and Cell B 66 at HRT 3 days xv Table 4.9 Significant differences between control, Cell A and Cell B 67 at HRT 6 days Table 4.10 Significant differences between control, Cell A and Cell B 67 at HRT 9 days Table 4.11 Percentage removal for three cells at HRT 6 days 68 xvi LIST OF SYMBOLS Ca Calcium CW Constructed wetlands Fe Ferum FWS Free water surface FWSCW Free water surface constructed wetland HRT Hydraulic retention time mg/l milligram per litre N2 dinitrogen N2O Nitrous oxide NO3- Nitrate NO2- Nirite NO2 Nitric oxide NH4 Ammonium Mg Magnesium Mn Manganese NH3 Ammonia ppm Part per million SSF Sub-surface flow SSFCW Sub-surface flow constructed wetlands TSS Total suspended solid Zn Zinc VF Vertical Flow xvii LIST OF APPENDICES APPENDIX TITLE PAGE Appendix A Standard B Under Environmental Quality (Sewage 85 and Industrial Effluent) Regulations 1979 Appendix B Laboratory Analyses 86 Appendix C Analysis of Variance 96 Appendix D Figures Of The Whole Experiment 120 CHAPTER 1 INTRODUCTION 1.1 Reviews Over the last years, the high population growth rate, industrialization and urbanization, have been the causes for several environment all over the world. Nowadays, solid waste management and wastewater treatment are the most important problems that we are facing. The amount of solid waste produced around the world is increasing at high rate as well as in Malaysia. Kuala Lumpur and Selangor produced 7922 tonnes/day in year 2000, and this will increase to 11 728 tonnes/day in year 2010. For the states of Negeri Sembilan, Melaka and Johor, waste generated for 2000 for 2633 tonnes/day and 3539 tonnes/day are expected by year 2015 (Maseri, 2005). Although there are different alternatives to reduce them or for their treatment and disposition, landfill is still the most common practice in developed and developing countries. However, the landfill method causes generation of leachate (Galbrand, 2003). According to Pankratz (2001), leachate can be defined as any contaminated liquid that is generated from water percolation through a solid waste disposal site, accumulating contaminants and moving into subsurface areas. As these wastes are compacted or chemically react, bound water is release as leachate. Landfill leachate 2 refers to the liquid that seeps through a landfill site and enters the environment. This liquid may already be in the material dumped into the landfill, or it may be the result of rainwater entering the landfill, filtering through the waste material and picking up additional chemicals before leaking out into the environment. Landfill leachate that escapes from the environment is most likely to eventually mix with the groundwater near the site. The quantity of these leachates is small as compared to others wastewater, but their contents are extremely hazardous (Tizaoui, at el., 2006). Landfills are potential threats to groundwater quality (Howard, 1997), the primary concern being the production and treatment of leachate (Eyles and Boyce, 1997). Major environmental problems have arisen from the production and migration of leachates from landfill sites and subsequent contamination of surrounding land and water (McBean et al., 1995). To prevent the adverse impacts of landfill leachate on aquatic life and degradation of water quality, landfill leachate has to be collected and treated before final discharge into the environment (Sartaj, 2001). Conventional treatment systems are costly and require a long-term commitment. Moreover, the great variations in strength and flows of leachate as well as its toxic effect, due to presence of high concentrations of heavy metals and/or organic substances, make the use of these systems undesireable (Vesilind et al., 2002; Tchbanoglous et al., 1993). Many landfill operators are now considering nonconventional systems such as engineered constructed wetlands, which are low energy, do not require chemicals, and can satisfactorily address the leachate management problems (Sartaj, 2002). However, the modern landfill sites require that the landfill leachate to be collected and treated. Since there is no method to ensure that rainwater cannot enter the landfill site, landfill sites must now have an impermeable layer at the bottom. 1.2 Constructed Wetland and Landfill The role of wetlands in water resource management is fact gaining ground resulting in the construction wetlands in most developed countries. Constructed 3 wetlands are man-made system that involves altering the existing terrain to simulate wetlands conditions. They primarily attempt to replicate the treatment that has been observed to occur when polluted water enters the natural wetlands (Chew, 2006). Constructed wetlands have been used as an attractive low-cost method for controlling water pollution from both point and nonpoint sources (Olson, 1992; Mitsch, 1992). Dundabin and Bowmer (1992) have revealed that constructed wetland also show good potential for concentrating metals from industrial wastewaters. Wetlands prevent the contamination of groundwater or to prevent groundwater from infiltrating into the wetland (Kadlec et al., 2000). As reported by Olson (1992), constructed and natural wetlands also can contribute in reducing heavy metal and nutrient significantly to watershed water quality. On the other hand, constructed wetlands are also used to improve or restore some water bodies such as rivers and water basins (Nairn and Mitsch, 2000; Mitsch et al., 2005 and Mitsch and Day, 2006). Among the aquatic treatment systems, constructed wetlands have a greater potential in wastewater treatment because they can tolerate higher organic loading rate and shorter hydraulic retention time with improved effluent characteristics (Chongrak and Lim, 1998). The treatment of industrial and domestic wastewaters by passage through beds containing plants of the common reed (Phragmites australis), reedmace (Typha latifolia), or other species, has been widely practised in recent years, with varying degrees of success (Barr and Robinson, 1999). This has often been shown to limit the value of reed beds for treatment of raw landfill leachates. Engineered wetlands do however; have considerable capability for secondary polishing of leachates that have been pretreated in aerobic biological plants and for older leachates (Barr and Robinson, 1999). There are two types of constructed wetlands: free water surface (FWS) wetlands also known as surface flow wetlands) and subsurface flow (SSF) wetlands (also known as root zone method wetlands or rock-filters) (Liehr et. al., 2000). FWS 4 systems consist of several basins or cells with the water surface being 0.12 – 2.0 metres above the substrate (Tousignant et. al., 1999). However, both surface-flow and subsurface-flow constructed wetlands have been identified as promising technologies for the treatment of landfill leachate (Kadlec and Knight, 1996). Constructed wetlands have a small ecological footprint, utilize “low-tech” technology, and have an aesthetic value similar to that of natural wetlands. The application of wetland technology for treating landfill leachate is still developing (Nivala, et al., 2006). Wetland also was categorized in the Best Management Practices (BMP) which is one of the best to reduce non-point source pollution (Ayob and Supiah, 2005). 1.3 Objectives of the Study The aim of this study was to establish a diverse, self-sustaining, locally- modelled, native vegetation community bearing biological integrity treatment wetland site that effectively decontaminate the leachate input via phytoremediative, physiochemical and biophysical means. The hypothesis of this study is that “the selected native vegetation and vegetation establishment strategy will yield a successfully established site bearing biological integrity and that a naturalized system supporting biological integrity will effectively remediate the characterized contaminated leachate input”. The purpose of this project was to evaluate the efficiency in the context of treating real landfill leachate on-site using a laboratory scale system. The more specific goals of the study are given below: a) To investigate the feasibility of applying free water surface constructed wetland system to treat landfill leachate containing high organic matters and nutrient, under different concentration of leachate; 5 b) To determine the relationship between removal efficiency and different hydraulic retention time (HRT). 1.4 Scope of Study This study comprises of a series of laboratory scale experiment. Leachate from a municipal solid waste landfill will be used. This study will cover: a) A laboratory scale wetland which will be developed for the treatment of leachate; b) Each system contained 2 cells. Each cells were planted with same number of plant 40 no. to 80 no. of plant. c) The efficiency of landfill leachate treatment system is analysed in terms of ammonia nitrogen (NH3-N), nitrate nitrogen (NO3--N), orthophosphates (PO43-), COD, manganese (Mn), and iron (Fe). HACH DR/4000 spectrophotometer equipment was used for analysis of each particular parameter; d) The vegetation species that was used in this study is Limnocharis flava; e) All experiments were carried out in Environmental Engineering Laboratory, Faculty of Civil Engineering, Universiti Teknologi Malaysia. 1.5 Problem Statement As cities are growing in size with a rise in the population, the amount of waste generated is increasing becoming unmanageable. The local corporations have adapted different methods for the disposal of waste such as open dumps, landfills, 6 sanitary landfills, as well as incineration plants. Besides, landfilling methods will generate a leachate and it will contaminate the groundwater table. These leachates may migrate from the refuse and contaminate surface and ground waters, which may affect human health and the aquatic environment. Treatment of these leachates in classical wastewater treatment plants is rarely practiced due to the nature and high levels of pollutants present in them (i.e. high COD, low biodegradability, heavy metals, pathogens, etc.). Dedicated treatment facilities are therefore required before the leachate being discharged to the environment or to the sewer system. As an alterative, constructed wetlands are suitable for treating leachate from landfill sites which can be very harmful if not treated properly. The problem with leachate treatment is that leachate changes in terms of strength, biodegradability, and toxicity as the wastes in the landfill age over time. Also, bearing in mind that landfilled wastes may take up to a hundred years to stabilize. CHAPTER 2 LITERATURE REVIEW 2.1 Introduction Constructed wetlands treat a wide variety of wastewaters and runoff waters using emergent plants. Free water surface (FWS), subsurface flow (SSF), and vertical flow (VF) constructed wetland all use a combination of fixed-film biological activity and physical, chemical, or photochemical mechanisms. The treatment of landfill leachate is one particular application for which constructed wetlands have been used widely (Crites, 2005). The characteristics and flow of landfill leachates depend of the composition of solid wastes, precipitation, runoff, age of the landfill and permeability and type of cover. Solid waste composition varies substantially with socio-economic conditions, location, season, waste collection and disposal methods, sampling and sorting procedures and many others factors (El-Fadel et al., 1997). In addition to the leachate generation induced by precipitation, it is also produced as a result of biochemical processes that convert solid materials to liquid forms. 8 2.2 What is Constructed Wetlands? Natural wetlands are called by other names such as bogs, swamps, and marshes. Bogs occur at higher elevations and are described as spongy, with poorly drained soil. Swamps are characterized by the presence of trees, while marshes have a lot of sedges and grasses with trees growing on the edges of the wetland. Nivala et al (2006) have revealed that constructed wetlands have a small ecological footprint, utilize “low tech” technology, and have an aesthetic value similar to that of natural wetlands. In Malaysia, we have one man-made wetlands called Putrajaya Wetland. Constructed wetlands are engineered systems that have been designed and constructed to utilize the natural processes involving wetland vegetation, soils, and their associated microbial assemblages to assist in treating wastewater (Vymazal, J., 2006). Constructed wetland technology is more widespread in industrialized countries due to more stringent discharge standards, finance availability, change in tendency to use on-site technologies instead of centralized systems, and the existing pool of experience and knowledge based on science and practical works (Korkusuz et. al., 2005). Constructed wetlands are becoming increasingly common features emerging in landscapes across the globe. Although similar in appearance to natural wetland systems (especially marsh ecosystems), they are usually created in areas that would not naturally support such systems to facilitate contaminant or pollution removal from wastewater or runoff (Hammer, 1992; and Mitsch and Gosselink, 2000). According to Lim et. al. (2003), the constructed wetlands have higher tendency o remove pollutants such as organic matters, suspended solids, heavy metal and other pollutants simultaneously. Some of the studies show that the ability of wetland systems to effectively reduce total suspended solid, biochemical oxygen demand (Watson et al., 1990 and Rousseau, 2005), and fecal coliform (Nokes et. al., 1999 and Nerall et. al., 2000) are well established. Nitrogen (ammonia and total nitrogen) and phosphorus are processed with relatively low efficiency by most wetland systems (Steer et al., 2005). 9 Fields (1993) stated that constructed wetlands are built specifically for water quality improvement purposes, typically involving controlled outflow and a design that maximizes certain treatment functions. In addition to this, wetlands are usually utilized as secondary and even tertiary treatment because of toxic effects on the aquatic plants due to high organic loading of the influents (Solano et. al., 2004). 2.3 Types of Constructed Wetland There are several types of constructed wetlands; surface flow wetlands, subsurface flow wetlands, and hybrid systems that incorporate surface and subsurface flow wetlands. Constructed wetland systems can also be combined with conventional treatment technologies (Davis, 1995) The basic classification is based on the type of macrophytic growth, further classification usually based on the water flow regime (Vymazal, J. 2006) as illustrate in Figure 2.2. Figure 2.1 shows the typical surface flow (SF) and subsurface flow (SSF) constructed wetlands. Constructed wetland design include horizontal surface and sub-surface flow wetlands are similar to natural marshes as they tend to occupy shallow channels and basins through which water flows at low velocities above and within the substrate. The basins normally contain a combination of gravel, clay- or peat-based soils and crushed rock, planted with macrophytes (Shutes, 2001). (Source: Water pollution control federation, 1990) Figure 2.1: Typical surface flow and subsurface flow constructed wetlands 10 Constructed wetlands Free floating plants Floating leaves plants Emergent plants Surface flow (Free water surface) Downflow Submerged plants Subsurface flow Vertical flow Horizontal flow Upflow Hybrid systems Figure 2.2: Classification of constructed wetlands for wastewater treatment (Vymazal, 2001) 2.3.1 Free Water Surface Wetlands (FWS) Free water surface (FWS) wetlands are treatment wetlands in which the surface water flowing through them is exposed to the atmosphere. They typically consist of several basins or cells with the water surface being 0.15 to 2.0 metres above the substrate (Tousignant et al., 1999). The near surface layer is aerobic while the deeper waters and substrate are usually anaerobic (Galbrand, 2003 and Chew, 2006). As reported by Vymazal et. al. (2006), in free water surface wetlands, oxygen is mainly supplied to the wetland through algal photosynthesis and atmospheric diffusion. The FWS wetlands technology started with the ecological engineering of natural wetlands wastewater treatment. Constructed FWS treatment wetlands mimic the hydrological regime of natural wetlands (Noor, 2006). In surface flow (SF) wetlands, water flows over the soil surface from an inlet point to an outlet point or, in 11 a few cases, is totally lost to evaporation and infiltration within the wetlands (Chew, 2006 and Nazaitulshila, 2006). As stated by Lim et al. (1998), the FWS system consist of basins or channels and barriers such as constructed clay layer or geotechnical material to prevent seepage. Figure 2.3 shows the free water surface constructed wetland. These systems are primarily constructed to treat municipal wastewater, mine drainage, urban storm water, agricultural runoff and livestock wastes, and landfill leachate (USEPA, 2000). Figure 2.4 shows the free water surface constructed wetlands in a foreign country. Free water surface wetlands are sometimes called surface flow wetlands. The advantages of surface flow wetlands are that their capital and operating costs are low, and their construction, operation, and maintenance are straightforward (Davis, 1995). An addition to, Galbrand (2003) has revealed that there are a few more advantage of using FWS such as (a) significant reduction in the levels of nitrogen and phosphorus, metals, persistent organic and fecal coliforms, (b) superiority in their abilities to remove biochemical oxygen demand (BOD), chemical oxygen demand (COD), and total suspended solids (TSS). The main disadvantage of surface flow systems are (a) require a large land area than other systems (Davis, 1995; and Galbrand, 2003), (b) wastewater are exposed and are therefore accessible to humans and animals, hence it may not prove prudent to establish these wetlands in high use area such as parks, playgrounds, or similar public facilities, (c) pollutants such as phosphorus, metals and some persistent organics can become bound in wetland sediments and accumulate over time (USEPA, 2000 ; Davis, 1995; and Liehr et al., 2000). Moreover, this system will contribute to the odour problem and as attraction of unwanted pests such as mosquitoes that breed easily in the water. 12 Figure 2.3: Free water surface flow (FWS) constructed wetland (Source: Earthpace Resources) Figure 2.4: The free water surface constructed wetlands in a foreign 2.3.2 Sub-Surface Flow Wetlands (SSF) Many of the earliest treatment wetlands in Europe were subsurface flow (SSF) systems constructed to treat mechanically pretreated municipal wastewater as shown in Figure 2.5. Moreover, the subsurface flow constructed wetlands first emerged as a wastewater treatment technology in Western Europe based on research 13 by Seidel commencing in the 1960s, and by Kickuth in the late 1970s and early 1980s as reported by Sherwood (1993). Soil and gravel-based SSF wetlands are still the most prevalent application of this technology in Europe. SSF wetlands that use gravel substrates have also been used extensively in the United States. According to Liehr et al. (2000), a SSF system consists of a sealed basin with a porous substrate of rock, grave or coarse sand planted with emergent macrophytes such as reeds, Eurasian watermilfoil and duckweeds. This technology is generally limited to systems with low flow rates and can be used with less than secondary pretreatment. Subsurface flow wetlands differ from FWS wetlands in that they incorporate a rock or gravel matrix that the wastewater is passed through in a horizontal or vertical fashion (DeBusk et.al, 2001). Unless the matrix clogs, the top layer of the bed in horizontal flow systems will remain dry. The SSF configuration offers several advantages, including a decreased likelihood of odour production and no insect proliferation within the wetlands as long as surface ponding is avoided. Unlike FWS wetlands, SSF systems provide no aesthetic or recreational benefits and few, if any, benefits to wildlife. (Source: USGS) Figure 2.5: The subsurface constructed wetlands in a foreign country. Subsurface flow wetlands continue to provide effective treatment of most wastewater constituents through the winter in temperature climates. The subsurface microbial treatment processes still function, albeit at a reduced rate, even when the 14 surface vegetation has senesced or died, and the matrix surface is covered with snow and ice. Subsurface flow wetlands also can be operated in a vertical flow fashion which can reduce matrix clogging problems and enhance certain contaminant removal processes such as nitrification. Because of the high cost of the gravel or rock matrix, SSF wetlands never attain the large spatial footprint of the large FWS wetlands. Concerns over matrix clogging and the potential high cost of renovation also limit the deployment of extremely large SSF wetlands. However, SSF are finding increased use for small applications, such as for small communities or single family homes. The limitations of septic systems for nutrient control have become more apparent in the past two decades (Hagedorn et.al., 1981), and SSF wetlands are one technology that is being deployed to improve nutrient removal performance (Mitchell et.al., 1990). Subsurface flow systems are the only wetlands configuration suitable for this purpose, because they crate no standing water, thereby limiting the likelihood of human exposure to wastewater pathogens (House et.al., 1999). a) Horizontal-flow systems (HF) The system is called horizontal flow because the wastewater enters the inlet and flows slowly through the porous medium under the surface of bed in an ore or less horizontal way until it flows out through the outlet. As the wastewater flows from the inlet to the outlet, it comes into contact with three zones, which are aerobic zones, anaerobic zones and anoxic zones. These zones are categorized as biological treatment methods (Uygur and Kargi, 2004). Aerobic zones are found in the area where there are presence of oxygen such as around the roots and rhizomes. As the wastewater passes through this zone, it is cleaned by microbiological degradation and by physical and chemical process (Cooper et al., 1990). Organic compound are degraded aerobically and anaerobically by the bacteria that are attached to the roots and rhizomes. Components such as nitrogen is removed by the major process which are nitrification and denitrification and also other processes such as volatilization, adsorption and plant uptake. Ammonia is oxidized to nitrate by nitrifying bacteria in aerobic zones and nitrates are converted to nitrogen 15 gaseous by nitrifying bacteria in anoxic zones (Cooper et al., 1990). As for phosphorus removal, it occurred through ligand exchange reactions. Phosphates replace water or hydroxyl ions from the surface of Fe and Al hydrous oxides. The media, which is used in horizontal sub-surface flow constructed wetlands like gravel and crushed stones do not contain high quantities of Fe, Al or Ca, so the removal of phosphorus is rather low. Figure 2.6 shows a typical arrangement for the subsurface constructed wetland with horizontal flow (HF). Figure 2.6: Longitudinal constructed wetlands with horizontal SSF. Key: 1) Inflow of mechanically pretreated wastewater; 2) Distribution zone filled with large stone; 3) Impermeable liner; 4) Medium (Gravel, sand, crush stones); 5) Vegetation; 6) Outlet collector; 7) Collection zones filled with large stones; 8) Water level in the bed maintained with outlet structure; 9) outflow (Vymazal, 1997). b) Vertical Flow Systems Vertical-flow (VF) treatment wetlands are frequently planted with common reed. Other emergent wetlands plants such as cattail or bulrush can also be used. VF reed beds typical look like the system show in Figure 2.7. They are composed of a flat bed of gravel topped with sand, with reed growing at the same sort of densities as horizontal-flow (HF) systems (Chew, 2006). They are fed intermittently. The liquid is dosed on the bed in a large batch, flooding the surface. The liquid then gradually drains vertically down through the bed and is collected by a drainage network at the base. The bed drains completely free, allowing air to refill the bed. The next dose of 16 liquid trap air this together with the aeration caused by the rapid dosing on the bed leads to good oxygen transfer and hence the ability to decompose BOD and to nitrify ammonia nitrogen. Figure 2.7: Typical arrangement of a vertical flow (VF) reed bed system As with the horizontal flow (HF) systems, the reeds in vertical flow (VF) systems will transfer some oxygen down into the rhizosphere, but it will be small in comparison with the oxygen transfer created by the dosing system. Vertical flow (VF) treatment wetlands are very similar in principle to a rustic biological filter. They are less good at the removal of suspended solid and in most cases will be followed by a horizontal flow bed as part of a multistage treatment wetlands system. The advantages cited for sub-surface flow (SSF) wetlands are greater cold tolerance, minimization of pest and odor problems, and possibly, greater assimilation potential per unit of land area than in surface flow (SF) systems. It has been claimed that the porous medium provides greater surface area for treatment contact than is found in surface flow (SF) wetlands, so that the treatment responses should be faster for sub-surface flow (SSF) wetlands which can, therefore, be smaller than a surface flow (SF) system designed for the same volume of wastewater. Since the water surface is not exposed, public access problems are minimal. Several subsurface systems are operating in parks, with public access encouraged. 17 The disadvantages of sub-surface flow (SSF) wetlands are that they are more expensive to construct, on a unit basis than surface flow (SF) wetlands. Because of cost, subsurface wetlands are often used for small flows. Sub-surface flow (SSF) wetlands may be more difficult to regulate than surface flow (SF) wetlands, and maintenance and repair costs are generally higher than for surface wetlands. A number of systems have had problems with clogging and unintended surface flows. 2.3.3 Hybrid Systems Various types of constructed wetlands may be combined in order to achieve higher treatment effect, especially for nitrogen (Vymazal, 2005). Single stage systems require than all of the removal processes occur in the same space. In hybrid or multistage systems, different cells are designed for different types of reactions. Effective wetland treatment of mine drainage may require a sequence of different wetland cells to promote aerobic and anaerobic reactions as may the removal of ammonia from agricultural wastewater. However, hybrid systems comprise most frequently VSSF (VF) and HSSF (HF) systems arranged in a stage manner as shown in Figure 2.8. However, there are been a growing interest in achieving fully nitrified effluents (Vymazal, 2006). Vymazal (2005) revealed that there are now many fine examples of HF systems for secondary treatment and they proved very satisfactory where the standard required only BOD5 and SS removal. However, there has been a growing interest in achieving fully nitrified effluents. HF systems cannot do this because of their limited oxygen transfer capacity. Moreover, Vymazal (2005) add that VF systems, on the other hand do provide a good conditions for nitrification but no denitrification occurs in these systems. In combined systems (hybrid system), the advantages of HF and VF systems can be combined to complement each other. A research done by Cooper (1999, 2001), it is possible to produce an effluent low in BOD, which is fully nitrified and partly denitrified and hence has a much lower total-N concentrations. 18 Figure 2.8: Hybrid constructed wetlands for wastewater treatment (Cooper, 1999) 2.4 Theory of Operation The deliberate uses of wetlands (both natural and constructed) as biological treatment systems for effluent purification have developed rapidly over the last 25-30 years (Brix, 1993). Theoretically, wastewater flows through the root zone, which the plants supply with oxygen and channels for wastewater flow. The efficiency and cost effectiveness of this method of treatment are highly controversial. Although many sites are in operation, the tremendous variation in site design, soil type, loading rate, and wastewater characteristics have made comparison difficult. Further studies are needed to evaluate optimal loading regimes and the specific area needed for maximum performance efficiency (Forsburg, 1996). Several types of natural wetlands, such as southern swamps, bottomland hardwood forests, freshwater marshes, northern bogs, and brackish and saltwater marshes have been used for the improvement of water quality for centuries. Because of their transitional position between terrestrial and aquatic ecosystem, some wetlands have been subjected to both municipal and industrial wastewater 19 discharges. Wetland has also received agricultural runoff, combined sewer overflow, stormwater runoff, mine drainage, and other sources of water pollution (Bastian et al., 1989). In early 1980’s there were over 500 natural wastewater treatment wetlands in operation in U.S (U.S EPA, 1983). There are still too few data from natural wetland leachate system to allow indisputable predictions of the treatment performance and the effects of leachate discharge on the receiving ecosystems. Exploiting this technology without adequate evaluation could to unfortunate results. Also, using natural wetlands for wastewater treatment has several advantages (Forsburg, 1996). Wetland systems are effective in reducing many contaminants (e.g., nitrogen, phosphorus, trace organic compounds, metals, and pathogens) (Wildeman and Laudon, 1989). The pollutants in these systems are removed through a combination of physical, chemical, and biological processes. Low-cost immobilization of pollutants for long periods of time is the goal of using constructed wetlands for water pollution treatment. As reported by Kadlec and Knight (1996), some possible metal removal mechanisms associated with municipal solid waste (MSW) landfill leachate include bioaccumulation in plants, adsorption in sediments, precipitation as insoluble salts, incorporation by a range of organic materials such as algae, detritus and bacteria. Bioaccumulation and adsorption have been reported to have finite capacities to retain metals and, if dominant in controlling metal retention, may indicate poor long-term treatment performance. But metal removal in constructed wetland systems has received little attention to date because most existing systems treat wastewaters having low concentrations of heavy metals. 2.5 Aquatic Macrophytes Thousands of plants have adapted to life in water or wetlands, with a significant proportion of them occurring only in wetlands and shallow water. Many 20 wetlands are readily identified by vegetation and traditional methods relied on plants for wetland identification and delineation. Plants also serve as a basis for wetland classification. Rooted emergent aquatic macrophytes, such as common reeds (Phragmites australis), cattails (Typha latifolia) and bulrushes (Scirpus lacustris), are the dominant plants in wetlands (Mitsch and Gosselink, 1993). These species produce aerial stems and leaves, and an extensive root and rhizome system (Forsburg, 1996). According to Cronk and Fennessy (2001), the emergent plants are rooted in the soil where their leaves and stems which are the photosynthetic parts of the plants are called aerial. Plants growing in wetlands and water are technically called hydrophytes. Most wetland plants do not grow strictly in water or very wet soils, but also grow in terrestrial habitats, especially under mesic soil conditions. Many of these species are more common on the latter sites, but have populations that tolerate varying degrees of soil wetness. Unfortunately, due to lack of distinctive morphological differences, individuals of these wetland populations can only be recognized as hydrophytes when associated with more typical hydrophytic species or after identification of hydric soils (i.e., periodically anaerobic soils due to excessive wetness) and other reliable signs of wetland hydrology at a given location. The categories used to group wetland plants include emergent, submerged, floating-leaved, and floating. The general characteristics of each group are described in next sub-section. The major types of aquatic macrophytes are submerged, floating and emergent weeds; some of these are shown in Figure 2.9 and 2.10, respectively. (a) (b) Figure 2.9: Floating aquatic weeds (a) water lettuce (Pistia stratiotes); (b) water lily (Nymphaeaceae) 21 (a) (b) Figure 2.10: Emergent aquatic weeds: (a) Cattails (Typha latifolia); (b) Common reeds (Phragmites australis) Submerged plants are either suspended in the water column or rooted in the bottom sediments. In submerged species, all photosynthetic tissues are normally underwater (Cook, 1996). These species are not effective for wastewater treatment due to the requirement of light penetration into the water bodies. The second types of aquatic weeds, namely the floating type, have their root portions submerged but not attached to the soil. According to Galbrand (2003), there are two sub-types of floating weeds, i.e floating unattached weeds where their roots are hanging free in the water and are not anchored in the sediments whereas the floating attached weed, their leaves are floating on the water surface while their roots are anchored in the substrate. Emergent plants are rooted in the soil with basal portions that typically grow beneath the surface of the water, but whose leaves, stems (photosynthetic parts), and reproductive organs are aerial. These plants tend to have a higher potential in wastewater treatment because they can serve as a microbial habitat and as a filtering medium (Chongrak and Lim, 1998). Cattails (Typha spp.) and reeds (Phragmites app.) are easy to propagate and produce a large biomass. They thrive under a wide range of water quality and other environmental conditions, including acidic waters with iron concentrations of up to 100 mg/l. The rhizospheres of Typha and Phragmites app. provide an effective matrix which traps and filters sediment particles and associated metals. Moreover, bulrushes (Scirpus spp.) are also easy to 22 propagate, produce a large biomass, and can thrive under a wide range of water quality and environmental conditions. They are reported to be more susceptible to transplanting stress than cattails and have a slower rate of spread. The floating-leaved plants are also known as floating attached (Cronk and Fennessy, 2001). The plant leaves float on the water’s surface while their roots are anchored in the substrates. Floating-leaved species shade the water column below and are often able to outcompete submerged species for light, particularly when turbidity levels are high and light penetration is reduced (Haslam, 1978). Example of floating-leaved plants is Nymphaeaceae or better known as water lily as shown in previous Figure 2.9. However, the pathway of metal transfer from the sediment and interstitial water to the roots and rhizomes is still not fully understood and requires further investigation. The common types of aquatic weeds, their scientific names and some of the environmental requirements are given in Table 2.1. 2.6 Treatment Process Mechanisme An understanding of the treatment mechanisms is essential so that the design of wetland systems can be improved for better treatment performance. The principal pollutant removal mechanisms operatives in wetland systems are listed in Table 2.2 and they include sedimentation, chemical precipitation, and adsorption, microbial metabolic activity and plant uptake (Chongrak and Lim, 1998). 2.6.1 Biodegradable Organic Matter Removal In wetland systems, microbial degradation plays a dominant role in the removal of soluble/colloidal biodegradable organic matter (BOD or COD) in wastewater, the remaining BOD associated with settleable solids being removed by 23 sedimentation. Both the SF and FWS systems essentially function as attached growth biological reactors. For the FWS systems, however, the contribution of suspended microbial growth in the water column to BOD removal cannot be neglected. The mechanism of BOD removal in the attached biofilm is similar to that of trickling filters (Chongrak and Lim, 1998). Biodegradation takes place when dissolved organics is carried by the diffusion process into the biofilms on the submerged plant stems (FWS systems), the root system and surrounding soil or media (Chongrak and Lim, 1998). The role of wetland vegetations is confined to providing a support medium for microbial degradation to take place as in Figure 2.11, and to conveying oxygen to the rhizosphere for aerobic biodegradation to occur in Figure 2.12. Figure 2.11: Aerobic condition (oxygen from water column if FWS systems and from atmosphere if SF systems) (Chongrak and Lim, 1998) Figure 2.12: Aerobic condition (oxygen from plant roots) (Chongrak and Lim, 1998) Water hyacinth, Eichhornia crassipes Water fern Azolla app. Duckwed, Lemna spp. Cattails, Typha spp. Common reed, Phrgmites communis Rushes, Juncus spp. Bulrushes, Scirpus spp. Sedges, Carex spp. Floating Note: 5 5 12-24 10-30 - >10 20-30 10-30 12-33 12-26 16-27 14-32 Worldwide Worldwide Worldwide Worldwide Worldwide Worldwide - 10-25++ Temperate region 10 - 15-25++ Worldwide 20-30 23-26++ 18-26++ Worldwide Tropical and subtropical region Worldwide Survival* Desirable Distribution Ambient temperature *Temperature range for seed germination; roots and rhizomes can survive in frozen soils. +ppt = parts per thousand ++Water temperature (only for submerged types) Pondweed Potamogeton spp. Eurasian watermillfoil, Myriophyllum spacitum Coontail, Ceratophyllum demersum Submerged Emergent Common name, scientific name Types of aquatic weeds 12-100 -30-150 -10-10 -75-200 5-95 2.5 16.6 7 30 45 20 20 - - - Water level, cm pH 5-7.5 4-9 5-7.5 2-8 4-10 4.5-7.5 3.5-11 5.9-7.0 7.1-8.7 5.0-10 6.3-10 Optimum 3.8 10 15 Maximu m salinity tolerance, ppt Table 2.1: Some environmental requirements of the aquatic weeds (Adapted from Stephenson et. al., 1980; Reed et. al., 1988 and USEPA, 1988). 24 P I Bacterial & virus Volatilization of NH3 from the wastewater Interparticle attractive forces (van der Waals force) Particulates filtered mechanically as water passes through substrate, and root masses Gravitational settling of solids (and constituent pollutants) in wetland settings. Description S P S S S S P P P S Natural decay of organisms in an unfavourable environment Under proper conditions, significant quantities of these pollutants will be taken up by plants. Uptake and metabolism of organics by plants. Root excretion may be toxic to organism of enteric origin Decomposition of alteration of less stable compounds by phenomena such as UV irradiation, oxidation, and reduction Removal of colloidal solids and soluble organics by suspended, benthic, and plantspported bacteria. Bacterial nitrification/denitrification. Notes: a P = primary effects; S = secondary effect; I = incidental effect (effect occurring incidental to removal of another pollutant) b The term metabolism includes both biosynthesis and catabolic reactions. Natural die-off Plant Adsortion Plant Metabolism Biological bacteria metabolismb Decomposition Adsorption on substrate and plant surfaces S I Refractory organics P I Heavy metals P I P Adsorption S I N Formation of or co-precipitation with insoluble compounds P I BOD P P S S S Colloidal solids P S P Settleable solids Chemical Precipitation Volatilization Adsorption Filtration Physical Sedimentation Mechanisms Pollutant affecteda Table 2.2: Summary of removal mechanisms in wetland for the pollutant in wastewater (Adapted from Stowell et. al., 1981) 25 26 2.6.2 Metal Removal Mechanisms The potential for uptake by vegetation appears to be a small and unimportant source of metal removal in wetland systems (Dunbabin and Bowmer, 1992). A preliminary iron mass balance for a constructed wetland receiving AMD emphasizes the small role of vegetation and the dominant role of sediments in removing and storing iron (Fennessy and Mitsch, 1992). Forsburg (1996) reported that the current information suggests there are two complementary processes for iron and manganese retention and degradation in constructed wetlands: biologically mediated oxidation and reduction processes. The anaerobic conditions found in wetlands enhance retention or metals. This coupled with aerated conditions in the rhizosphere allow many processes to occur simultaneously. Reduction processes as removal mechanisms, have not been fully explored (Spratt et al., 1987). Questions remain concerning the exact mechanisms, controlling factors, and long-term functional capabilities of these processes. In an experiment to determine if metal uptake by vegetation represents a major flux of metals out of the ecosystem, Shutes et al. (1993) concluded that the significance of the uptake of metals in the plant tissue is negligible, as the amount of metals taken up during a growing season constituted less than 3% of the total content introduced with the wastewater. Forsburg (1996) suggested that the subsurface introduction of effluent into CW would maximize the purification potential, and that metals will become immobilized on the increased sediment – root surfaces. 2.6.3 Removal of Nitrogen Nitrogen has a complex biogeochemical cycle with multiple biotic/abiotic transformations involving seven valence states (+5 to -3). The compounds include a variety of inorganic and organic nitrogen forms that are essential for all biological life (Vymazal, 2006). The most important inorganic forms of nitrogen in wetlands are ammonium (NH4+), nitrite (NO2-) and nitrate (NO3-). Gaseous nitrogen may exist 27 as dinitrogen (N2), nitrous oxide (N2O), nitric oxide (NO2 and N2O4) and ammonia (NH3). Removal of nitrogen in wetlands is achieved through three main mechanisms: nitrification/denitrification, volatilization of ammonia and uptake by plants. Chongrak and Lim (1998) reported that there is still no general consensus among the researchers on the relative importance of the removal mechanisms specifically between nitrification/denitrification and plant uptake. (a) Nitrogen Transformation in Wetlands Mitsch and Gosselink (1986) define nitrogen mineralization as the biological transformation of organically combined nitrogen to ammonium nitrogen during organic matter degradation. This can be both an aerobic and anaerobic process and is often referred to as ammonificaton. Mineralization of organically combined nitrogen releases inorganic nitrogen as nitrates, nitrites, ammonia and ammonium, making it available for plants, fungi and bacteria. Mineralization rates may be affected by oxygen levels in a wetland. Wetzel (1983) defines nitrification as the biological conversion of organic and inorganic nitrogenous compounds from a reduced state to a more oxidized state. Nitrification is strictly an aerobic process in which the end product is nitrate (NO3-) this product is limited when anaerobic conditions prevail (Patrick and Reddy, 1976). Nitrification will occur readily down to 0.3 ppm dissolved oxygen (Keeney, 1973). The process of nitrification oxidizes ammonium (from the sediment) to nitrite (NO2-), and then nitrite is oxidized to nitrate (NO3-). The overall nitrification reactions are as follow (Davies and Hart, 1990): 2NH4+ + 3O2 ↔ 4H+ + 2H2O + 2NO2- (1) 2NO2- + O2 ↔ 2NO3- (2) According to Wetzel (1983), denitrification by bacteria is the biochemical reduction of oxidized nitrogen anions, nitrate-N and nitrite-N, with contaminant 28 oxidation of organic matter. The general sequence as given by Wetzel (1983) is as follows: NO3- → NO2- → N2O → N2 (3) The end product, N2O and N2 are gases that re-enter the atmosphere. Denitrification is most commonly defined as the process which nitrate is converted into dinitrogen via intermediates nitrite, nitric oxide and nitrous oxide (Hauck, 1984; Paul and Clark, 1996; Jetten et al., 1997). The nitrate can be removed either through plant uptake as its main nitrogen nutrient or reduce through denitrification process (Galbrand, 2003). Denitrification occurs intensely in anaerobic environments but will also occur in aerobic conditions (Bandurski, 1965). As reported by Hammer and Knight (1994), the denitrification process occurs in anaerobic environment and the denitrifying bacteria are Pseudomonas, Achtomobacter, Aerobacter, Bacillus, Proteus and Micrococcus. Liehr et al. (200) stated that ammonification process can occur in both aerobic and anaerobic condition. Ammonia volatilization is a physiochemical process where ammonium-N is known to be in equilibrium between gaseous and hydroxyl forms (Vymazal, 2006). According to Reddy and Patrick (1984), the losses of NH3 through volatilization from flooded soils and sediments are insignificant if the pH value is below 8.0. At pH of 9.3 the ratio between ammonia and ammonium ions is 1:1 and the losses via volatilization are significant. Ammonification rates are dependent on temperature, pH, C/N ratio, available nutrients and soil conditions such as texture and structure (Reddy and Patrick, 1984). Vymazal (2006) revealed that algal photosynthesis in wetlands as well as photosynthesis by submerged macrophytes often creates high pH values during the day. The pH of shallow flood water is greatly affected by the total respiration activity of all the heterotrophic organisms and the gross photosynthesis of the sepsis present. The optimal ammonification temperature is reported to be 40 - 60 ĖC while optimal pH is between 6.5 and 8.5 (Vymazal, 1995). Volatilization of ammonia can be result in nitrogen removal rates as high as 2.2 g N m-2 d-1. Table 2.3 shows the nitrogen transformations in constructed wetlands, while Figure 2.13 illustrates the simplified nitrogen cycle in wetlands. 29 Table 2.3: Nitrogen transformations in constructed wetlands (Vymazal, 2006) Process Transformation Volatilization Ammonia-N (aq) Ammonification Organic-N Nitrification Ammonia-N Nitrate-ammonification Nitrate-N Denitrification Nitrate-N N2, Fixation Gaseous N2 Plant/microbial uptake (assimilation) Ammonia-, nitrite-, nitrate-N Ammonia adsorption Ammonia-N • Organic nitrogen burial • ANAMMOX (anaerobic ammonia ammonia-N (g) ammonia-N nitrite-N nitrate-N ammonia-N nitrite-N gaseous N2, N2O ammonia-N (organic-N) organic-N gaseous N2 oxidation) Figure 2.13: Simplified wetlands nitrogen cycle (Kadlec and Knight, 1996) 2.6.4 Removal of Phosphorus Phosphorus in wetlands occurs as phosphate in organic and inorganic compounds. Free orthophosphate is the only form of phosphorus believed to be utilized directly by algae and macrophytes and thus represents a major link between 30 organic and inorganic phosphorus cycling in wetlands (Vymazal, 2006). Meanwhile, according to Chongrak and Lim (1998), the phosphorus removal mechanism in wetland systems include vegetative uptake, microbial assimilation, adsorption onto soil (mainly clay) and organic matter and precipitation with Ca2+, Mg2+, Fe2+ and Mn2+. Adsorption and precipitation reactions are the major removal pathways when the hydraulic retention time is longer and finer-textured soils are being used, since this allows greater opportunity for phosphorus sorption and soil reactions to occur (Reed and Brown, 1992). Similar to that of nitrogen removal, the relative importance of phosphorus removal via plant uptake pathway is still a subject for debate. Nonetheless, it is the only mechanism by which phosphorus is removed from the wetland systems. Adsorption and precipitation reactions merely trap the phosphorus in the wetland soil. Once the storage capacity has been exceeded, the soil/sediment has to be dredged for ultimate disposal (Lim and Chongrak, 1998). Figure 2.14 depicted the removal process of phosphorus in constructed wetlands. Figure 2.14: Phosphorus removal process in constructed wetlands 31 2.6.5 Solids Removal Settleable solids are removed easily via gravity sedimentation as wetland systems generally have long hydraulic retention times. Nonsettling/colloidal solids are removed via mechanisms which include: straining (if sand media is used); sedimentation and biodegradation (as a result of bacterial growth); and collisions (inertial and Brownian) with an adsorption (Van der Waals forces) of other solids (plants, soil, sand and gravel media). For gravel media which forms an important component in a subsurface flow wetland system, Sapkota and Bavor (1994) suggested that the suspended solids removal is primarily by sedimentation and biodegradation similar to what is occurring within a trickling filter. On the other hand, the solid removal mechanism are very depends on the sizes and nature of solids present in the wastewater, as well as the types of filter media used. In all cases, wetland vegetation has a negligible role to play in solids removal. 2.7 Landfill Leachate Prior to 1965 very few people were aware of the fact that water passing through solid waste in a sanitary landfill would become highly contaminated. This water, termed leachate, was generally not a matter of concern until few cases of water pollution were noted where leachate had caused harm (Boyle and Ham, 1974). Boyle and Ham (1974) also reported that many contaminants released from sanitary landfill, if allowed to migrate, may pose a severe threat to surface and ground water. Kouzeli-Katsiri et al. (1999) also revealed that the production of leachate can becomes harmful to all organisms if it moves out of landfill into the surrounding soil. The composition and quantity of leachate is subject to seasonal and even daily fluctuations, which significantly impact the design of leachate treatment plants. Figure 2.15 depicted a typical layout of a landfill. 32 Figure 2.15: Typical layout of landfill 2.7.1 Leachate Generation Organic and mineral compounds generated as products of waste mineralization within biological processes and accompanying physical and chemical processes are washed out by percolating rainwater through the deposit of wastes in landfill and form heavy polluted waters, or leachate. Leachate generation accompanies landfill during its exploitation and a long time after its closing and recultivation. According to Lu et al. (1985), there are a number of factors that contribute to leachate generation such as availability of water, landfill surface condition, refuse condition and underlying of soil conditions. The composition and amount of leachate depend on many factors such as quality of wastes and its crumbling, techniques of landfilling and degree of waste compaction, age of landfill, biochemical and physical processes of waste decomposition, moisture and absorption capacity of wastes, precipitation, humidity, and evapotranspiration rate, topography of landfill site, lining system, hydrogeology, vegetation. Precipitation and climate have the strongest influence on leachate generation, causing the amount to vary during the year. Absorption capacity of wastes is another affecting leachate production. Initial moisture of municipal wastes depends on type of waste, seasonal trends, and treatment after collection and amounts on average to 33 35% of dry weight (Blakey, 1992). Additionally, wastes can absorb liquid up to the moment when downward percolation begins. The absorption capacity is influenced by waste density and pathways of liquid infiltrating through the deposit of wastes. Generally, an increase of waste density decreases leachate production (Harrington, 1986 and Blakey, 1992). The amount of leachate generated in municipal landfill can be calculated with the following water balance equation (Blakey, 1992): LP = P − ( R + āU + ET + āU W ) (4) where: LP = leachate production, P = precipitation, R = surface runoff, āU = changes in soil moisture storage, ET= evaporation from soil/evapotranspiration from a vegetated surface, and āUW = changes in moisture content in wastes. Landfill leachates are due to toxicity, classified as problematic wastewaters and represent a dangerus source of pollution for the environment. Their purification is difficult and often insufficient; therefore they seriously endanger the quality of the surface and underground waters (Tjasa et.al., 1997). The characteristics of the landfill leachates can usually be represented by the basic parameters COD, BOD, ratio of BOD/COD, colour, NH3-N, pH, alkalinity, oxidation-reduction potential and heavy metal (Wang, 2004). 2.7.2 Leachate Composition More than 200 organic compounds have been identified in leachate. They may be classified as cyclic hydrocarbons, bicyclic compounds, aromatic hydrocarbons, substituted benzenes, alcohols and ethers, cyclic ethers, ketones and ene-ones, acids and esters, phenols, phthalates, furans and nitrogen-, phosphorus-, sulfur-, and silica-containing compounds, and others that remain unidentified. 34 Among the abovementioned compounds are 35 substances recognized as priority pollutants (Michal, et. al, 2004). Many factors influence leachate production and composition, resulting in a different amount and quality of leachate produced in a particular landfill. Moreover, the composition of leachate is changed significantly by the anaerobic processes occurring in the deposit of wastes and age of landfill (Harrington, 1986). As an example, Table 2.5 shows the composition of leachate for a new landfill and a mature landfill. Moreover, according to Harrington et al. (1986), the composition of leachate is change significantly by the anaerobic processes occurring in the deposit of wastes and age of landfill, as an example, Table 2.4 shows the composition of leachate from different sources, which point at highly varying ranges of respective parameters. The leachate characteristics showed a wide variation depending on tropical climatic changes such as monsoon and dry periods, similar to those found in other places (Tchobanoglous et. al., 1993). Table 2.4: Landfill leachate composition from three different sources (Harrington et al., 1986) Parameter Range Range Range pH 4.5-9.0 5.8-7.5 5.3-8.5 COD (mg/L) 500-60,000 100-62,000 150-100,000 BOD (mg/L) 20-40,000 2-38,000 100-90,000 Sulfate (mg SO4/L) 10-1,750 60-460 10-1,200 Chloride (mg Cl/L) 100-5,000 100-3,000 30-4,000 Ammonia nitrogen (mg N-NH4/L) 30-3,000 5-1,000 1-1,200 Young landfill leachate contains large amount of free volatile fatty acid, resulting in high concentration of COD, BOD, NH3-N and alkalinity, a low oxidation-reduction potential and black colour. Therefore, biological processes are commonly employed for young landfill leachate treatment to remove the bulk biodegradable organics (Wang, 2004). Old landfill leachate or biologically treated young landfill leachate has a large percentage of recalcitrant organics molecules. As a result, this kind of leachate is characterized by high COB, low BOD, fairly high NH3-N and alkalinity, low ratio of BOD5/COD, a high oxidation-reduction potential 35 and dark brown or yellow colour. The treatment processes for this kind of leachate include chemical precipitation and coagulation, chemical oxidation, electrochemical oxidation, reverse osmosis and nanofiltration (Wang, 2004). Table 2.5: Landfill Leachate Composition from new and mature landfill (Tchobanoglous et. al., 1993). New landfill < 2 years Constituent Range Typical Mature landfill years > 10 BOD5 2000-30000 10000 100-200 TOC 1500-20000 6000 80-160 COD 3000-6000 18000 100-500 Total suspended solid 200-2000 500 100-400 Organic nitrogen 100-800 200 20-40 Ammonia nitrogen 10-800 200 20-40 Nitrate 5-40 25 5-10 Total phosphorus 5-100 30 5-10 Orthophosphorus 4-80 20 4-80 Alkalinity as CaCO3 1000-10000 3000 200-1000 pH 4.5-7.5 6 6.6-7.5 Total hardness 300-1000 3500 200-500 Calcium 200-3000 1000 100-400 Magnesium 50-1500 250 50-200 Potassium 200-1000 300 50-400 Sodium 200-2500 500 100-200 Chloride 200-3000 500 100-400 Sulfate 50-1000 300 20-50 Total iron 50-1200 60 20-200 All units in mg/l As landfill ages, the pH of leachate also undergoes changes. Owing to the stability of the second, methanogenic phase of anaerobic waste decomposition, the pH of leachate increases to 8.5-9.0 (Henry, 1987). The degree to which landfill age and waste decomposition influence the BOD5/COD ratio and pH of leachate is presented in Table 2.6. 36 Table 2.6: Landfill Aged Influence on BOD5/COD Ratio and pH of leachate (Henry, 1987 and Amokrane, 1997) Landfill age Young (<5years) Mature (ageing) Old (>10years) 2.8 Degree of waste decomposition Fresh, not decomposed wastes Partially decomposed Well-stabilized wastes pH of leachate <6.5 6.5-7.5 >7.5 BOD5/COD ratio 0.7 0.5-0.3 0.1 Leachate Contol Strategies The leachate control strategies cover of waste input, control of water input, control of landfill reactor and control of leachate dischage into the environment (Christensen et al., 1992). To control waste input, the amount of waste to be landfilled should be reduced to a minimum level (Wang, 2004). The reduction of waste can be done by separation of collection activities, recycling centers, incineration and composting. Separation of hazardous fractions of municipal waste such as batteries, paint, expired medicine and pesticide can reduce heavy metal and other toxic compounds concentration in leachate. To control water input depends on the quality of waste to be landfilled (SBC, 2002). For non-biodegradable waste, water infiltration should be prevented through introduction of top sealing. For biodegradable waste, water input must be given so that a certain degree of biostabilization can be obtained. To control the water input, there are several important parameters to be considered. The parameters are siting of landfill in low precipitation areas, usage of cover and topsoil systems that are suitable for vital vegetation and biomass production, vegetation of the topsoil with species which optomize the evaporation effect, surface lining in critical hydrological conditions, limitation on sludge disposal, surface water drainage and diversion high compaction of the refuse in the place and measures to prevent risks of cracking owing to differential settlement (Christensen et al., 1992). 37 2.9 Type of Landfill Landfill is land disposal sites that employ an engineering method of solid waste disposal to minimize environmental hazards and protect the quality of surface and subsurface waters (Pankratz, 2001). Landfill sites are classified into 5 types according to structure as shown in Table 2.7 and Figure 2.16. In terms of quality of leachate and gases generated from landfill site, either semi-aerobic or aerobic landfill method is desirous. Table 2.7: Classification of Landfill Structure (Pankratz, 2001) Types of Landfill Classification Anaerobic landfill Solid wastes are filled; in dug area of plane field or valley. Wastes are filled with water and in anaerobic condition. Anaerobic sanitary landfill Anaerobic landfill with cover like sandwich shape. Condition in solid waste is same as anaerobic landfill. Improved anaerobic sanitary landfill (Improved sanitary landfill) This has leachate collection system in the bottom of the landfill site. Others are same as anaerobic sanitary landfill. The condition is still anaerobic and moisture content is much less than anaerobic sanitary landfill. Semi-aerobic landfill Leachate collection duct is bigger than the one of improved sanitary landfill. The opening of the duct is surrounded by air and the duct is covered with small crushed stones. Moisture content in solid waste is small. Oxygen is supplied to solid waste from leachate collection duct. Aerobic landfill In addition to the leachate collection pipe, air supply pipes are attached and air is enforced to enter the solid waste of which condition becomes more aerobic than semi-aerobic landfill. 38 Figure 2.16: Classification of landfill structures (Chew, 2005) CHAPTER 3 RESEARCH METHODOLOGY 3.1 Introduction In this chapter, the methodology applied in order to carry out the tests and analysis on the treatment of leachate using free water surface constructed wetlands (FWSCW) is discussed. The pilot scale experiments on FWSCW treatment of landfill leachate were conducted under ambient condition with an average temperature of about 30ĖC. Sanitary landfill leachate samples, collected from Tanjung Langsat, Pasir Gudang municipal landfill site, located 42 km north-east of Johor. This sanitary landfill began its operations in June 2002. The experiments were conducted separately in the three (3) cells filled with different leachate concentration where Cell A is 50% leachate concentration, Cell B is 33% leachate concentration and Cell C act as control unit where there is no Limnocharis flava was planted. Same number of wetland plants (60 no. of plants), Limnocharis flava is placed in each of the two cells for leachate treatment. Sequence of the experiment was conducted as shown in Appendix D. Figure 3.1 shows the simplified research methodology. 40 Experimental Set Up Set up of pilot scale constructed wetlands Experimental Works System 1 System 2 Cell A with 50% leachate concentration and 40 no.m-2 to 60 no.m-2 of plant Cell B with 33% leachate concentration and 40 no.m-2 to 60 no.m-2 of plant Sampling and Preservation Data Analysis • • Based on the parameter observed in the experiment Removal efficiencies of pollutant Conclusions and recommendation Figure 3.1: The framework of study 41 3.2 Experimental Set Up and Operating Conditions of Constructed Wetland Three pilot scale FWSCW units, made of reinforce concrete, were built at the Environmental Laboratory, Faculty of Civil Engineering, Universiti Teknologi Malaysia, each with a dimension of 0.5m x 4.0m x 0.5m (width x length x depth), and a bed slope of 1% (Sawaittayothin and Chongrak, 2006) as shown in Plate 3.1. The support media of these units consisted of large gravel (2 cm in diameter), medium gravel (1 cm in diameter) and sand at depth 10 cm, respectively. Gravel was selected because of its high hydraulic conductivity, ease of maintenance and consistency of specification, allowing greater predictability of performance than other soil media (Barr and Robinson, 1999). Plate 3.1: Lab-scale constructed wetland A species of wetland plant called Limnocharis flava (yellow burhead) illustrated in Figure 3.2 has been chosen for various reasons. Firstly, it is one of the most common wetland plants available in this region as it is also one of the wetland plants in Putrajaya wetland (Lim et al, 1998). The plants were planted at a density of 60 no.m-2 for each unit. The campus domestic wastewater was fed continuously for one week to the FWSCW units to acclimatize the soil microbes and to support growth of the yellow burhead plant. After the plants were fully grown to an average height of 3 cm, the FWSCW units were continuously fed with the diluted landfill leachate for one week to let the FWSCW units used to new condition. After that, the landfill leachate diluted with tap water and fed into the FWSCW unit as shown in Plate 3.3 and 3.4 according to the 42 concentration chosen. The effects of different concentration on the treatment performance of FWSCW were studied by varying the hydraulic retention time (HRT) at 3, 6 and 9 day and the efficiencies of the system in terms of percentage removal of the pollutant. Harvesting of the yellow burhead plants was conducted once every two weeks by cutting the plant stems at about 30 cm above the FWSCW beds. About 50% of the burhead plants were harvested and 70% of the burhead plants were planted each time to allow for the FWSCW beds to maintain treatment efficiencies. The different concentrations of leachate are use for this study were Cell A is 50% leachate and 50% tap water (1 leachate:1 water) and Cell B is 33% leachate and 67% tap water (1 leachate:2 water). All the physical, chemical and biological parameters of the wastewater were analyzed according to the methods described in Standard Methods for the examination of water and wastewater (APHA, 2002). Yellow burhead belongs to Limnocharitaceae family. It is a perennial herb that is native to tropical America and West Indies. This herb is a large hydrophyte and can reach 70 cm in height. The leaves are rice paddle-shaped and soft. It blooms yellow trefoil flowers on the trigonal floral axes. The young leaves and flowers are used for a spicy herb or fodder in tropical areas. The characteristics of the Limnocharis flava as stated in Table 3.1. Figure 3.2: Limnocharis flava (yellow burhead) 43 Table 3.1: The characteristics of the Limnocharis flava Alternative Name(s): Yellow Burrhead. Family: Limnocharitaceae. Form: Water plant Origin: Native from Mexico to Paraguay and to the Caribbean Islands. Flowers/Seedhead: Flowers: At the end of long stems. Flowers recurving when fruiting and fruit buried in mud or water. Flowers year round. Description: Perennial herb to 1 m high and rooting in mud. Leaves broad-ovate, thick, 5–30 cm long, 4–25 cm wide, leaf stalk (petiole) 5–75 cm long, green. Fruit compound, to 2 cm wide, each fruit containing about 1,000 seeds. Seeds dark brown, horseshoe-shaped, to 1.5 mm long with obvious ridges. (Source: http://www.weeds.org.au/) Plate 3.2: Dilution of landfill leachate before pour into the cells 44 50% 33% Plate 3.3: Different concentration of leachate used during the experiment 3.3 Experimental Analysis The entire tests were carried out in Environmental Laboratory, Faculty of Civil Engineering, Universiti Teknologi Malaysia. The tests include parameter such as Total suspended solid (TSS), turbidity, biochemical oxygen demand (COD), test for nutrients such as nitrate, ammonia, phosphorus, manganese, and iron. 3.3.1 Analysis of Leachate The leachate was sampled in each of two cells by using grab sampling according to the standard methods (APHA, 2002). Sampling was done every 3, 6 and 9 days according to the HRT used and the analysis for each parameter was done in Environmental Laboratory, Faculty of Civil Engineering, Universiti Teknologi Malaysia, Skudai Johor. The parameter for leachate analysis was listed as follow: 45 (a) Turbidity Turbidity test was conducted according to the Standard Method APHA by using Spectrophotometer HACH DR 4000 Model, method used is 10047 (Attenuated Radiation Method – Direct Reading) and Hach program is 3750. (b) Biochemical Oxygen Demand Biochemical Oxygen Demand (COD) test was conducted according to the Standard Method APHA by using Spectrophotometer HACH DR 4000 Model, method used is 8000 (Reactor Digestion Method) and Hach program is 2720. (c) Ammonia Nitrogen Ammonia Nitrogen (NH3-N) analysis was conducted according to Standard Method APHA 4500-NH3-N by using Spectrophotometer HACH DR 4000 Model, method used is 8038 (Nessler Method) and Hach program is 2400. (d) Nitrate Nitrogen Nitrate Nitrogen (NO3—N) analysis was conducted according to the Standard Methods APHA 4500- NO3--N by using Spectrophotometer HACH DR 4000 Model, method used is 8093 (Cadmium Reduction Method) and Hach program is 2530. (e) Orthophosphate Orthophosphate (PO43-) analysis was conducted according to the Standard Methods APHA 4500-P (C) by Spectrophotometer HACH DR 4000 Model, method used is 8048 (PhosVer 3 – Ascorbic Acid Method) and Hach program is 3025. 46 (f) Total Iron Total iron was measured according to the Standard Methods APHA 3500-Fe (B) by using Spectrophotometer HACH DR 4000 Model, method used is 8112 (TPTZ Method) and Hach program is 2190. (g) Manganese (Mn) Manganese was measured according to the Standard Methods APHA 3500- Mn (B) by using Spectrophotometer HACH DR 4000 Model, method used is 8034 (Periodate Oxidation Method) and Hach program is 2250. CHAPTER 4 RESULTS AND DISCUSSION 4.1 Introduction In this chapter, the results from the laboratory analysis of the FWSCW will be analyzed and discussed in details. The data will be shown in graphical approach to evaluate the removal efficiency of the FWSCW system in treating landfill leachate. The experimental studies were carried out for five months from May until September. The effluent from the FWSCW was conclusively subdivided into three categories, namely the physical parameters (TSS and Turbidity), nutrients (NH3-N, NO3-N, P, Mn and Fe) and the organic matter (COD) The difference leachate concentration was compared to evaluate the trends for the overall performance. Analysis of variance (ANOVA) has been used to reveal significant differences for all treatments. Statistical significance differences were tested at p≤0.05 (95% levels of significance). Thus, an extensive discussion had been concluded in the behavior obtained comparing significant differences between the three tanks (control, 50% leachate concentration and 33% leachate concentration) and comparing significant differences between HRT 3, 6 and 9 days. 48 4.2 Pollutant Removal in Leachate The quality of the pre-treated leachate taken from the Tanjung Langsat municipal landfill site, had characteristics as shown in Table 4.1. These data were obtained from analyses of leachate samples collected six times during the study. The quality of leachate, which is taken from the landfill, was found not to comply with Standard B under Environmental Quality (Sewage and Industrial Effluent) Regulations 1979 as shown in Appendix A. Table 4.1: Characteristics of landfill leachate used in FWSCW experiments Parameters Unit Range Average SD COD mg/L 192-446 297.45 163.07 Orthophosphate mg/L 48.9-52.7 50.84 9.42 Nitrate-nitrogen mg/L 77.2-195 135.43 60.65 Ammonia-nitrogen mg/L 26.3-69.68 52.6 25.34 Manganese mg/L 0.66-2.0 1.16 0.78 Iron mg/L 0.02-0.42 0.55 0.72 Zinc mg/L 0.003-0.04 0.071 0.08 Chromium mg/L 0.02-0.08 0.16 0.15 Turbidity FAU 2-6 4.95 1.97 Suspended solid mg/L 2.5-7.5 1.53 0.70 SD = standard deviation; FAU = Formazin Attenuation Units The quality of pre-treated landfill leachate after being 50% and 33% diluted as shown in Table B1 (Appendix B) and the effluent quality after the leachate was treated accordingly to the HRT by using the FWS constructed wetlands are summarize in Table 4.2 and Table 4.3, while Table 4.4 shows the effluent quality for the control unit. The percentages of removal for three (3) cells in terms of hydraulic retention time (HRT) are depicted in Table 4.5, 4.6 and 4.7. All the parameters are given in milligram per liter (mg/l) except for turbidity given in FAU (Formazin Attenuation Units). A FAU is equivalent to a NTU (Nephelometric Turbidity Units). 49 Table 4.2: Effluent concentration after treated by FWSCW for Cell A Description NH3-N (inf) NH3-N (eff) NO3-N (inf) NO3-N (eff) PO43- (inf) PO43- (eff) COD (inf) COD (eff) Mn (inf) Mn (eff) Zn (inf) Zn (eff) Fe (inf) Fe (eff) Turbidity (inf) Turbidity (eff) TSS (inf) TSS (eff) Experimental unit HRT (day) (Cell A) 3 6 9 66.35 66.95 66.15 12.85 4.91 16.03 54.53 55.00 55.17 9.34 8.51 16.36 4.38 4.95 3.69 1.09 0.64 0.35 279 289 248 93 25 55 1.15 2.83 1.15 0.15 0.12 0.12 0.32 0.22 0.24 0.04 0.01 0.03 0.20 0.18 0.17 0.05 0.01 0.05 4.00 4.00 4.00 1.00 0.00 0.00 0.05 0.05 0.05 0.005 0.005 0 All units in mg/l, except for turbidity = FAU (Formazin Attenuation Units) Table 4.3: Effluent concentration after treated by FWSCW for Cell B Description NH3-N (inf) NH3-N (eff) NO3-N (inf) NO3-N (eff) PO43- (inf) PO43- (eff) COD (inf) COD (eff) Mn (inf) Mn (eff) Zn (inf) Zn (eff) Fe (inf) Fe (eff) Turbidity (inf) Turbidity (eff) TSS (inf) TSS (eff) Experimental unit HRT (day) (Cell B) 3 6 9 27.83 31.58 27.98 4.70 6.61 7.05 15.15 15.92 15.30 4.10 0.35 6.90 3.16 2.92 3.31 0.38 0.07 1.46 265 296 266 60 55 95 1.10 1.18 1.10 0.10 0.14 0.20 0.06 0.09 0.07 0.05 0.01 0.04 0.21 0.23 0.31 0.02 0.04 0.06 4.00 4.00 4.00 0.00 0.00 0.00 0.05 0.05 0.05 0.005 0.005 0 All units in mg/l, except for turbidity = FAU (Formazin Attenuation Units) 50 Table 4.4: Effluent concentration after treated by FWSCW for control unit Description NH3-N (inf) NH3-N (eff) NO3-N (inf) NO3-N (eff) PO43- (inf) PO43- (eff) COD (inf) COD (eff) Mn (inf) Mn (eff) Zn (inf) Zn (eff) Fe (inf) Fe (eff) Turbidity (inf) Turbidity (eff) TSS (inf) TSS (eff) Experimental unit HRT (day) (control unit) 3 6 9 69.67 69.18 68.38 39.14 50.94 20.61 70.55 78.24 67.14 50.92 25.64 50.14 53.80 48.43 55.25 41.33 7.73 12.32 403 461.5 400 40.40 30.02 50.40 2.00 2.00 2.20 1.03 0.48 1.14 0.43 0.39 0.10 0.08 0.08 0.06 0.42 0.31 0.42 0.35 0.18 0.15 6.00 5.00 7.10 0.08 0.05 0.05 7.5 0.02 0.15 0.005 0 0 All units in mg/l, except for turbidity = FAU (Formazin Attenuation Units) Table 4.5: Removal efficiencies in FWSCW at HRT 3 day Description NH3-N NO3-N PO43COD Mn Zn Fe Turbidity TSS Cell A 80.63 % 82.88 % 75.11 % 66.67 % 86.96 % 84.38 % 74.87 % 75 % 90 % HRT = 3 day Cell B Control unit 83.11 % 43.82 % 72.94 % 27.82 % 23.18 % 88.07 % 77.36 % 89.98 % 90.91 % 48.50 % 19.13 % 80.93 % 16.67 % 91.71 % 98.67 % 100 % 99.93 % 90 % 51 Table 4.6: Removal efficiencies in FWSCW at HRT 6 day Description NH3-N NO3-N PO43COD Mn Zn Fe Turbidity TSS Cell A 92.67 % 84.53 % 87.07 % 91.35 % 89.57 % 94.96 % 94.44 % 100 % 90 % HRT = 6 day Cell B Control unit 79.07 % 26.36 % 97.81 % 67.23 % 97.67 % 84.04 % 81.42 % 93.50 % 88.14 % 76 % 90.32 % 79.33 % 83.04 % 41.29 % 100 % 99 % 9% 100 % Table 4.7: Removal efficiencies in FWSCW at HRT 9 day Description NH3-N NO3-N PO43COD Mn Zn Fe Turbidity TSS 4.3 Cell A 75.76 % 70.36 % 90.65 % 77.82 % 89.57 % 86.29 % 69.64 % 100 % 100 % HRT = 9 day Cell B Control unit 74.80 % 69.86 % 54.89 % 25.32 % 55.95 % 77.70 % 64.29 % 87.40 % 81.82 % 48.18 % 42.47 % 45.00 % 79.34 % 63.33 % 100 % 99.35 % 100 % 100 % Water Quality Analysis There are several water quality parameters such as pH, alkalinity, conductivity, dissolved oxygen, temperature, colour and etc. However, only two water quality parameter that consider in this study, namely, total suspended solid (TSS) and turbidity. Turbidity is a water quality parameter that refers to how clear the water is. The greater the amount of total suspended solids (TSS) in the water, the murkier it appears and the higher the measured turbidity. Analysis for both parameters will be discussed in detailed in next sub-section. 52 4.3.1 Total Suspended Solid Removal Suspended solids were identified as one of the contaminants of concern in most landfill leachate effluent. Total suspended solids (TSS) include all particles suspended in water that will not pass through a filter. Abundant suspended solids such as clay and silt, fine particles of organic and inorganic matter (such as iron particulate), soluble coloured compounds and phytoplankton can result in; decreased light penetration in water reducing photosynthesis of water plants, decreased water depth due to sediment build-up, the smothering of aquatic vegetation, habitat and food, the smothering of macro and micro-organisms, larva, eggs and the clogging of fish gills, the reduced efficiency of predation by visual hunters, and increased heat absorbed by the water, lowering dissolved oxygen, facilitating parasite and disease growth and increasing the toxicity of ammonia (Mason, 1998; and Boulton and Brock, 1999). Suspended solid removal in constructed wetlands is best facilitated through the encouragement of settling. Effective settling in treatment wetland systems is most commonly accommodated by the creation of a settling pond or a forebay at the head of the wetland. They are typically designed to support long retention times in order to allow the suspended solids and other debris to settle out. The increased depth accommodates sediment build up, reducing the need for frequent dredging (Tousignant et al., 1999). On comparing the performance of different concentration, greater level of TSS removal was observed in control unit at HRT 6 day was 100% removal, whereas at HRT 9 day the greatest level of TSS removal occur in Cell A, B and control unit with removal of 100% as shown in Figure 4.1. Roser et al. (1987) has reported that the percentage removal of TSS for retention times 3-5 days is 89% compared to retention times 6-9 days is 94%. It shows that the higher retention time, gives the higher TSS removal. Other study performed by Gersberg et al. (1986), the removal efficiencies for the vegetated beds were not significantly different from the unvegetated bed. They concluded that the removal of SS was almost due entirely to sedimentation and filtration rather than biological processes. 53 Moreover, the percentage of removal for those cells can reach up 100% removal at HRT 9 days as shown Figure 4.1. The figure shows obviously increase in TSS for control unit. 100 TSS removal (%) 98 96 94 Control unit 92 Cell A 90 Cell B 88 86 84 3 6 HRT (days) 9 Figure 4.1: Percentage of removal for Cell A and B for total suspended solids (TSS). The FWSCW system can reach until 100% removal for both cells. The TSS concentrations in those cells are shown in Figure 4.2 where the concentration at HRT 6 and 9 day reaches 0 mg/l. According to Chongrak and Lim (1998), settleable solids are removed easily via gravity sedimentation as wetland systems generally have long hydraulic retention times (HRT). It was believed that all the particles are trapped in the media. It shows that the media plays an important role in terms of removal of suspended solid as well as to support the growth of rooted emergent plant. According to Davit et al. (2001), solids are removed by physical filtration and settling within the gravel/root hair matrix. Organic matter may also be removed by these physical processes, but is ultimately removed through biodegradation. TSS concentration (mg/l) 54 0.0050 0.0045 0.0040 0.0035 0.0030 0.0025 0.0020 0.0015 0.0010 0.0005 0.0000 Control unit Cell A Cell B 3 6 HRT (days) 9 Figure 4.2: Concentration of TSS as a function of sampling day for Cell A, B as well as control unit where the concentration at HRT 9 day reaches 0 mg/l. It was believed that all the particles are trapped in the media. 4.3.2 Turbidity Removal Figure 4.3 illustrate the overall performance of turbidity removal for Cell A, B and control unit free water surface constructed wetland systems in terms of different hydraulic retention time (HRT). 100 Tubidity removal (%) 90 80 70 60 Control unit 50 Cell A 40 Cell B 30 20 10 0 3 6 HRT (day) 9 Figure 4.3: Percentage removal for Cell A, B and control unit in different HRT. The percentage removals are increasing steadily where the system can reach until 100% removal for those cells in FWSCW. 55 As TSS, similar trend was observed in turbidity removal. On comparing the performance of different HRT, greater level of turbidity removal was observed at HRT 6 and 9 day for Cell A, B and control unit as well where the removal are 100%, 100% and 99% respectively. While for HRT 3 day, the removal are 75%, 100% and Turbidity concentration (FAU) 98.67% for Cell A, B and control unit. 1.00 0.90 0.80 0.70 0.60 0.50 0.40 0.30 0.20 0.10 0.00 Control unit Cell A Cell B 3 6 HRT (day) 9 Figure 4.4: The turbidity concentration with different HRT for Cell A, B and control unit where the leachate concentration are decrease due to sedimentation and filtration that occur during the process. Figure 4.4 shows the reduction of turbidity up to 0 FAU due to sedimentation and filtration. However, at HRT 3 d, turbidity removal for Cell A is 1 FAU but others is less than 0.1 FAU. Typically, a biological process associated with the plants was not contributed to turbidity removal since the percentage between both concentrations was not significantly different (Nazaitulshila, 2006). Results are given in FAU (Formazin Attenuation Units) not Nephelometric Turbidity Units (NTU). A FAU is equivalent to a NTU. 56 4.4 Organic Matter Analysis 4.4.1 Biochemical Oxygen Demand Removal For this research, the biodegradable organic matter being studied in landfill leachate is Chemical Oxygen Demand (COD). In wetland systems, microbial degradation plays a dominant role in the removal of soluble/colloidal biodegradable organic matter (BOD or COD) in wastewater, the remaining BOD associated with settleable solids being removed by sedimentation (Chongrak and Lim, 1998). However, the BOD test is neglect in this study due to shortage of time and equipment. Figure 4.5 showed the COD removal efficiency in control experiment and different leachate concentration with different HRT wetlands with exposure to natural environmental condition. 100 90 COD removal (%) 80 70 60 Control Unit 50 40 Cell A 30 Cell B 20 10 0 3 6 HRT (day) 9 Figure 4.5: The percentage of removal of COD for Cell A, B and control unit. The removals are increase steadily up to 94% removal in control unit. On the other hand, the removal of control unit higher than Cell A and B which was probably due to the presence of non-biodegradable organic compounds in the landfill leachate. The treatment performance of the three (3) units operating at the various HRT is shown in Table 4.2 through 4.7. At steady state conditions, the FWSCW units operating at HRT of 6 day had more than 80% of organic (COD) removal for Cell A, 57 B and control unit with the effluent COD concentrations being less than 100 mg/L as shown in Figure 4.6 which is comply with Standard B under Environmental Quality (Sewage and Industrial Effluent) Regulations 1979. COD is used to evaluate the organic strength of domestic and industrial wastewaster (Pouliot, 1999). It measures the amount of oxygen necessary to complete oxidize all organic matter. The percentages of COD removal in the experimental FWSCW unit of Cell A (50% concentration) and Cell B (33% concentration) are slightly higher than those control unit which was probably due to the presence of non-biodegradable organic COD concentration (mg/l) compounds in the landfill leachate. 100 90 80 70 60 50 40 30 20 10 0 95.00 93 60 55.00 55 50.40 Control unit Cell A 40 30 3 Cell B 25 6 HRT (day) 9 Figure 4.6: The effluent quality for Cell A, B and control unit with different HRT. The highest COD removal occurs in Cell B at HRT 9 day with 95.0 mg/l. The effluent quality for HRT 3 day can be observed in Cell A with 93.0 mg/l. Chemical oxygen demand (COD) is a measure of the amount of the oxygen required to chemically oxidize reduced minerals and organic matter. It does not differentiate between biologically available and inert organic matter (Galbrand, 2003). In general, the greater the COD value in water, the more oxygen influent demands, from the water body, thus resulting in depleted dissolved oxygen which is essential to the metabolisme of all aerobic aquatic organisme (Silva et. al., 2003; Cusso et. al., 2001). According to Crites and Tchobanoglous (1998), the COD removal in control unit increased due to the algae decay that released and recycled back the organic and inorganic matter in the leachate. Thus, the COD in the control unit did not decrease 58 but increased throughout the experiment as illustrated in Figure 4.5. As reported by Wood et al. (1989), the poor COD removal efficiency was due to the high surface loading rate and incapacity of the macrophytes to meet the oxygen demand. 4.5 Chemical Water Quality Analysis 4.5.1 Ammonia Nitrogen Removal Ammonia was identified as one of the contaminants of concern in most landfill leachate effluent. Ammonia nitrogen is a pungent, gaseous compound of nitrogen and hydrogen and includes both ammonia (NH3) and ammonium ion (NH4-). More common in landfill leachate is the ionized form NH4+ which is formed when NH3 is combined with water at pH less than 8.5 and low temperatures to produce an ammonium ion and a hydroxide ion (OH-) (Galbrand, 2003). Ammonia concentrations are typically less than 0.1 mg/l in natural waters. Figure 4.7 depicted the NH3-N removal efficiency of Cell A, B and control unit under different hydraulic retention time (HRT) with exposure to natural environmental condition. 92.67 100 Ammonia nitrogen removal (%) 90 80.63 83.11 79.07 80 69.86 75.7674.80 70 60 50 43.82 Control Unit 40 Cell A 26.36 30 Cell B 20 10 0 3 6 HRT (day) 9 Figure 4.7: The percentage of removal for NH3-N with different hydraulic retention time (HRT). The highest removal can be obtained in Cell A at HRT 6 day. The lowest removal of NH3-N occurs in control unit with 26% at HRT 6 day. 59 Removal of ammonia nitrogen (NH3-N) was the highest in Cell A under three different HRT which is 81% removal at HRT 3 day, 93% removal at HRT 6 day and 76% removal at HRT 9 day. An overall, the lowest removal can be obtained at HRT 9 day where the removals are 70% removal in control unit, 76% removal in Cell A and 75% removal in Cell B due to the plant wilting. As reported by El-Gendy (2003), plant wilting will increase the nutrient concentration in leachate which included NH3N. Figure 4.7 indicated the significance of HRT on treatment performance of FWSCW. The HRT 3 and 9 day were found to be too short and too long for the FWSCW units to effectively treat the landfill leachate. According to Chongrak and Lim (1998), the HRT is one of the major factors affecting the treatment performance. In general, a too long HRT can result in stagnant anaerobic conditions whereas the shorter HRT do not provide sufficient time for degradation of pollutants. However, the best performance of NH3-N can be obtained at HRT 6 day. Plant uptake for NH3-N was not significant in the wetlands since the NH3-N removal efficiency in control unit is nearly to removal efficiency in Cell A and B. Thus, most of the NH3-N removal mechanisms involved in nitrification by Nitrosomonas and Nitrobacter bacteria (Boulton and Brock, 1999). However, the plants provided aerobic zone in the root for nitrification to be occurred as reported by Chongrak and Lim (1998). 4.5.2 Nitrate Nitrogen Removal In aerobic conditions, nitrite is typically rapidly oxidized to nitrate by Nitrobacter bacteria. Nitrate is an inorganic compound of nitrogen which is bioavailable for plant uptake and is essential to plant growth (Boulton and Brock, 1999; Freedman, 2001). Natural levels of nitrate in waterbodies are typically lower than 1 mg/l where nitrite and ammonia are toxic, nitrate is virtually harmless, with direct toxic effect typically not observed until concentrations greater than 1000 mg/l (Mason, 1998). However, if phosphorus concentrations are sufficient, high nitrate 60 content in waters can increase the severity of eutrophication, which can have chronic effects of aquatic life. In this study, only ammonia nitrogen (NH3-N) and nitrate (NO3-N) will be considered, the others are possible due to their transformation are to short and the limitation of the laboratory apparatus. Nitrification is usually defined as the biological oxidation of ammonium to nitrate with nitirite as an intermediate in the reaction sequence. The nitrate nitrogen (NO3-N) removal in the FWSCW unit ranged from 28% to 83% for HRT 3 day, 67% to 98% for HRT 6 day and 25% to 70% for HRT 9 day. The laboratory analyses for the effluent of the FWSCW are shown in Nitrate-nitrogen removal (%) Figure 4.8. 97.81 100 84.53 82.88 90 72.94 70.36 80 67.23 70 54.89 60 50 40 27.82 25.32 30 20 10 0 3 6 9 HRT (day) Control Unit Cell A Cell B Figure 4.8: The percentage of removal for NO3-N with different hydraulic retention time (HRT). The highest removal can be obtained in Cell B at HRT 6 day with removal 98%. The lowest removal of NO3-N occurs in control unit with 25% at HRT 9 day. Figure 4.8 indicates the overall performance of NO3-N removal efficiency of three different hydraulic retention times (HRTs) in FWSCW with expose to natural environmental condition. NO3-N removal in control unit is slightly lower due to unvegetated beds. In comparison among three cells, Cell B was the most efficient in removing NO3-N which was 98%. On the other hand, the best HRT for NO3-N removal is HRT 6 day where 67% removal achieved in control unit instead of 28% and 25% at HRT 3 and 9 61 days, 85% NO3-N removal can be obtained in Cell A (HRT = 6 day) instead of 83% and 79% in HRT3 and 9 days, and the highest removal occurred in Cell B with 98% removal instead of 73% and 55% at HRT 3 and 9 days. As a conclusion, the best HRT in terms of NO3-N removal is HRT 6. According to Gersberg et al. (1983), the plant uptake was not a significant pathway in the overall nitrogen removal and that the major loss of nitrogen from the system was due to denitrification. Moreover, Gersberg et al. (1986) investigated the wetland beds planted achieved ammoniacal nitrogen efficiencies of 94% as compared with only 11% for unvegetated beds at the HLR of 4.7cm/d or HRT of 6 days. Research performed by Roser et al. (1987), both planted and unplanted gravel beds yielded similar percentages of N removal. Average percentage of N removal was about 51% for HRT of 3-5 day and 54% for HRT of 6-9 days. NO3-N removal was lower in Cell A than Cell B due to the plant wilting that eventually increased NO3-N concentration in the leachate (Crites and Tchobanoglous, 1998). As stated by Nivala et al. (2006), low concentration of effluent NO3-N can mean one of two thing; (Case I) that nitrification is not occurring and NO3-N is not being formed (corresponding to minimal net removal of nitrogen), or (Case II) that both nitrification and denitrification processes are occurring to completion (corresponding to high net removal of nitrogen). 4.5.3 Orthophosphate Removal Phosphorus in wetland occurs as phosphate in organic and inorganic compounds. Free orthophosphate is the only form of phosphorus believed to be utilized directly by algae and macrophytes and thus represents a major link between organic and inorganic phosphorus cycling in wetlands. Moreover, according to Lee and Jones-Lee (2001), the phosphorus is an essential macronutrient that is a limiting factor to plant growth. It is essential to all life as a component of nucleic acids and a universal energy molecule. In excess, phosphorus triggers eutrophic conditions which involve the profilic growth of algal and other aquatic plants. Algal growth can 62 have lethal impacts on aquatic life and, at high concentrations, can be toxic in itself (Galbrand, 2003). Figure 4.9 indicates the PO43- removal efficiency under different hydraulic retention time (HRTs) in FWSCW with expose to natural environmental condition. 97.67 100 Ortgophosphate removal (%) 90 80 88.07 75.11 87.07 84.04 90.65 77.70 70 55.95 60 Control Unit 50 40 30 Cell A 23.18 Cell B 20 10 0 3 6 HRT (day) 9 Figure 4.9: The percentage removal of orthophosphate under different HRT. The highest removal can be obtained in Cell B at HRT 6 day with removal 98%. The lowest removal of PO43- occurs in control unit with 23% at HRT 3 day. PO43- removal efficiency was low in the control unit at HRT 3 day and HRT 9 days with removal of 56% in Cell B. According to Chongrak and Lim (1998), the low removal efficiency was due to the reason that the plant uptake and microoganisms biodegradation were not the major mechanisms in PO43- removal. Instead, adsorption and precipitation was the major removal pathway where phosphorus was adsorbed to the soils or precipitated with calcium/aluminium (Kadlec and Knight, 1996; Boulton and Brock, 1999). The highest removal efficiency can be obtained at HRT 6 days where Cell A is 87% removal, Cell B is 98% removal and control unit is 84% removal. Research performed by Roser et al. (1987), both planted and unplanted gravel beds yielded similar percentages of P removal. The authors suggested that filtration was a significant P removal mechanism as shown by the ability of the unplanted bed to match the P removal efficiency achieved by the planted systems. 63 It shows not much different due to the settlement of the nutrient at the surface of the soil media. As revealed by Rosolen (2000), the phosphorus absorbed onto suspended sediments will be filtered out as the suspended solids are removed. Phosphorus has very low solubility, and is readily moved from solution by several precipitation and adsorption reactions by binding it in an insoluble form. Kim and Geary (2000) reported that soil substrates are the ultimate sink for phosphorus. The absorption of sunlight by algal blooms reduces amount of light reaching aquatic plants in sediments. If an algal bloom is prolonged, aquatic plants will die. Large amounts of decaying algae result in the consummation of large quantities of oxygen by the bacteria and fungi that break it down. This results in the dramatic reduction of oxygen concentrations in the water column, particularly at night. This reduction affects invertebrate predators with high oxygen requirements. The subsequent lack of predators results in critical disruptions in food chain and increases of nuisance species such as mosquitoes. Algal blooms can also contain toxic strains of blue-green algae which may kill birds, domestic animals, aquatic macroinvertebrates and even humans if consumed (Lee and Jones-Lee, 2001; Sharpley et. al., 1994). 4.5.4 Manganese Removal Manganese was also identified as one of the contaminants of concern in the landfill leachate effluent needing treatment. Manganese (Mn) is a transition metal which is grey, white of silver in colour. It is soft and ductile if pure but usually occurs in compounds and complexes with organic compounds (Sample et. al., 1997). Zhu et al., (1997) declared that a metal such as Fe and Mn correlates to the ability of a particle to remove phosphorus. Adsorption is dependent on composition of the material, which is oxides of these metals, while the availability of these minerals in the soluble form will direct precipitation reactions. Manganese is an essential micronutrient forming a vital part of the enzyme systems that metabolise proteins and energy in all animals (Galbrand, 2003). There 64 are about eight nutrients essential to plant growth and health that are only needed in very small quantities. These are manganese, boron, copper, iron, chlorine, cobalt, molybdenum, and zinc. Though these are present in only small quantities, they are all necessary. Figure 4.10 indicates the Mn removal efficiency for Cell A, B and control unit under different hydraulic retention time (HRT) with exposure to natural Manganese removal (%) environmental condition. 90.91 100 89.57 88.14 89.57 86.96 81.82 90 76.00 80 70 48.18 60 48.50 50 40 30 20 10 0 3 6 9 HRT (days) Control unit Cell A Cell B Figure 4.10: The percentage removal of manganese under different HRT. The highest removal can be obtained in Cell B at HRT 3 day with removal 91%. The lowest removal of Mn occurs in control unit with 48% at HRT 9 day. Different HRT that use in the FWSCW gives not much different in remove manganese (Mn). At HRT 3 days 87% removal in Cell A, 91% removal in Cell B, and 49% removal in control unit. Therefore, at HRT 6 days, 90% removal occurred in Cell A, 88% removal in Cell B and 76% removal in control unit. The longer HRT in this experiment is 9 days where 90% removal in Cell A, 82% in Cell B, and 48% removal in control unit. Mn uptake by plants Limnocharis flava was less than Fe. According to Kamal et al. (2004), F2+ was the micronutrient for plants that was required in higher concentration than Mn2+. Mn removal was slightly higher at HRT 3 days. This was due to the plant wilting that minimized plant uptake for Mn (Soltan and Rashed, 2003). 65 4.5.5 Iron Removal The iron (Fe) removal efficiency was observed in the study as shown in Figure 4.11. The percentages of removal for three cells are fluctuating. At HRT 6 days, the iron (Fe) concentrations are increased due to the accumulation of the iron in the media bed. Iron (Fe) removal in the FWSCW was rather effective, where the 94% removal in Cell A and 83% in Cell B at HRT 6 days. Also, over the course of sampling, the iron concentration at HRT 9 days fluctuated drastically than HRT 3 and 6 days, decreasing throughout the rainy days. Rain likely brought more iron into the treatment wetland. The lowest percentage removal of manganese can be obtained at HRT 9 days where 70% removal in Cell A, 79% removal in Cell B and 63% Iron removal (%) removal in control unit. 100 90 80 70 60 50 40 30 20 10 0 94.44 91.71 83.04 74.87 79.34 69.64 63.33 41.29 Control unit Cell A Cell B 16.67 3 6 HRT (day) 9 Figure 4.11: The percentage removal of iron (Fe) under different HRT. The highest removal can be obtained in Cell A at HRT 6 days with removal 94%. The lowest removal of Mn occurs in control unit with 17% at HRT 3 days. As reported by King et al. (1992), Fe is an essential micronutrient element required by both plants and wildlife at significant concentrations. The results of vegetated treatment system described that the Limnocharis flava as an emergent plants play a crucial part in the treatment systems. Emergent plants help in reducing heavy metals by retaining it either in the root of in the leaves. Capacity in accumulating and removing heavy metals are varied according to plant species. Uptake and accumulation of elements by plants may follow two different paths 66 which were n root system and foliar surface (Sawidis, et al., 2001). Nevertheless, the result also indicated that the capability of hydraulic retention time (HRT) in FWSCW those systems assist Fe removal. 4.6 Analysis of Variance Analysis of variance (ANOVA) has been used to reveal significant differences for all types of treatment systems. Statistical significance differences were tested at p≤0.05 (95% levels of significance). Table 4.8 through 4.10 shows the p value when comparing significant differences between control, 50% leachate concentration and 33% leachate concentration and different HRT used in the FWSCW to treat landfill leachate. The details calculation of ANOVA for HRT 3, 6 and 9 day as presented in Table C1 until C24 in Appendix C. Table 4.8: Significant differences between control, Cell A and Cell B at HRT 3 days ANOVA Two Factor Without Replication 95% levels of significance p value p value Parameters Significant Significant p ≥ 0.05 p ≤ 0.05 TSS 0.244 Turbidity 0.571 NH3 N 0.00315 NO3-N 7.31E-05 PO431.69E-05 COD 0.00089 Fe 0.0682 Mn 0.000205 67 Table 4.9: Significant differences between control, Cell A and Cell B at HRT 6 days ANOVA Two Factor Without Replication 95% levels of significance p value p value Parameters Significant Significant p ≥ 0.05 p ≤ 0.05 TSS 0.7164 Turbidity 0.00768 NH3-N 9.53E-05 NO3-N 0.00189 PO430.3705 COD 0.124 Fe 0.0572 Mn 0.00133 Table 4.10: Significant differences between control, Cell A and Cell B at HRT 9 days ANOVA Two Factor Without Replication 95% levels of significance p value p value Parameters Significant Significant p ≥ 0.05 p ≤ 0.05 TSS 0.1296 Turbidity 0.5274 NH3-N 0.0045 NO3-N 0.000157 PO430.5102 COD 0.2710 Fe 0.00727 Mn 0.9816 4.7 Conclusion From the results and analysis, the constructed wetland vegetated with Limnocharis flava have shown their ability to remove suspended solid (TSS), turbidity, nitrate (NO3-N), phosphorus (P), ammoniacal nitrogen (NH4-N), ferum (Fe) and manganese (Mn) from leachate. The leachate concentration used in this experiment was 50% (Cell A), 33% (Cell B) and 100% (control unit). Study done by Hui (2005) had revealed that 50% leachate concentration will give the highest removal efficiency in removing NO3-N and Mn. 68 The different hydraulic retention time (HRT) also affects the pollutant removal in the FWSCW. An overall, the hydraulic retention time of 6 days shows the greater removal in all parameters except for manganese. On comparing between control unit and Cell A and B, Cell A and B gives the highest removal especially at HRT 6 days as shown in Table 4.11. However, both cells show the removal more than 80%. Table 4.11: Percentage removal for three cells at HRT 6 days Description NH3-N (%) NO3-N (%) PO43- (%) COD (%) Mn (%) Zn (%) Fe (%) Turbidity (%) TSS (%) Cell A 92.67 84.53 87.07 91.35 89.57 94.96 94.44 100.00 90.00 HRT = 6 day Cell B Control unit 79.07 26.36 97.81 67.23 97.67 84.04 81.42 93.50 88.14 76.00 90.32 79.33 83.04 41.29 100.00 99.00 90.00 100.00 In a constructed wetland systems, the HRT is one of the major factors affecting the treatment performance. In general, a too long HRT can result in stagnant anaerobic conditions whereas shorther HRTs do not provide sufficient time for the degradation of pollutants. CHAPTER 5 CONCLUSIONS 5.1 Introduction Wetlands are, as the word indicates, wet lands, with soils that are morw or less water saturated, at least periodically. The plants growing in wetlands (often called wetlands plants or macrophyte) are adapted to growing in water saturated soils (Brix, 1994). The quality of landfill leachate is highly dependent upon the stage of fermentation (age of landfill), waste decomposition, operational procedures and codisposal of industrial wastes. Lab-scale free water surface constructed wetland systems, employing natural soil and the yellow burhead (Limnocharis flava), were used to evaluate the landfill leachate effluent. Several aspects were investigated during this experiment; water quality parameters (TSS and turbidity) were monitored, and pollutant (NH3, NO3, P, Fe, and Mn) removal efficiencies were evaluated. The wetland system was proven effective in pollutants removal in leachate. Wetland of 33% leachate concentration showed high removal efficiency especially at 70 hydraulic retention time (HRT) 6 days. During the experiment, there about 50% of the Limnocharic flava were harvest and about 70% of Limnocharis flava were planted each time to allow for the FWSCW beds to maintain treatment efficiencies. According to Mbuligwe (2005), the plant harvesting could be done in the wetland to promote active growth of the plants, avoid mosquito proliferation and to improve the efficiency of the treatment performance. In this study, the different HRT are used to evaluate the efficiencies of FWSCW in removal of pollutants with different leachate concentration. However, the laboratory results shows that the removal efficiencies for 50% leachate concentration and 33% leaachate concentration not much different. Both cells shows the removal more than 80% pollutant removal. The FWSCW were effective in treating the leachate wastewater, resulting in a treated effluent suitable for reuse in agriculture or discharge to nearby environment since the the effluent from FWSCW does not exceed the limit of Standard B Environmental Quality Act. Better removal efficiencies were obtained for all parameters in Cell B (33% leachate concentration) especially at HRT 6 days. Therefore, the FWSCW system is suitable for tertiary landfill leachate treatment. It could be concluded that higher leachate concentration was more efficient in removing pollutants from leachate due to the presence of microorganisms for biodegaradation (Stottmeister et al., 2003). 5.2 Recommendations For future research, there are more extensive studies could be carried out in order to understand more clearly the processes/mechanisms that happen in constructed wetland. There are some recommendations for future research: 71 i) A better understanding of the nitrogen removal and nitrogen transformations occurring in free water surface flow constructed wetlands systems is necessary and this could ensure a better removal of ammonia nitrogen and nitrate in the system. ii) A better understanding and control of the incoming raw landfill leachate is necessary and this could give useful information during operating the system. iii) Use other types of plant such as reeds and bulrushes to determine the performance and removal efficiency of the constructed wetlands systems. iv) The use of specialized media other than the media in this study to improved the porosity and penetration of plant root and avoids clogging from occurring. v) Longer period of the test is necessary to determine the fullest capacity of the free water surface flow constructed wetlands in terms of pollutant removal. 5.3 Conclusions Constructed wetlands are getting much attention nowadays as their potential to provide an effective, low-cost, natural method of removing pollutants from wastewater are recognized. Biotic component of wetlands especially the vegetation affects water conditions through many mechanisms physically, chemically and biologically. There are many unpredictable long-range effects that may develop as constructed wetlands evolved. Removal efficiency of the FWSCW in this study did show an effective performance as predicted. Presence of Limnocharis flava and the second cultivation of the selected plant did increase the ability of the free water surface flow 72 constructed wetlands to decrease the level of organic matters and increase removal of nutrients as the analyses was made. Analysis of variance (ANOVA) has been used to reveal significant differences for all types of treatment systems. Statistical significance differences were tested at p≤0.05 (95% levels of significance). 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APPENDICES 85 APPENDIX A Standard B under Environmental Quality (Sewage and Industrial Effluent) Regulations 1979 THIRD SCHEDULE ENVIRONMENTAL QUALITY (SEWAGE AND INDUSTRIAL EFFLUENTS) REGULATIONS 1979 [REGULATIONS 8(1), 8(2), 8(3)] PARAMETER LIMITS OF EFFLUENTS OF STANDARDS A AND B ____________________________________________________________________ Parameter Unit Standard A B ______________________________________________________________ (1) (2) (3) (4) (i) Temperature 40 40 (ii) pH value 60-9.0 5.5-9.0 (iii) BOO at 20’C mg/l 20 50 (iv) COD mg/l 50 100 (v) Suspended Solids mg/l 50 100 (vi) Mercury mg/l 0.005 0.05 (vii) Cadmium mg/l 0.01 0.02 (viii) Chromium, Hexavalent mg/l 0.05 0.05 (ix) Arsenic mg/l 0.05 0.10 (x) Cyanide mg/l 0.05 0.10 (xi) Lead mg/l 0.10 0.5 (xii) Chromium, Trivalent mg/l 0.20 1 .0 (xiii) Copper mg/l 0.20 1.0 (xiv) Manganese mg/l 0.20 1.0 (xv) Nickel mg/l 0.20 1.0 (xvi) Tin mg/l 0.20 1.0 (xvii) Zinc mg/l 1 .0 1 .0 (xviii) Boron mg/l 1 .0 4.0 (xix) Iron (Fe) mg/l 1.0 5.0 (xx) Phenol mg/l 0.00 1.0 (xxi) Free Chlorine mg/l 1.0 2.0 (xxii) Suiphide mg/l 0.50 0.50 (xxiii) Oil and Grease mg/l Not Detected 10.0 _________________________________________________________________________ 86 APPENDIX B Laboratory Analysis Table B1: Pre-treated Leachate (Landfill) and influent for Cell A and B Parameter Pre-treated Leachate (Landfill) Influent 50% leachate concentration (Cell A) Influent 33% leachate concentration (Cell B) 6.00 10.20 4.00 4.0 4.0 2.5 69.68 70.55 52.70 2.00 0.42 66.95 55.00 4.25 1.15 0.19 27.98 15.30 3.31 1.10 0.21 446.00 286.00 266 0.43 0.22 0.07 Physical Turbidity TSS Nutrients NH3-N NO3-N P Mn Fe Organic Matters COD Heavy Metals Zn All units in mg/l except turbidity in FAU (Formazin Attenuation Units) is equivalent to NTU 87 APPENDIX B Laboratory Analysis Table B1: Influent and effluent quality at HRT 3 day for Cell A HRT = 3 day Dilution = 50% leachate, 50% water Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (% removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 3 66.95 53.99 19.36 55.00 35.76 34.98 4.25 2.63 38.24 286 256 10.49 1.15 0.15 86.70 0.32 0.16 28.13 0.29 0.08 55.08 4.00 2.00 50 6 66.84 35.58 46.77 54.94 15.40 71.97 4.05 1.90 53.09 292 216 26.03 1.28 0.52 54.78 0.28 0.01 97.77 0.19 0.07 62.03 4.00 2.00 50 9 67.95 20.85 69.32 55.48 16.09 70.99 3.27 1.83 44.19 288 154 46.60 2.15 0.20 82.61 0.21 0.02 92.86 0.29 0.04 76.47 4.00 1.00 75 FAU (Formazin Attenuation Units) is equivalent to NTU 12 66.95 19.45 70.96 54.62 12.97 76.25 3.19 1.55 51.41 276 119 56.88 2.16 0.20 82.61 0.22 0.02 89.29 0.16 0.07 60.96 4.00 1.00 75 15 66.35 12.85 80.63 54.53 9.34 82.88 4.38 1.09 75.11 279 93 66.67 1.15 0.15 86.96 0.32 0.04 84.38 0.20 0.05 74.87 4.00 1.00 75 88 APPENDIX B Laboratory Analysis Table B2: Influent and effluent quality at HRT 6 day for Cell A HRT = 6 day Dilution = 50% leachate, 50% water Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (% removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 6 66.94 25.58 61.79 55.00 15.40 72.00 4.98 0.90 81.94 286 216 24.48 1.15 0.52 54.78 0.22 0.01 97.77 0.19 0.07 62.03 4.00 1.87 50 12 67.30 17.45 74.08 56.00 12.97 76.84 4.85 1.05 78.36 297 105 64.65 2.15 0.20 82.61 1.22 0.02 89.29 0.29 0.07 60.96 4.00 1.00 75 18 67.94 15.78 76.78 55.83 11.88 78.72 4.72 1.22 74.15 296 98 66.89 2.33 0.10 91.30 0.42 0.03 87.28 0.28 0.00 97.86 4.00 0.00 100 FAU (Formazin Attenuation Units) is equivalent to NTU 24 66.71 9.90 85.16 56.73 13.23 76.68 4.82 0.55 88.59 285 64 77.54 1.85 0.13 89.13 0.72 0.04 84.02 0.18 0.03 82.03 4.00 0.00 100 30 66.95 4.91 92.67 55.00 8.51 84.53 4.95 0.64 87.07 289 25 91.35 2.83 0.12 89.57 0.22 0.01 94.96 0.18 0.01 94.44 4.00 0.00 100 89 APPENDIX B Laboratory Analysis Table B3: Influent and effluent quality at HRT 9 day for Cell A HRT = 9 day Dilution = 50% leachate, 50% water Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (% removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 9 66.95 20.85 68.86 55.00 16.09 70.74 4.25 1.83 57.06 286 154 46.22 1.15 0.20 82.61 0.22 0.02 92.86 0.19 0.04 76.47 4.00 1.00 75 18 67.95 15.78 76.79 56.89 18.88 66.81 4.38 1.22 72.15 227 135 40.53 1.25 0.10 92.00 0.22 0.03 87.28 0.29 0.00 98.61 4.00 0.00 100 27 65.97 8.87 86.55 56.37 10.40 81.54 4.67 1.89 59.53 278 75 73.02 1.38 0.12 91.23 0.24 0.02 90.46 0.23 0.02 90.80 4.00 0.00 100 FAU (Formazin Attenuation Units) is equivalent to NTU 36 66.73 17.66 73.53 55.92 11.65 79.16 3.21 1.57 51.09 255 65 74.51 1.15 0.15 86.96 0.21 0.03 84.63 0.18 0.05 72.30 4.00 0.00 100 45 66.15 16.034 75.76 55.173 16.356 70.36 3.69 0.345 90.65 248 55 77.82 1.15 0.12 89.57 0.24 0.03 86.29 0.17 0.05 69.64 4.00 0.00 100 90 APPENDIX B Laboratory Analysis Table B4: Influent and effluent quality at HRT 3 day for Cell B HRT = 3 day Dilution = 33% leachate, 67% water Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (%removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 3 27.98 4.86 82.63 15.30 13.50 11.76 3.31 1.84 44.41 266 203 23.68 1.10 0.40 63.64 0.07 0.05 35.62 0.21 0.14 34.15 4.00 2.00 50 6 27.96 7.20 74.24 15.28 11.20 26.70 3.29 1.25 62.13 258 144 44.19 1.08 0.40 62.96 0.07 0.06 17.81 0.21 0.15 29.27 4.00 2.00 50 9 27.88 8.00 71.30 15.20 9.20 39.47 3.21 0.74 77.10 263 127 51.71 1.00 0.20 80.00 0.07 0.02 70.59 0.21 0.05 76.10 4.00 1.00 75 FAU (Formazin Attenuation Units) is equivalent to NTU 12 27.89 5.08 81.80 15.19 6.20 59.18 3.20 0.65 79.69 268 98 63.43 1.10 0.20 81.82 0.07 0.05 25.76 0.21 0.02 92.20 4.00 0.00 100 15 27.83 4.70 83.11 15.15 4.10 72.94 3.16 0.38 88.07 265 60 77.36 1.10 0.10 90.91 0.06 0.05 19.13 0.21 0.02 91.71 4.00 0.00 100 91 APPENDIX B Laboratory Analysis Table B5: Influent and effluent quality at HRT 6 day for Cell B HRT = 6 day Dilution = 33% leachate, 67% water Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (%removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 6 28.98 7.20 75.15 15.30 8.20 46.41 3.31 0.95 71.42 266 144 45.86 1.10 0.40 63.64 0.17 0.06 65.32 0.41 0.15 64.20 4.00 2.00 50 12 27.84 5.08 81.77 15.10 6.20 58.94 3.11 0.65 79.10 293 98 66.55 1.10 0.20 81.82 0.17 0.05 71.68 0.32 0.13 59.46 4.00 0.50 87.5 18 30.78 8.08 73.76 14.37 1.70 88.17 2.61 0.72 72.34 257 62.00 75.88 0.95 0.20 78.95 0.07 0.02 67.12 0.51 0.11 78.02 4.00 0.00 100 FAU (Formazin Attenuation Units) is equivalent to NTU 24 28.93 6.30 78.22 14.81 2.40 83.79 3.44 0.62 82.10 268 96.00 64.18 1.06 0.20 81.13 0.14 0.03 76.22 0.28 0.07 75.27 4.00 0.00 100 30 31.58 6.61 79.07 15.92 0.35 97.81 2.92 0.07 97.67 296 55.00 81.42 1.18 0.14 88.14 0.09 0.01 90.32 0.23 0.04 83.04 4.00 0.00 100 92 APPENDIX B Laboratory Analysis Table B6: Influent and effluent quality at HRT 9 day for Cell B HRT = 9 day Dilution = 33% leachate, 67% water Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (%removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 9 30.98 8.00 74.17 20.30 9.20 54.68 3.31 0.74 77.79 289 127 56.06 1.12 0.20 82.14 0.07 0.02 72.60 0.21 0.05 76.10 4.00 1.00 75 18 29.98 6.08 79.73 19.30 13.70 29.02 3.31 1.22 63.08 272 62.00 77.21 1.10 0.20 81.82 0.05 0.02 54.72 0.24 0.05 78.30 4.00 0.00 100 27 29.98 5.94 80.18 16.73 13.96 16.56 4.72 1.18 75.00 278 187 32.73 1.24 0.36 70.97 0.07 0.03 53.42 0.24 0.05 78.30 4.00 0.00 100 FAU (Formazin Attenuation Units) is equivalent to NTU 36 32.98 6.943 78.94 16.39 8.18 50.09 4.13 0.982 76.22 291 105 63.92 1.12 0.37 66.96 0.06 0.02 62.50 0.24 0.05 78.30 4.00 0.00 100 45 27.98 7.05 74.80 15.30 6.90 54.89 3.31 1.46 55.95 266 95.00 64.29 1.10 0.20 81.82 0.07 0.04 42.47 0.31 0.06 79.34 4.00 0.00 100 93 APPENDIX B Laboratory Analysis Table B7: Influent and effluent quality at HRT 3 day for control unit HRT = 3 day Dilution = 100% leachate Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (%removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 3 69.68 60.34 13.40 70.55 68.92 2.30 52.70 47.92 9.07 446.00 105 76.46 2.00 1.53 23.50 0.43 0.07 84.88 0.42 0.37 11.90 6.00 4.80 20 6 70.48 55.21 21.66 69.45 65.92 5.08 51.62 45.63 11.60 450.00 85 81.04 2.00 1.23 38.50 0.43 0.08 82.56 0.42 0.29 30.95 6.00 3.90 35 9 68.38 58.94 13.80 69.52 58.62 15.67 53.84 45.77 14.99 435.00 91 79.08 2.00 1.38 31.00 0.43 0.06 87.21 0.42 0.32 22.86 6.00 0.08 98.67 FAU (Formazin Attenuation Units) is equivalent to NTU 12 68.62 28.34 58.70 70.54 53.37 24.34 53.94 41.80 22.50 428.50 86 80.02 2.00 1.55 22.50 0.43 0.04 91.40 0.42 0.18 57.14 6.00 0.08 98.67 15 69.67 39.14 43.82 70.55 50.92 27.82 53.80 41.33 23.18 403.00 40 89.98 2.00 1.03 48.50 0.43 0.08 80.93 0.42 0.10 76.19 6.00 0.08 98.67 94 APPENDIX B Laboratory Analysis Table B8: Influent and effluent quality at HRT 6 day for control unit HRT = 6 day Dilution = 100% leachate Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (%removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 6 70.48 55.21 21.66 79.45 65.92 17.02 51.62 45.63 11.60 450.00 185 58.82 2.00 1.23 38.50 0.43 0.08 82.56 0.48 0.28 41.67 6.00 4.00 33.33 12 69.48 60.73 12.59 75.45 55.32 26.68 49.22 15.83 67.84 465.89 155 66.66 2.33 0.76 67.38 0.33 0.05 84.85 0.32 0.17 46.88 6.50 3.90 40.00 18 69.43 58.73 15.41 78.45 55.03 29.85 49.62 10.76 78.32 460.31 95 79.29 2.26 0.83 63.27 0.37 0.08 77.57 0.33 0.20 39.39 5.50 1.90 65.45 FAU (Formazin Attenuation Units) is equivalent to NTU 24 69.78 54.12 22.43 78.33 30.92 60.52 48.24 5.93 87.71 463.55 64 86.23 2.06 0.50 75.73 0.35 0.06 84.29 0.27 0.06 79.26 5.00 1.00 80.00 30 69.18 50.94 26.36 78.24 25.64 67.23 48.43 7.73 84.04 461.53 30 93.50 2.00 0.48 76.00 0.39 0.08 79.33 0.31 0.05 83.23 5.00 0.05 99.00 95 APPENDIX B Laboratory Analysis Table B9: Influent and effluent quality at HRT 9 day for control unit HRT = 9 day Dilution = 100% leachate Soil : sand = 1: 1 Parameter NH3-N (inf), mg/l NH3-N (eff), mg/l NH3-N (%removal) NO3-N (inf), mg/l NO3-N (eff), mg/l NO3-N (%removal) PO43- (inf), mg/l PO43- (eff), mg/l PO43- (%removal) COD (inf), mg/l COD (eff), mg/l COD (%removal) Mn (inf), mg/l Mn (eff), mg/l Mn (%removal) Zn (inf), mg/l Zn (eff), mg/l Zn (%removal) Fe (inf), mg/l Fe (eff), mg/l Fe (%removal) Turbidity (inf), FAU Turbidity (eff), FAU Turbidity (%removal) 9 71.38 58.94 17.42 69.52 60.93 12.35 55.33 40.62 26.59 459 91 80.17 2.00 1.57 21.50 0.43 0.06 87.21 0.42 0.32 22.86 6.00 0.10 98.33 18 70.68 48.92 30.78 68.57 60.41 11.90 54.88 30.13 45.10 447 174.00 61.07 2.59 0.64 75.29 0.23 0.06 76.09 0.42 0.22 46.67 6.10 0.06 99.02 27 70.50 47.52 32.59 68.33 55.82 18.31 54.27 19.53 64.01 443 150 66.14 2.19 0.13 94.06 0.15 0.06 63.33 0.42 0.22 46.67 6.18 0.06 99.03 FAU (Formazin Attenuation Units) is equivalent to NTU 36 69.98 27.49 60.72 67.93 50.77 25.26 54.75 15.92 70.92 444 85 80.86 2.20 0.17 92.27 0.10 0.06 45.00 0.42 0.12 70.48 7.40 0.05 99.38 45 68.38 20.61 69.86 67.14 50.14 25.32 55.25 12.32 77.70 400 50.40 87.40 2.20 0.10 95.45 0.10 0.06 45.00 0.42 0.12 70.48 7.10 0.05 99.35 96 APPENDIX C Analysis of Variance Table C1: Result of ANOVA for TSSat HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 80.000 85.000 85.000 6 80.000 90.000 90.000 9 80.000 90.000 90.000 12 80.000 90.000 90.000 15 99.930 90.000 90.000 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count 5 5 5 Sum 419.93 445 445 Average Variance 83.986 79.44098 89 5 89 5 3 3 3 3 3 250 260 260 260 279.93 83.33333 86.66667 86.66667 86.66667 93.31 ANOVA Source of Variation Rows Columns Error SS 83.80065 159.1613 198.6026 Total 441.5646 df 8.333333 33.33333 33.33333 33.33333 32.8683 MS F P-value F crit 2 41.90033 1.687806 0.244603 4.45897 4 39.79033 1.602812 0.26395 3.837853 8 24.82533 14 97 APPENDIX C Analysis of Variance Table C2: Result of ANOVA for Turbidity at HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 20.00 50.00 50.00 6 35.00 50.00 50.00 9 98.67 75.00 75.00 12 98.67 75.00 100.00 98.67 75.00 100.00 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Count 5 5 5 Column 1 Column 2 Column 3 Column 4 Column 5 ANOVA Source of Variation Sum 351 325 375 Average 70.2 1547.533 65 187.5 75 625 3 120 40 300 3 135 45 75 3 248.6667 82.88889 186.7037 3 273.6667 91.22222 197.8148 3 273.6667 91.22222 197.8148 SS Rows Columns Error 250.1333 7775.6 1664.533 Total 9690.267 df MS F P-value F crit 2 125.0667 0.601089 0.571212 4.45897 4 1943.9 9.342679 0.004151 3.837853 8 208.0667 14 98 APPENDIX C Analysis of Variance Table C3: Result of ANOVA for NH3-N at HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 13.398 19.356 82.627 6 21.660 46.767 74.244 9 13.799 69.316 71.300 12 58.697 70.956 81.800 15 43.821 80.633 83.109 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Count Column 1 Column 2 Column 3 Column 4 Column 5 ANOVA Source of Variation Sum Average Variance 5 151.3749 30.27499 405.4545 5 287.0281 57.40561 606.4759 5 393.0811 78.61622 29.76093 3 3 3 3 3 SS Rows Columns Error 5871.392 2344.554 1822.211 Total 10038.16 115.3815 142.6717 154.415 211.4533 207.5626 38.4605 47.55723 51.47167 70.48442 69.18753 1471.908 691.7415 1065.413 133.6059 484.1329 df MS F P-value F crit 2 2935.696 12.8885 0.003147 4.45897 4 586.1385 2.573306 0.118899 3.837853 8 227.7764 14 99 APPENDIX C Analysis of Variance Table C4: Result of ANOVA for NO3-N at HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 2.303 34.978 11.765 6 5.076 71.969 26.702 9 15.673 70.993 39.474 12 24.341 76.254 59.184 15 27.824 82.881 72.937 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 75.21737 15.04347 127.9607 5 337.0759 67.41517 350.7549 5 210.0609 42.01219 601.7478 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 6859.03 3623.013 698.8411 Total 11180.88 49.04638 103.747 126.1397 159.7786 183.6425 df 16.34879 282.6692 34.58232 1165.263 42.04657 770.048 53.25953 700.0698 61.21417 860.885 MS F P-value F crit 2 3429.515 39.25945 7.31E-05 4.45897 4 905.7532 10.36863 0.002976 3.837853 8 87.35514 14 100 APPENDIX C Analysis of Variance Table C5: Result of ANOVA for PO43- at HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 9.070 38.235 44.411 6 11.604 53.086 62.128 9 14.990 44.190 77.103 12 22.503 51.411 79.688 15 23.178 75.114 88.070 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 81.34534 16.26907 40.45527 5 262.0361 52.40723 196.358 5 351.3985 70.27969 296.7986 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 7570.899 1615.961 518.4869 Total 9705.346 91.71638 126.8181 136.2823 153.6009 186.3622 df 30.57213 42.2727 45.42743 51.20031 62.12074 356.2838 725.8617 965.653 817.5562 1179.338 MS F P-value F crit 2 3785.449 58.40764 1.69E-05 4.45897 4 403.9902 6.233372 0.014026 3.837853 8 64.81086 14 101 APPENDIX C Analysis of Variance Table C6: Result of ANOVA for COD at HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 76.457 10.490 23.684 6 81.040 26.027 44.186 9 79.080 46.597 51.711 12 80.016 56.884 63.433 15 89.975 66.667 77.358 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 406.5694 81.31388 26.33761 5 206.6649 41.33297 524.2311 5 260.3726 52.07452 409.1651 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 4281.323 2945.127 893.8077 Total 8120.258 110.6311 151.2534 177.3887 200.3332 234.0003 df 36.87704 50.41781 59.12957 66.77774 78.00011 1218.479 785.7228 305.0663 142.1669 136.1305 MS F P-value F crit 2 2140.661 19.15993 0.00089 4.45897 4 736.2819 6.59007 0.011956 3.837853 8 111.726 14 102 APPENDIX C Analysis of Variance Table C7: Result of ANOVA for Mn at HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 23.500 86.696 63.636 6 38.500 54.783 62.963 9 31.000 82.609 80.000 12 22.500 82.609 81.818 15 48.500 86.957 90.909 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 164 32.8 118.7 5 393.6522 78.73043 183.6733 5 379.3266 75.86532 148.7163 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 6620.726 903.9264 900.4324 Total 8425.085 173.832 156.2456 193.6087 186.9269 226.3656 df 57.94401 52.08186 64.53623 62.30896 75.4552 1022.725 155.0797 845.2105 1188.721 548.843 MS F P-value F crit 2 3310.363 29.41132 0.000205 4.45897 4 225.9816 2.007761 0.186292 3.837853 8 112.554 14 103 APPENDIX C Analysis of Variance Table C8: Result of ANOVA for Fe at HRT 3 days Time (day) Control (%) Cell A (%) Cell B (%) 3 11.905 55.08 34.146 6 30.952 62.03 29.268 9 22.857 76.47 76.098 12 57.143 60.96 92.195 15 76.190 74.87 91.707 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Count Column 1 Column 2 Column 3 Column 4 Column 5 ANOVA Source of Variation Sum Average Variance 5 199.0476 39.80952 692.1315 5 329.4118 65.88235 87.13432 5 323.4146 64.68293 951.0529 3 3 3 3 3 SS Rows Columns Error 2166.529 4656.725 2264.55 Total 9087.804 101.1313 122.2528 175.4253 210.3005 242.7641 33.71044 40.75092 58.4751 70.10018 80.92137 466.1724 340.3751 951.5138 369.7873 87.69088 df MS F P-value F crit 2 1083.264 3.826859 0.068217 4.45897 4 1164.181 4.112715 0.042302 3.837853 8 283.0688 14 104 APPENDIX C Analysis of Variance Table C9: Result of ANOVA for TSS at HRT 6 days Time (day) Control (%) Cell A (%) Cell B (%) 6 80.000 85.000 85.000 12 85.000 90.000 90.000 18 90.000 90.000 90.000 24 100.000 90.000 90.000 5 5 5 Sum 455 445 445 Average 91 89 89 Variance 80 5 5 3 3 3 3 3 250 265 270 280 280 83.33333 88.33333 90 93.33333 93.33333 8.333333 8.333333 0 33.33333 33.33333 30 100.000 90.000 90.000 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count ANOVA Source of Variation Rows Columns Error SS 13.33333 206.6667 153.3333 Total 373.3333 df MS F P-value F crit 2 6.666667 0.347826 0.716393 4.45897 4 51.66667 2.695652 0.108483 3.837853 8 19.16667 14 105 APPENDIX C Analysis of Variance Table C10: Result of ANOVA for Turbidity at HRT 6 days Time (day) Control (%) Cell A Cell B 6 33.33 50.00 50.00 12 40.00 75.00 87.50 18 65.45 100.00 100.00 24 80.00 100.00 100.00 30 99.00 100.00 100.00 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 317.7879 63.55758 749.6454 5 425 85 500 5 437.5 87.5 468.75 3 133.3333 44.44444 92.59259 3 202.5 67.5 606.25 3 265.4545 88.48485 397.7961 3 280 93.33333 133.3333 3 299 99.66667 0.333333 ANOVA Source of Variation Rows Columns Error SS 1732.112 6145.083 728.4987 Total 8605.694 df MS F P-value F crit 2 866.056 9.510584 0.007683 4.45897 4 1536.271 16.87054 0.000577 3.837853 8 91.06234 14 106 APPENDIX C Analysis of Variance Table C11: Result of ANOVA for NH3-N at HRT 6 days Time (day) Control (%) Cell A Cell B 6 21.660 61.787 75.151 12 12.587 74.079 81.768 18 15.405 76.781 73.762 24 22.432 85.160 78.220 30 26.356 92.672 79.066 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 98.44098 19.6882 31.16248 5 390.4782 78.09564 136.5552 5 387.9658 77.59316 10.15704 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 11274.45 347.867 363.6318 Total 11985.94 158.5978 168.4336 165.9481 185.8113 198.0942 df 52.86594 56.14452 55.31604 61.93709 66.0314 775.0018 1437.706 1196.94 1182.525 1226.866 MS F P-value F crit 2 5637.223 124.0205 9.53E-07 4.45897 4 86.96676 1.913293 0.201655 3.837853 8 45.45397 14 107 APPENDIX C Analysis of Variance Table C12: Result of ANOVA for NO3-N at HRT 6 days Time (day) Control (%) Cell A (%) Cell B (%) 6 17.024 72.000 46.405 12 26.675 76.839 58.940 18 29.849 78.716 88.170 24 60.523 76.681 83.795 30 67.227 84.535 97.808 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 201.2987 40.25974 492.6644 5 388.7707 77.75415 20.49963 5 375.1184 75.02367 461.6435 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 4369.694 2748.458 1150.772 Total 8268.924 135.4296 162.4547 196.7349 220.999 249.5696 df 45.1432 54.15158 65.57829 73.66632 83.18988 756.7749 646.3119 979.7828 142.2032 235.1601 MS F P-value F crit 2 2184.847 15.18874 0.001888 4.45897 4 687.1145 4.776721 0.028977 3.837853 8 143.8465 14 108 APPENDIX C Analysis of Variance Table C13: Result of ANOVA for PO43- at HRT 6 days Time (day) Control (%) Cell A (%) Cell B (%) 6 11.604 81.942 71.420 12 67.838 78.359 79.100 18 78.315 74.153 72.337 24 87.706 88.589 82.099 30 84.039 87.071 97.671 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 329.503 65.9006 977.6224 5 410.1141 82.02282 35.9917 5 402.6269 80.52537 112.1111 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 793.4205 2192.23 2310.671 Total 5296.322 164.9662 225.2974 224.8049 258.3941 268.7814 df 54.98873 75.09913 74.93497 86.13136 89.59381 1439.354 39.67699 9.393355 12.39092 51.23071 MS F P-value F crit 2 396.7103 1.37349 0.307054 4.45897 4 548.0576 1.897484 0.204372 3.837853 8 288.8338 14 109 APPENDIX C Analysis of Variance Table C14: Result of ANOVA for COD at HRT 6 days Time (day) Control (%) Cell A (%) Cell B (%) 6 58.818 24.476 45.865 12 66.662 64.646 66.553 18 79.292 66.892 75.875 24 86.232 77.536 64.179 30 93.496 91.349 81.419 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 384.4995 76.89991 200.0045 5 324.8993 64.97987 624.3453 5 333.8911 66.77821 185.3234 3 129.158 43.05265 3 197.861 65.95367 3 222.0596 74.01986 3 227.9474 75.98247 3 266.2639 88.75465 ANOVA Source of Variation Rows Columns Error SS 412.9501 3435.653 603.0391 Total 4451.643 df 300.7781 1.284556 41.02451 123.3963 41.5111 MS F P-value F crit 2 206.475 2.739127 0.124115 4.45897 4 858.9133 11.39446 0.002188 3.837853 8 75.37989 14 110 APPENDIX C Analysis of Variance Table C15: Result of ANOVA for Mn at HRT 6 days Time (day) Control (%) Cell A (%) Cell B (%) 6 38.500 54.783 63.636 12 67.382 82.609 81.818 18 63.274 91.304 78.947 24 75.728 89.130 81.132 30 76.000 89.565 88.136 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 320.8845 64.17689 235.9019 5 407.3913 81.47826 233.6106 5 393.6696 78.73392 82.90926 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 864.6261 2005.52 204.1673 Total 3074.313 156.919 231.8089 233.5261 245.9907 253.7008 df 52.30632 77.26962 77.84202 81.99689 84.56694 162.5582 73.48034 197.3367 45.4662 55.55526 MS F P-value F crit 2 432.3131 16.93956 0.001332 4.45897 4 501.3799 19.64584 0.000337 3.837853 8 25.52091 14 111 APPENDIX C Analysis of Variance Table C16: Result of ANOVA for Fe at HRT 6 days Time (day) Control (%) Cell A (%) Cell B (%) 6 41.667 62.03 64.198 12 46.875 60.96 59.464 18 39.394 97.86 78.020 24 79.259 82.03 75.273 30 83.226 94.44 83.043 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 290.4207 58.08413 456.2477 5 397.3262 79.46524 303.8634 5 359.9972 71.99944 96.7363 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 1177.543 2299.88 1127.509 Total 4604.933 167.8963 167.3012 215.2747 236.5641 260.7078 df 55.96543 55.76708 71.75823 78.85469 86.9026 154.5132 59.86349 884.0036 11.54499 42.60073 MS F P-value F crit 2 588.7714 4.177501 0.057248 4.45897 4 574.9701 4.079577 0.043148 3.837853 8 140.9387 14 112 APPENDIX C Analysis of Variance Table C17: Result of ANOVA for TSS at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 95.00 95.00 95.00 18 95.00 90.00 90.00 27 100.00 95.00 95.00 36 100.00 100.00 100.00 Average 98 96 96 Variance 7.5 17.5 17.5 45 100.00 100.00 100.00 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count 5 5 5 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 13.33333 150 20 Total 183.3333 Sum 490 480 480 285 95 0 275 91.66667 8.333333 290 96.66667 8.333333 300 100 0 300 100 0 df MS F P-value F crit 2 6.666667 2.666667 0.1296 4.45897 4 37.5 15 0.000868 3.837853 8 2.5 14 113 APPENDIX C Analysis of Variance Table C18: Result of ANOVA for Turbidity at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 98.33 75.00 75.00 18 99.02 100.00 100.00 27 99.03 100.00 100.00 36 99.38 100.00 100.00 45 99.35 100.00 100.00 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 495.1093 99.02187 0.177581 5 475 95 125 5 475 95 125 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 53.9181 689.8546 310.8557 Total 1054.628 248.3333 299.0164 299.0291 299.3784 299.3521 df 82.77778 99.67213 99.67638 99.79279 99.78404 181.4815 0.322494 0.314199 0.128804 0.139919 MS F P-value F crit 2 26.95905 0.693802 0.527401 4.45897 4 172.4637 4.438424 0.034986 3.837853 8 38.85696 14 114 APPENDIX C Analysis of Variance Table C19: Result of ANOVA for NH3-N at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 17.422 68.857 74.173 18 30.782 76.785 79.733 27 32.593 86.554 80.183 36 60.717 73.529 78.945 45 69.857 75.761 74.799 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 211.3714 42.27429 486.104 5 381.4872 76.29745 42.18772 5 387.8329 77.56658 8.154833 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 4007.886 747.363 1398.423 Total 6153.672 160.4521 187.2999 199.3309 213.1912 220.4175 df 53.48405 982.4131 62.43331 753.539 66.44362 869.552 71.06372 87.61744 73.47249 10.03312 MS F P-value F crit 2 2003.943 11.46402 0.004477 4.45897 4 186.8408 1.068865 0.431701 3.837853 8 174.8029 14 115 APPENDIX C Analysis of Variance Table C20: Result of ANOVA for NO3-N at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 12.350 70.740 54.680 18 11.900 66.808 29.016 27 18.308 81.543 16.557 36 25.261 79.161 50.092 45 25.320 70.355 54.889 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 93.13984 18.62797 43.39165 5 368.6076 73.72152 39.6984 5 205.2328 41.04657 300.9416 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 7675.91 569.1628 966.9639 Total 9212.037 137.7697 107.7237 116.4087 154.5141 150.5642 df 45.92322 35.90789 38.80289 51.50471 50.18806 909.8607 789.3402 1370.828 727.8004 523.6075 MS F P-value F crit 2 3837.955 31.75263 0.000157 4.45897 4 142.2907 1.177216 0.389715 3.837853 8 120.8705 14 116 APPENDIX C Analysis of Variance Table C21: Result of ANOVA for PO43- at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 26.586 57.059 77.795 18 45.098 72.146 63.082 27 64.013 59.529 75.000 36 70.922 51.090 76.223 45 77.701 90.650 55.952 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 284.3213 56.86427 434.5339 5 330.4746 66.09492 247.3725 5 348.0506 69.61011 92.23459 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 433.3634 731.2691 2365.295 Total 3529.927 161.4393 180.3261 198.5422 198.2355 224.3034 df 53.81311 663.4818 60.1087 189.5233 66.18072 63.36208 66.07849 175.507 74.76781 307.455 MS F P-value F crit 2 216.6817 0.73287 0.510201 4.45897 4 182.8173 0.618332 0.661997 3.837853 8 295.6619 14 117 APPENDIX C Analysis of Variance Table C22: Result of ANOVA for COD at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 80.174 46.224 56.055 18 61.074 40.529 77.206 27 66.140 73.022 32.734 36 80.856 74.510 63.918 45 87.400 77.823 64.286 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 375.6439 75.12879 121.795 5 312.1064 62.42128 309.3365 5 294.1983 58.83966 270.5075 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 732.7407 908.0833 1898.473 Total 3539.297 182.4534 178.8083 171.8954 219.2832 229.5083 df 60.81781 59.60278 57.29845 73.0944 76.50276 305.1701 337.9281 464.4053 73.22929 134.874 MS F P-value F crit 2 366.3703 1.543853 0.271015 4.45897 4 227.0208 0.956646 0.480352 3.837853 8 237.3091 14 118 APPENDIX C Analysis of Variance Table C23: Result of ANOVA for Mn at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 21.500 76.098 82.143 18 75.290 78.298 81.818 27 94.064 78.298 70.968 36 92.273 78.298 66.964 45 95.455 79.344 81.818 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 ANOVA Source of Variation Rows Columns Error Total Count Sum Average Variance 5 378.5808 75.71615 984.9846 5 390.3354 78.06709 1.417499 5 383.7112 76.74225 52.41256 3 3 3 3 3 SS 13.89159 1165.594 2989.665 4169.15 179.7404 59.91347 1115.833 235.4056 78.46854 10.67752 243.3295 81.10985 139.2888 237.5349 79.1783 160.7107 256.617 85.539 75.26865 df MS F P-value F crit 2 6.945794 0.018586 0.981628 4.45897 4 291.3984 0.779749 0.568659 3.837853 8 373.7081 14 119 APPENDIX C Analysis of Variance Table C24: Result of ANOVA for Fe at HRT 9 days Time (day) Control (%) Cell A (%) Cell B (%) 9 22.857 76.47 82.609 18 46.667 98.61 92.000 27 46.667 90.80 91.232 36 70.476 72.30 86.957 45 70.476 69.64 89.565 Anova: Two-Factor Without Replication SUMMARY Row 1 Row 2 Row 3 Column 1 Column 2 Column 3 Column 4 Column 5 Count Sum Average Variance 5 257.1429 51.42857 396.8254 5 407.8127 81.56253 157.4408 5 442.3623 88.47246 14.48347 3 3 3 3 3 ANOVA Source of Variation Rows Columns Error SS 3880.088 666.8394 1608.159 Total 6155.086 181.9364 237.2729 228.6986 229.7278 229.6821 df 60.64548 79.09098 76.23285 76.57593 76.56071 1080.388 799.4128 655.666 81.64458 127.0124 MS F P-value F crit 2 1940.044 9.651005 0.007372 4.45897 4 166.7099 0.82932 0.542431 3.837853 8 201.0199 14 APPENDIX D Figures Of The Whole Experiment Plate D1: Constructed wetlands made of concrete, divided by 3 cells, build in front of the environmental laboratory Sand Gravel Medium Gravel Large Gravel Plate D2: Each cell filled with large gravel, medium gravel and sand 120 APPENDIX D Figures Of The Whole Experiment Plate D3: After all the filling complete Plate D4: All three cells wash out with tap water to clean all the debris that trapped in the CWs 121 APPENDIX D Figures Of The Whole Experiment Plate D5: Domestic wastewater taken from oxidation pond in UTM Plate D6: Domestic wastewater then fed into the CWs to acclimatize the plant as long as 1 week 122 APPENDIX D 123 Figures Of The Whole Experiment (a) (c) (b) (d) Plate D7: (a) Secondary Treatment of Landfill Leachate (b) About 23 bottles samples is required for this study (c) Method of collected landfill leachate (d) Method of collected landfill leachate APPENDIX D Figures Of The Whole Experiment Plate D8: Dilution of landfill leachate before poured into the CWs Plate D9: Leave the CWs with leachate for 3-5 day for plant to adopt a new environment 124 125 APPENDIX D Figures Of The Whole Experiment Plate D10: During experiment From landfill Before treatment After treatment Plate D11: Before and after treatment by using a FWSCW