LEACHATE TREATMENT USING SUBSURFACE FLOW AND FREE WATER SURFACE CONSTRUCTED WETLAND SYSTEMS AIN NIHLA BINTI KAMARUDZAMAN A project report submitted in partial fulfilment of the requirements for the award of the degree of Master of Engineering (Civil – Wastewater) Faculty of Civil Engineering Universiti Teknologi Malaysia NOVEMBER 2006 iii This work is dedicated to my beloved family members, especially to abah (Kamarudzaman Hj. Abd. Rahim), mak ( Saodah Hj. Abd. Karim), my bothers and sisters (Mohd. Suffian, Ainul Zakiah, Ahmad Zaki, Kamaliah and Atiqah). Thanks for all your love and support! iv ACKNOWLEDGEMENT In the name of Allah, the Most Gracious, the Most Graceful. With His blessing and permission, finally this Master’s project report has been accomplished successfully in the given time frame. First of all, I would like to extend my gratitude to everyone who has been helping me directly or indirectly from the beginning until the final stage in this project. All the help and cooperation from various parties had been a motivation factor for me to complete this project. I would like to express my utmost gratitude and appreciation to the thesis supervisor Dr. Johan Sohaili for his cooperation, guidance, facilitation and advice for me to finish this project. All staff in the Environmental Engineering Laboratory, Faculty of Civil Engineering UTM, who has been helping me in providing the equipments for data collection in this project, to all of you I extend my gratitude. Thank you for your cooperation and assistance. Not to forget, thank you very much to my fellow friends Siti Kamariah, Shila and Kak Ida who have been helping me during the data collection process and provided support to the completion of the project. Finally, to my parents, my siblings and others that are involves I would like to express my greatest appreciation for the support and encouragement. May all the good deeds that were done will be blessed by Allah. Wassalam. v ABSTRACT The sanitary landfill plays a most important role in the framework of solid waste disposal. Discharge of leachate into the environment constitutes the major environmental concern associated with sanitary landfill and need to prevent. Based on previous study, constructed wetland system has high efficiency in treating landfill leachate with low operating and maintenance cost. A combination system utilizing a subsurface flow (SSF) wetland followed by a free water surface (FWS) wetland was studied to treat landfill leachate. In this study, Limnocharis flava and Eichhornia crassipes were used as aquatic plants in wetland system. SSF and FWS constructed wetland systems were arranged in series and operated for around 3 weeks with hydraulic loading rate (HLR) (0.13 m/cycle/day). Two lab scale systems of constructed wetlands were used in the experiments. Performance of SSF-FWS constructed wetland was evaluated with comparison to a Control system (unplanted). The result demonstrated that a combination system utilizing a SSF-FWS constructed wetland systems have shown higher performance in treating leachate landfill. The result demonstrated that the removal efficiency of pollutants in leachate using Limnocharis flava and Eichhornia crassipes in SSF-FWS constructed wetlands were NH4-N (93.1%), NO3-N (96.4%), PO43- (95.9%), Fe (99.5%) and Mn (97.7%). Removal efficiency of SS and turbidity were achieved 87.3% and 99.6%, respectively. Limnocharis flava had higher capacity to accumulate heavy metals (Fe and Mn) in leachate constituents compared than Eichhornia crassipes. From the study, it shows that Fe and Mn uptake is more significant in roots compare to leaves. This study concludes that SSF-FWS constructed wetlands can increase the performance of nutrient and heavy metal removal and also enhance leachate water quality. vi ABSTRAK Tapak pelupusan sampah memainkan peranan penting dalam rangka kerja pelupusan sisa pepejal. Pelepasan air larut lesap ke alam sekitar menimbulkan kebimbangan yang tinggi terhadap alam sekitar berkaitan dengan tapak pelupusan sampah dan keadaan ini perlu dielakkan. Berdasarkan kajian yang dijalankan sebelum ini, sistem tanah bencah yang dirangka menunjukkan tahap efisyen yang tinggi dalam mengolah air larut lesap dengan kos operasi dan penyelenggaraan yang murah. Gabungan sistem menggunakan tanah bencah buatan aliran subpermukaan (SSF) dan diikuti dengan tanah bencah buatan aliran permukaan bebas (FWS) telah dikaji untuk mengolah air larut lesap. Dalam kajian ini, Limnocharis flava dan Eichhornia crassipes telah digunakan sebagai tumbuhan akuatik dalam sistem tanah bencah. Sistem tanah bencah buatan SSF dan FWS disusun secara bersiri dan beroperasi dalam jangka masa 3 minggu dengan kadar masukan hidraulik (0.13 m/kitaran/hari). Dua sistem tanah bencah buatan berskala makmal telah digunakan di dalam kajian ini. Prestasi sistem tanah bencah buatan SSF-FWS ini telah dinilai dan diperbandingkan dengan sistem kawalan iaitu tanpa tumbuhan. Keputusan yang diperolehi menunjukkan bahawa gabungan sistem tanah bencah buatan SSF dan FWS menunjukkan prestasi yang lebih baik dalam mengolah air larut lesap. Keputusan menunjukkan bahawa kadar penyingkiran bahan pencemar dalam air larut lesap menggunakan Limnocharis flava dan Eichhornia crassipes dalam sistem tanah bencah buatan SSF-FWS adalah NH4-N (93.1%), NO3-N (96.4%), PO43- (95.9%), Fe (99.5%) and Mn (97.7%). Tahap penyingkiran yang efisien bagi SS dan kekeruhan pula dicapai sebanyak 87.3% dan 99.6%. Limnocharis flava mempunyai kapasiti yang lebih tinggi untuk mengumpul logam berat (Fe and Mn) dalam juzuk air larut lesap jika dibandingkan dengan Eichhornia crassipes. Daripada kajian yang dijalankan, ia menunjukkan bahawa pengambilan Fe and Mn adalah lebih ketara di akar berbanding dengan daun. Kajian ini dapat memberi kesimpulan bahawa sistem tanah bencah buatan SSF-FWS boleh meningkatkan prestasi penyingkiran kandungan nutrien and logam berat dan juga meningkatkan kualiti dalam air larut lesap. vii TABLE OF CONTENTS CHAPTER 1 2 TITLE PAGE DECLARATION ii DEDICATION iii ACKNOWLEDGEMENT iv ABSTRACT v ABSTRAK vi TABLE OF CONTENTS vii LIST OF TABLES x LIST OF FIGURES xi LIST OF SYMBOLS AND ABREVIATIONS xv LIST OF APPENDICES xvii INTRODUCTION 1 1.1 Introduction 1 1.2 Problem Statement 3 1.3 Objective of the Study 5 1.4 Scope of the Study 5 1.5 Important of the Study 6 LITERATURE REVIEW 7 2.1 Introduction 7 2.2 An Overview of Leachate 8 2.2.1 Leachate Generation 8 2.2.2 Leachate Characterization 10 viii 2.2.3 2.3 Leachate Composition 13 Treatment of Leachate 16 2.3.1 Biological Treatment of Leachate 16 2.3.2 Physical-Chemical Treatment of Leachate 18 2.4 Problem in Leachate Treatment 27 2.5 Wetland 28 2.6 Constructed Wetland 29 2.7 Types of Constructed Wetland 30 2.7.1 Free Water Surface Wetlands 31 2.7.2 Subsurface Flow Wetlands 34 2.7.3 Combine FWS-SSF Constructed Wetland System in Wastewater Treatment 2.8 Pollutants Removal Process Mechanisms 40 2.9 Wetland Plant 45 2.10 Role of Wetland Vegetation 47 2.11 Application of Constructed Wetlands in 2.12 3 37 Treating Landfill Leachate 49 Conclusion 57 METHODOLOGY 59 3.1 Introduction 59 3.2 Research Design and Operational Framework 59 3.3 Leachate Sample Collection and Preparation 61 3.4 Experiment Set up 61 3.5 Plants 64 3.6 Media 67 3.7 Sampling and Analysis 67 3.8 Analysis Procedure 67 3.8.1 3.9 Analysis of Heavy Metals in Plant Tissues 68 Performance Evaluation 69 ix 4 5 RESULTS AND DISCUSSIONS 70 4.1 Introduction 70 4.2 Basic Characteristics of the Landfill Leachate 71 4.3 Nutrients Removal 71 4.3.1 Ammonia Nitrogen 71 4.3.2 Nitrate Nitrogen 75 4.3.3 Orthophosphate 78 4.4 Suspended Solid Removal 81 4.5 Turbidity 84 4.6 Heavy Metals Removal 87 4.6.1 Ferum 87 4.6.2 Manganese 90 4.7 Heavy Metal in Plant’s Tissues 93 4.8 Comparison with Other Researchers 96 4.9 Conclusion 98 CONCLUSIONS 100 5.1 Conclusion 100 5.2 Recommendations 101 REFERENCE 102 APPENDICES 113 x LIST OF TABLES TABLE NO. TITLE PAGE 2.1 Data on the composition of leachate from landfill 14 2.2 Leachate sampling parameters 15 2.3 Physical, chemical and biological treatment processes applicable to process trains for leachate treatment 2.4 Summary of biological and physical-chemical treatment processes applied to leachate treatment 2.5 24 Advantages and disadvantages of Free Water Surface Flow wetlands 2.6 21 32 Advantages and disadvantages of Subsurface Flow wetlands 35 2.7 Overview of pollutant removal process 41 2.8 Roles of macrophytes in constructed wetlands 48 2.9 Wastewater pollutants removal in constructed wetland 51 2.10 Leachate pollutants removal in constructed wetland 54 3.1 Summary of experimental design 64 3.2 The parameter observed in leachate analysis 68 4.1 Influent characteristics of the Pasir Gudang leachate 71 4.2 Comparison of different models of constructed wetlands for landfill leachate treatment 97 xi LIST OF FIGURES FIGURE NO. TITLE 2.1 How leachate is generated 2.2 Factors influencing gas and leachate composition in PAGE 9 landfills 10 2.3 Wetland design categories 31 2.4 Types of Free Water Surface (FWS) treatment wetlands 2.5 Typical arrangement of horizontal subsurface flow constructed wetland system 2.6 37 Plan view of constructed wetland at Munroe Country wastewater treatment , New York 2.8 36 Typical arrangement of vertical subsurface flow constructed wetland system 2.7 33 38 Layout of the pilot-scale FW-SSF series constructed wetlands system for treating fishpond water. (A) Sampling location for the influent; (B) sampling location for the FWS effluent; (C) sampling location for the SSF effluent 2.9 Schematic diagram of the recirculating aquaculture system 2.10 2.11 39 40 Major pollutants uptake and release pathway in wetland system 41 Nitrogen transformation in wetland system 43 xii 2.12 Summary of the major physical, chemical and biological processes controlling contaminant removal in wetlands 45 2.13 Types of wetland plants 46 3.1 Frameworks and experimental design 60 3.2 Schematic diagram of SSF-FWS constructed wetland used in experiment. (1) Storage tank; (2) Media without plant; (3) water tank without plant; (4) SSF tank with Limnocharis flava (5) FWS tank with Eichhornia crassipes; (6) Settling tank; and (A) Sampling location for the influent; (B) sampling location for the SSF effluent; (C) sampling location for the FWS effluent. 3.3 Arrangement of SSF-FWS constructed wetland systems 3.4 62 63 Two-stage lab-scaled system comprised of a SSF and FWS constructed wetland located outside of the building in an open area 64 3.5 Short description of Limnocharis. flava 65 3.6 Short description of Eichhornia crassipes 66 3.7 Plants digestion for root and leaves 69 4.1 NH4-N concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 4.2 72 NH4-N concentration in profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 4.3 72 Comparison of NH4-N concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland 4.4 73 NO3-N concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 76 xiii 4.5 NO3-N concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 4.6 76 Comparison of NO3-N concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland 4.7 77 PO43- concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 4.8 79 PO43- concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 4.9 79 Comparison of PO43- concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland 4.10 80 SS concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 4.11 82 SS concentration in profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 4.12 82 Comparison of SS concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland system 4.13 83 Turbidity measure in Control and Planted system through SSF constructed wetland within 18 days of treatment 4.14 85 Turbidity measure in Control and Planted system through FWS constructed wetland within 18 days of treatment 4.15 85 Comparison of turbidity value (C/CO) for overall performance in Control and Planted system through SSF-FWS wetland 86 xiv 4.16 Fe concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 4.17 88 Fe concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 4.18 88 Comparison of Fe concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS wetland 4.19 89 Mn concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 4.20 91 Mn concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 4.21 91 Comparison of Mn concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS wetland 4.22 92 Heavy metal (Fe) accumulation by Limnocharis flava and Eichhornia crassipes in SSF-FWS wetland systems 4.23 94 Heavy metal (Mn) accumulation by Limnocharis flava and Eichhornia crassipes in SSF-FWS wetland systems 95 xv LIST OF SYMBOLS AND ABREVIATIONS BOD - Biochemical Oxygen Demand cm/day - Centimeter per day CAP - Consumers Association of Penang Ca2- - Calcium CaCO3 - Calcium carbonate C/CO - Present concentration over initial concentration Cl - Clorine Cl2 - Chlorine gas Cd - Cadmium Cr - Chromium COD - Chemical Oxygen Demand CWs - Constructed wetland Fe - Ferum FWS - Free Water Surface HCO3- - Bicarbonate HF-SSF - Horizontal Subsurface Flow HLR - Hydraulic Loading Rate HRT - Hydraulic Retention Time IUCN - International Union for the Conservation of Nature kg - Kilogram kg/m3 - Kilogram per meter cube m - Meter mm - Millimeter m/day - Meter per day mg/g - Milligram per gram xvi mg/L - Milligram per liter mL/s - Milliliter per second Mg2+ - Magnesium MLVSS - Mix liquor Volatile Suspended Solid Mn - Manganese N2 - Nitrogen gas N2O - Nitrogen Oxides NH4+ - Ammonia NH4-N - Ammonia Nitrogen NO2- - Nitrite - - Nitrate NO2 -N - Nitrite Nitrogen NO3 -N - Nitrate Nitrogen P - Phosphorus PO43- - Orthophosphate SO4- - Sulfate SSF - Subsurface Flow SSF-FWS - Combine Subsurface Flow and Free Water Surface System SS - Suspended Solid TIN - Total Inorganic Carbon TKN - Total Kjeldahl Nitrogen TN - Total Nitrogen TP - Total Phosphorus TOC - Total Organic Carbon TSS - Total Suspended Solid VF - Vertical Flow VF-SSF - Vertical Subsurface Flow VFA - Volatile Fatty Acid VOC - Volatile Organic Carbon RBC - Rotating Biological Reactor Zn - Zinc µg/g - Microgram per gram % - Percent ˚C - Degrees Celsius NO3 xvii LIST OF APPENDICES APPENDIX TITLE PAGE A Raw Data 113 B Varian Analysis Calculation (ANOVA) 117 C Lab Apparatus and Equipments 124 CHAPTER 1 INTRODUCTION 1.1 Introduction Solid waste disposal creates a problem primarily in highly populated areas. In general, the more concentrated the population, the greater the problem becomes, although some very populated areas have developed creative solutions to minimize the problem. Various estimates have been made of the quantity of solid waste generated and collected per person per day. Malaysia, like most of the developing countries, is facing an increase of the generation of waste and accompanying problems with the disposal of this waste. Municipal, industrial, agricultural, and urban activities produce huge amounts of wastes which require permanent disposal. Overall, the local communities generate 16,000 tonnes of domestic waste per day and the amounts per capita vary from 0.45 to 1.44 kg per day depending on the economic status of the areas concerned. On average, waste generation in Malaysia is about 1 kg per capita per day (Lina, 2004). There are different alternatives to reduce, treat and dispose the solid wastes. In many developing countries including Malaysia, sanitary landfills have been the most popular method of municipal solid waste disposal. There are 230 official dumping sites in Malaysia, the majority of which are crude landfills, with only 10% providing leachate treatment ponds and gas ventilation systems and with most having 2 no control mechanisms and supervision (Zaman, 1992). However, the amount of waste produced rapidly increases; space for permanent disposal becomes crucial. Since the production of solid waste is increasing much more rapidly than it degrades, land space for disposal has become more difficult and expensive to attain. Incineration of solid waste can be used but this is expensive and the emissions are of health concern. This is why landfills remain the major solid waste disposal option for most countries. In conjunction with the increasing number of sanitary landfills, leachate treatment has become a major environmental issue, especially with regulatory agencies and environmentalists. The treatment of landfill leachates is of concern because they have the potential to degrade the environment. Leachates are a potential hazardous waste from landfill sites. Malaysian solid wastes contain very high organic waste and consequently high moisture content and bulk density of above 200 kg/m3. A recent study conducted in Kuala Lumpur has revealed that the amount of organic wastes for residential area range from 62 to 72% (CAP, 2001). Therefore, leachate production may arise because most of solid wastes contain high moisture content and organic matter. Most organic matter contained in the solid wastes is biodegradable and can be broken down into simpler compounds by anaerobic and aerobic microorganisms, leading to the formation of gas and leachate. Leachate is defined as liquid that has percolated through solid waste and has extracted dissolved or suspended materials from it. It arises from the biochemical and physical breakdown of waste (Lu et al., 1985). Landfill leachate characteristics vary depending on the operation type of the landfill and the age of the landfill. Leachate initially is a high-strength wastewater, contains high concentration of organic matter, inorganic matter and heavy metal (Qasim and Chiang, 1994). The main environmental aspects of leachate are the impacts on surface water quality and groundwater quality, because leachate may migrate from the refuse and contaminate the surface waters and groundwater. If not dealt properly its can affecting aquatic ecosystems, human health problems and effect the environment. It is important that leachates are treated and contained to prevent these occurrences. 3 Therefore, the treatment of leachates by natural systems seems to be environmentally sustainable for treatment of many constituents. Constructed wetlands have proven very effective technology for the treatment of variety of wastewaters. Constructed wetlands are increasingly being employed to treat landfill leachate, and the use of natural systems in waste management seems to be gaining in popularity as a result of their sustainability and cost savings. Wetland has been shown to improve leachate quality through processes that include microbial mediated transformations, biotic uptake of organic chemicals and nutrients, precipitation, complexation and adsorption reactions (Kadlec and Knight, 1996; Brix, 1997; Mutamoottil et al., 1999). A thorough understanding of these mechanisms is required before a constructed wetland system can be developed that can provide successful, long-term treatment of landfill leachate on a large scale. The environmental benefit treatment of leachate in a constructed wetland include; decreased energy consumption by using natural processes rather than conventional, electrically driven wastewater-treatment processes; efficiently removed many pollutants from wastewater and also enhance the environment by providing a habitat for vegetation, fish and other wildlife (Jin et al., 2003). Studies of the longterm use of wetlands for leachate treatment have demonstrated significant economic advantages, mainly through lowered construction, transportation and operation costs (Kadley and Knight, 1996). 1.2 Problem Statement Landfill leachate with its variable and complex characteristics poses a well established threat to the environment. Leachate is often quite varies in water quality but generally has very high concentrations of Chemical Oxygen Demand (COD), Biochemical Oxygen Demand (BOD), and ammonia content, with high COD and BOD ratio and the presence of heavy metals ions present unique difficulties treatment of landfill leachate (Aeslina, 2004). Landfill leachates will cause environmental problems if it is not properly handled. Increase in landfill leachate creates challenges for those seeking cost effective treatment methods to process this 4 wastewater. Enhancement of the environmental quality through the minimization of the leachate problem should therefore be the major objective of good landfill management. The need to control and manage landfill leachate has resulted in various treatment alternatives which include both biological and physical-chemical processes (Ho et al., 1974; Lu et al., 1984; Qasim and Chiang, 1994). Usually several physical-chemical wastewater treatment technologies are used to treat the leachate. These physical-chemical approaches to leachate treatment are undesirable since the costs of operation and maintenance are high, and labors and services are required even after landfill site closure. Some of these processes even require extensive pretreatment process (Britz, 1995). However, these types of treatment systems were hardly comply with the Environmental Quality Act, 1974. For a small community with limited funds for expanding or updating wastewater treatment plants, constructed wetlands are an attractive option. Rural municipalities have access to adequate inexpensive land, and wetlands blend into a natural landscape setting. Once the wetlands are designed and constructed, annual maintenance costs are low. Municipalities in general have small budgets and they normally face a lack of adequately trained staff. Investment into sustainable reclamation of landfill sites could be more favourable and justifiable from an economic, environmental and also human-resources point of view. In addition, wetlands add aesthetic value, and provide wildlife habitat and recreation opportunities (Renee, 2001). Therefore, constructed wetland was developed as an alternative method to treat leachate since constructed wetland has low cost of construction and maintenance. Constructed wetlands have great potential as a clean-up technology for a variety of wastewaters. Constructed wetlands have proven to be a very effective method for the treatment of municipal wastewater. For example, agricultural wastewater, industrial wastewater, storm water runoff, landfill leachate and airport runoff are all good candidates for remediation using constructed wetlands (Renee, 2001; Lin et al., 2005). The treatment of landfill leachate is one particular application for which constructed wetlands have been used widely (Crites, 2005). In numerous studies, wetland systems have shown great potential in removal of heavy 5 metals in landfill leachate (Lu et al., 1984; Qasim and Chiang, 1994; Renee et al., 2001; Nancy, 2004). Due to its high rate of the biological activities, the wetland can transform common pollutants into harmless byproducts and essential nutrients (Kadlec and Knight, 1996). In this research, a combination system utilizing a subsurface flow (SSF) wetland followed by a free water surface (FWS) wetland was studied to treat landfill leachates. 1.3 Objective of the Study The objectives of the study are: (i) To investigate the performance of the SSF-FWS constructed wetland system in treating landfill leachate. (ii) To examine the effect of the SSF-FWS constructed wetland system on leachate quality for Suspended solid (SS), Turbidity, Ammonia Nitrogen (NH4-N), Nitrate Nitrogen (NO3–N), Orthophosphate (PO43-) and heavy metal (Ferum (Fe) and Manganese (Mn)) removal. (iii) To examine the amount of heavy metal taken off by roots and leaves of the wetland plants for SSF and FWS constructed wetland system. 1.4 Scope of the Study The scope of study includes set-up a two-stage lab-scaled system comprised of a SSF and FWS constructed wetland to treat landfill leachate. The leachates were collected from Pasir Gudang Municipal Landfill, Pasir Gudang, Johor and initial water quality of the leachates were analysed. The efficiency of leachate treatment was evaluated in terms of water quality parameters SS, turbidity, NH4-N, NO3-N, PO43- and heavy metal (Fe and Mn) analysis. The experiment was carried out for 6 duration of 18 days. The amount of heavy metal (Fe and Mn) uptake by plants was determined by analysis the heavy metal concentration in plant leaves and roots. The vegetation species used are Limnocharis flava for SSF and Eichhornia crassipes for FWS constructed wetland. The experiment was carried out at Environmental Engineering Laboratory, Faculty of Civil Engineering, Universiti Teknologi Malaysia 1.5 Importance of the Study The use of constructed wetlands to treat water pollution is relatively new development in Malaysia. The recently completed Putrajaya Constructed Wetland and Lake system, which is designed to treat stormwater runoff. The abundance of wetland plant species and good conditions for plant growth in Malaysia provided an ideas environment for introducing constructed wetlands for the treatment of leachate. The potential to expand the use of constructed wetlands to the treatment of leachates beyond the more general treatment of wastewaters is relevant in today’s context. It also an environmental friendly approach to remove pollutants from leachate. Many studies have been conducted for leachate treatment in wastewater treatment using single type of constructed wetlands, whether SSF or FWS system. Nevertheless, the study of combine system of constructed wetland (SSF-FWS) for leachate treatment has not been investigated in Malaysia. Therefore, in this research, a combination system utilizing a SSF wetland followed by a FWS wetland were studied to treat landfill leachates and by incorporating local component and expertise. In term of removal efficiency, the percentage of removal under SSF-FWS constructed wetland systems should be much better to enhance leachate quality compare than one-single type constructed wetland system. Beside that, the performance of SSF-FWS constructed wetland system hope strongly supports the use of wetlands as efficient, low cost alternatives to conventional treatment of landfill leachate. CHAPTER 2 LITERATURE REVIEW 2.1 Introduction The major environmental concern associated with landfills is related to discharge of leachate into environment and the current landfill technology is primarily determined by the need to prevent and control leachate problems. Health problems and environmental pollution are often related to inadequate landfill leachate treatment. Proper collection, treatment and disposal of leachate are necessary to promote better environment and healthful condition. The use of constructed wetlands has considerable promise for the control of a large number of landfill leachate problems. Therefore, in order to develop a landfill leachate treatment by using constructed wetland system effectively, it is important to understand what factors those contribute the leachate generation, composition, and problem in leachate treatment. A brief discussion of constructed wetland system in term of definitions, types, role of wetland vegetation and mechanisms involved in wastewater treatment also included in this chapter. In addition, the specific influent wastewater must be characterized more fully, and a more fundamental understanding of the transport and fate processes must be developed. Therefore, information on the effects of constructed wetlands on leachate quality improvement has been collected from many operational constructed wetland treatment systems. 8 2.2 An Overview of Leachate Leachate is defined as the liquid produced when water percolates through any permeable material in the landfill cell. It can contain either dissolved or suspended material, or usually both (Tchobanoglous et al., 1993). Leachate also is defined as a liquid waste produced at every landfill site from liquid-waste disposal, waste moisture content and precipitation (Tjasa et al., 2004). Leachate poses a number of environmental problems. This is due primarily to the extreme variability of sources of this material, and, therefore, the heterogeneity of its composition. The production of leachate from municipal sanitary landfill is an important environmental problem. The leachate may migrate from the refuse and contaminate the surface water and groundwater (Paredes, 2003). To minimize leachate production, the factors that contribute to leachate generation need to be taken into consideration. Similarly, composition of the leachate is important to determine its potential effect on the quality of nearby surface and groundwater (Qasim and Chiang, 1994). Many factors interact to produce variable quantity and quality of leachate from landfills. 2.2.1 Leachate Generation The generation of leachate from landfill depends on many factors including availability of water, landfill surface condition, refuse condition, climatic condition on the site, underlying of soil condition, operating procedures and the physical phenomena of wastes (Paredes, 2003). Leckie et al. (1979) reported some of the most relevant factors that influent leachate generation. These factors are; annual precipitation, runoff, infiltration, evaporation, transpiration, freezing, mean ambient temperature, waste composition, waste density, initial moisture content and depth of the landfill. In most landfill, leachate is a liquid that has enter the landfill from external sources, such as surface drainage, rainfall, groundwater and water from underground springs and the liquid produced from the decomposition of the wastes (Tchobanoglous et al., 1993). Rainfall is the main contributor to generation of 9 leachate. Leachate formation is the result of the removal of soluble compounds by the non-uniform and intermittent percolation of water through the refuse mass. The precipitation percolates through the waste and gains dissolved and suspended components from the biodegrading waste through several physical and chemical reactions (Qasim and Chiang, 1994; Matthew, 2001). The sources of percolating water are primarily the precipitation, irrigation, and runoff which cause infiltration through the landfill cover, ground water intrusion, and to a lesser extent, the initial refuse moisture content (El-Fadel et al., 1997). Liquid fractions in the waste will also add to the leachate as well as moisture in the cover material. Moisture can be removed from the landfill by water consumed in the formation of landfill gas, water vapor removed in the landfill gas, and leachate leaking through the liner (Tchobanoglous et al., 1993). The major land surface conditions affecting surface runoff include surface topography (size, shape, slope and elevation), cover material, vegetation, soil permeability and soil moisture (Lu et al., 1985). Surface topography controls the flow at the surface. Meanwhile, in a not vegetation-covered landfill, the amount of infiltration of water through the refuse increased due to lower water evaporation by vegetation (Qasim and Chiang, 1994). Refuse decomposition due to microbial activity may also contribute to leachate formation but in smaller amounts (El-Fadel et al., 1997). Figure 2.1 was shown how leachate is generated. Precipitation Evapotranspiration Surface Runoff Percolation Into Waste Leachate Figure 2.1 : How leachate is generated (Bagghi, 1994) 10 2.2.2 Leachate Characterization When water percolates through solid wastes that are undergoing decomposition, both biological materials and chemical constituents are leached into solution (Tchobanoglous et al., 1993). Chian and DeWalle (1976); Chian (1977) and Lu et al. (1985) indicate that leachate quality was highly variable. It contains larger pollutant loads than raw sewage or many industrial wastes. The main factors influencing characteristics and flow of landfill leachates depend of the composition of solid waste composition, type and depth of solid waste, age of landfill, pH, operational procedures, and co-disposal of industrial wastes (Christensen et al., 1992; Qasim and Chiang, 1994; Paredes, 2003). The effects of some of these variables upon leachate quality are presented below in Figure 2.2. Refuse composition Nutrient Microbes Industrial waste co-disposal Gas and leachate Generation in Landfill Precipitation Water intrusion Temperature pH Oxygen Air intrusion Figure 2.2 : Factors influencing gas and leachate composition in landfills (Paredes, 2003) (a) Solid Waste Composition The nature of the waste organic fraction influences considerably the degradation of waste in the landfill and also the quality of the leachate produced. In particular, the presence of substances which are toxic to bacterial flora may slow down or inhabit biological degradation processes with consequences for the leachate (Christensen et al., 1992). The inorganic content of the leachate depends on the 11 contact between waste and leaching water as well as on pH and the chemical balance at the solid-liquid interface. In particular, the majority of metals are released from the waste mass under acid conditions (Qasim and Chiang, 1994). (b) Processed Refuse Leachate characteristics from shredded or baled refuse fills also differ greatly. Fungaroli and Steiner (1979); Kemper and Smith (1981) and Lu et al. (1984) conducted experiments with processed landfills i.e. shredded and baled. The results clearly indicated that leachates from shredded fills have significantly higher concentrations of pollutants than those from unshredded refuse. Christensen et al. (1992) reported, attainment of field capacity is also delayed, but the rate of pollutant removal, solid waste decomposition rate, and the cumulative mass of pollutants released per unit volume of leachate is significantly increased when compared with unshredded fills. Baling, however has shown opposite results on leachate generation and quality. Baling results in a large volume of dilute leachate with a longer period of stabilization than required for unbaled refuse. Lu et al. (1984) reported that once the field capacity of shredded and baled refuse is reached, in the long run, the cumulative mass of pollutant removal per kg of solid waste will be the same regardless of waste processing. (c) Depth of Refuse One of the earlier studies performed by Qasim and Burchinal (1970) reported that substantially greater concentrations of constituents are obtained in leachates from deeper fills under similar conditions of precipitation and percolation. Deeper fills, however, require more water to reach saturation, require longer time for decomposition, and distribute the bulk of extracted material over a longer period of time. Water entering from surface of the landfill and traveling down through the refuse will successively come in contact with solid waste, and the polluting chemicals will successively transfer to the percolating water (Qasim and Chiang, 12 1994). Deep fills offer greater contact time and longer travel distance, thus higher concentrations will result. (d) Age of Landfill Variations in leachate composition and in quantity of pollutants removed from waste are often attributed to landfill age, defined as time measured from the deposition of waste or time measured from the first appearance of leachate. Landfill age obviously plays an important role in the determination of leachate characteristics governed by the type of waste stabilization processes. It should be underlined that variations in composition of leachate do not depend exclusively on landfill age but on the degree of waste stabilization and volume of water which infiltrates into the landfill. The pollutant load in leachate generally reaches maximum values during the first years of operation of a landfill (2-3 years) and then gradually decreases over following years. This trend is generally applicable to organic components, main indicators of organic pollution i.e. COD, BOD, total organic carbon (TOC), microbiological population and to main inorganic ions i.e. heavy metals, chlorine (Cl) and sulphate (SO4) (Christensen et al., 1992). (f) pH pH influences chemical processes which are the basis of mass transfer in the waste leachate system, such as precipitation, dissolution, redox and sorption reactions. It will also affect the speciation of most of the constituents in the system. Generally, acid conditions, which are characteristic of the initial phase of anaerobic degradation of waste, increase solubilization of chemical constituents (oxides, hydroxides and carbonated species), and decrease the sorptive capacity of waste (Christensen et al., 1992). (g) Co-disposal of Industrial Wastes The co-disposal of industrial waste in the landfill may provide adverse effect on leachate. Industrial waste varies greatly in content, physical characteristics and the potential for environmental degradation (Lu et al., 1985). Addition of industrial 13 waste may result in occurrence of various toxic elements in leachate in excess of that initial content of municipal refuse leachate (Qasim and Chiang, 1994). Evidence suggests that the addition of industrial sludge which is high in trace metals and heavy metals will result in elevated metal concentrations in leachate. (h) Precipitation Water Intrusion The leachate generation induced by precipitation, it is also produced as a result of biochemical processes that convert solid materials to liquid forms. The leachate generated by biochemical processes is characterized by high concentrations of organic and inorganic constituents. The leachate is diluted by water percolating, that also it can aid in the formation of new leachate (Paredes, 2003). 2.2.3 Leachate Composition Leachate is most commonly encountered in connection with landfills where it is produced as a result of rain percolating through the waste and reacting with the chemicals and other materials in the waste (Lu et al., 1985; Tchobanoglous et al., 1993; Paredes, 2003). Landfill leachate initially is a high-strength wastewater, characterized by low pH, high BOD, COD, and by the presence of toxic chemicals (Lu et al., 1985; Qasim and Chiang, 1994). In addition, the leachate quality is variable from landfill to landfill, and over time as a particular landfill ages (Leckie et al., 1979; Qasim and Chiang, 1994). Qasim and Burchinal (1970) indicated from their lysimeter tests that leachate was high in dissolved solids and found BOD concentrations 40 to 85 times higher in leachate than in most raw domestic sewage sludge. Leachate contained larger pollutant loads than raw sewage or industrial waste; concentrations of heavy metals were higher than the applicable drinking water (Lu et al., 1985). Note that the chemical composition of leachate will vary greatly depending on the age of landfill and the events proceeding the time of sampling. For example, if a leachate sample is collected during the acid phase of decomposition, the pH value will be low and the 14 concentration of BOD, TOC, COD, nutrients and heavy metals will be high (Tchobanoglous et al., 1993). If, on the other hand, a leachate sample is collected during methane fermentation phase, the pH will be in range from 6.5 to 7.5, and the BOD, TOC, COD and nutrients concentration values will be significantly lower. Similarly, the concentrations of heavy metals will be lower because most metals are less soluble at neutral pH values (Tchobanoglous et al., 1993). The biodegradability of the leachate will vary with time. Changes in the biodegradability of the leachate can be monitored by checking the BOD/COD ratio. Initially, the ratios will be in the range of 0.5 or greater (Tchobanoglous et al., 1993). Ratios in the range of 0.4 to 0.6 are taken as an indication that organic matter in the leachate is readily biodegradable (Tchobanoglous et al., 1993). The characterization of the leachate is based mainly on an analysis of conventional physical-chemical parameters used in wastewater quality analysis. Representative data on the chemical characteristics of leachate are reported in Table 2.1. Table 2.1 : Data on the composition of leachate from landfill (Tchobanoglous et al., 1993) Value, mg/L Constituent BOD5 (5-day biochemical oxygen demand) TOC (total organic carbon) COD (chemical oxygen demand) Total suspended solids Organic nitrogen Ammonia nitrogen Nitrate Total phosphorus Orthophosphorus Alkalinity as CaCO3 pH Total hardness as CaCO3 Calcium Magnesium Potassium Sodium Chloride Sulfate Total iron Range Typical 2000-30,000 1500-20,000 3000-45,000 200-1000 10-600 10-800 5-40 1-70 1-50 1000-10,000 5.3-8.5 300-10,000 200-3000 50-1500 200-2000 200-2000 100-3000 100-1500 50-600 10,000 6,000 18,000 500 200 200 25 30 20 3,000 6 3,500 1,000 250 300 500 500 300 60 15 Table 2.2 : Leachate sampling parameters (Tchobanoglous et al., 1993) Physical Organic constituents Inorganic constituents Biological Appearance Organic chemicals Suspended solids (SS), total dissolved solids (TDS) Biochemical oxygen demand (BOD) pH Phenols Volatile suspended solids (VSS), volatile dissolved solids (VDS) Coliform bacteria (total; fecal; fecal streptocooci) Oxidation-reduction potential Chemical oxygen demand (COD) Chloride Standard plate count Conductivity Total organic carbon (TOC) Sulfate Color Volatile acids Phosphate Turbidity Tannins, lignins Alkalinity and acidity Temperature Organic-N Nitrate Nitrogen Odor Ether soluble (oil and grease) Methylene blue active substances (MBAS) Nitrite Nitrogen Organic functional groups as required Sodium Chlorinated hydrocarbons Potassium Ammonia Nitrogen Calcium Magnesium Hardness Heavy metals (Pb, Cu, Ni, Cr, Zn, Cd, Fe, Mn, Hg, Ba, Ag) Arsenic , Cyanide Fluoride, Selenium. 16 2.3 Treatment of Leachate Numerous treatability studies have been conducted with landfill leachate over the past three decades (Ho et al. 1974; Pohland 1975; Chian and DeWalle,1976; Palit and Qasim,1977; Uloth and Mavinec, 1977; Christensen et al., 1992 and Qasim and Chiang, 1994). Early studies utilized bench scale and pilot plant setup. Many treatment processes were tested and operational ranges and performance levels were established. The applicable methods of leachate treatment are biological, physical, chemical, and a combination of these processes. 2.3.1 Biological Treatment of Leachate Leachate treatment might be a very complex process if low discharge values have to be obtained. Using only the biological process the organic-degradable components can be reduced to very low values and almost complete nitrification and denitrification can be achieved (Christensen et al., 1992). Biological processes are in most cases less expensive than chemical-physical processes. Biological treatment processes involve placing a waste stream in contact with mixed culture of microorganism. The microorganisms consume the organic matter in the waste stream. The process must provide optimum environmental conditions for enhanced degradation of organic wastes (Qasim and Chiang, 1994). The methods for optimizing the biological degradation include controlling the dissolved oxygen level, adding nutrients, increasing the concentration of microorganisms and maintaining many environmental factors such as pH, temperature and mixing (Qasim and Chiang, 1994). Biologically treated leachate still has relatively high concentrations of COD and chlorinated hydrocarbons that can be further reduced by other methods. A basic problem in biological treatment is that the leachate metals and other contaminants may exert toxic effects on the biological treatment culture (Lu et al., 1985). Biological systems can be distinguished in anaerobic and aerobic treatment processes that are realized by mean of different techniques. In aerobic biological treatment 17 processes, the organics are decomposed to carbon dioxide and water. Oxygen is essential for decomposition of organic matter. In anaerobic treatment processes, organics are decomposed in the absence of free oxygen. Methane and carbon dioxide are the major end products (Qasim and Chiang, 1994). Some of the major biological treatment processes demonstrated is described below. (a) Activated Sludge Activated sludge process successfully treated the leachate in most case. The following generalizations can be made in treating leachate by activated sludge process (Chian and DeWalle, 1976; Palit and Qasim, 1977; Uloth and Mavinec, 1977; and Christensen et al., 1992): (1) BOD and COD removal, 90-99%,; (2) Metal removal, 80-99% and Operational range (MLVSS concentration of 5000-10,000 mg/L, food to microorganisms ratio 0.02-0.06 per day, hydraulic retention time 1-10 days and solids retention time 15-60 days). The operational parameters clearly indicate that large amounts of organic matter in leachate were not readily oxidized, and required extensive biological activity for stabilization. (b) Stabilization Pond and Aerated Lagoon Stabilization ponds and aerated lagoons have been effectively used for treatment and polishing of municipal wastewater. For pretreatment of leachate, they offer a relatively economical method, prior to disposal into municipal sewers or recycling into landfills. Early studies were conducted to evaluate the performance of aerobic and anaerobic ponds, and aerated lagoons for treatment of raw leachate, and also to evaluate their performance in conjunction with other treatment processes (Qasim and Chiang, 1994). Chian and DeWalle (1977) have reported that in treating raw leachate by aerated lagoon, a COD removal was 22-99%. The range of BOD/COD, and BOD/TOC ratios fed to aerated lagoon varied from 0.03 to 0.08, and 1.56 to 3.45 respectively. It is clearly noted that COD removal decreases for lower ratios. Chian and DeWalle (1977) treated high strength leachate in laboratory scale aerated lagoons. Nutrient addition was necessary. Removal efficiencies achieved were; 97% organics, over 99% iron, zinc, and calcium, and 76% magnesium. Vyda and Grimm (1977) studied the combination of aerated lagoon and polishing pond 18 each had a 10 days aeration period. The combination provided an effective leachate treatment system. (c) Anaerobic Treatment Processes Anaerobic processes have also been used for treatment of landfill leachates. The process offers several benefits over aerobic processes. Among these are (1) sludge production is significantly reduced, (2) stabilization of organics is lower, and (3) recovery of methane may provide energy. Many researchers demonstrated BOD removal in the range of 90-99% (Boyle and Ham, 1974; Pohland, 1975; and Chian and DeWalle, 1977). In these studies the average BOD/COD and TOD/TOC ratios were 0.68 and 2.86 respectively. Christensen et al. (1992) treated high strength leachate (BOD 38,500 mg/L and COD 60,000 mg/L) from existing landfill using upflow fixed film reactor, and found 95% BOD and TSS removal. 2.3.2 Physical-Chemical Treatment of Leachate Various physical-chemical treatment processes have been applied to leachate treatment. Physical or chemical treatment processes may be particularly useful in treating leachates from older landfills whose organic content is negligible, or as a polishing step for leachates previously treated by biological methods (Lu et al., 1985). Some of the major physical-chemical treatment processes demonstrated is described below: (a) Precipitation and Coagulation Chemical precipitation and coagulation experiences have been fairly successful in removing iron, color and suspended solids in leachates. Thornton and Blanc (1973) and Ho et al. (1974) have demonstrated that precipitation with lime is effective in the removal of iron and other multivalent ions, color, suspended solids and COD. BOD concentrations, however, are apparently unaffected. Iron precipitation by lime is particularly pronounced, as nearly 100 percent removal is 19 consistently reported at lime concentrations over 300 mg/L. Precipitation by sodium sulfide is reported by Ho et al. (1974). Iron removal occurred only at a very high chemical dose (1000 mg/L), and its effects on other constituents were negligible. Sulfides are apparently not as promising for leachate cation removal as lime. Coagulation is able to reduce colloidal suspension which is partially responsible for turbidity and color. Also, dissolved organic substances, principally those with higher dimension are involved in flocculation process, because they are adsorbed in the flocs and successively removed through gravity settling (Christensen et al., 1992). More favourable results were obtained for suspended solids and color removal (Thornton and Blanc, 1973 and Ho et al., 1974). A removal efficiency of 75% for suspended solid and 50-70% for certain heavy metals was obtained with high coagulant dosage. (b) Carbon Adsorption The removal of leachate organics by carbon adsorption was studies by Pohland (1975), for leachates previously treated by ion exchange. Through moderately successful, activated carbon was found to release solids which adversely affected the total solids concentration of the leachate. Pohland (1975) suggested that if leachate were to be treated with both carbon and mixed resins, the carbon treatment should precede the mixed resins. Activated carbon column tests performed by Ho et al. (1974) demonstrated complete color and odor removals at a detention time of 20 minutes, along with 55% COD removal. (c) Chemical Oxidation A typical problem for physico-chemical processes is the production of residues with concentrated pollutants. However, processes aimed at completely destroying pollutants, such as chemical oxidation may provide a final solution to the problem. Chemical oxidation was shown to be reasonable effective in removal of COD, iron and color (Ho et al., 1974), though only at high concentrations of the oxidizing agent. Oxidizing agents included chlorine, calcium hypochlorite, potassium permanganate and ozone. Most of these compounds have both a significant bacterial disinfection and oxidation capacity. They are less frequently 20 used for organic compound oxidation, principally for economic reasons due to the high dosage required. However, since leachate is a wastewater often with a low flow rate, chemical oxidation for refractory organic compounds removal has been proposed (Christensen et al., 1992). Early studies by Ho et al. (1974), examined the most favourable results were obtained with calcium hydrochlorite, but the COD removal efficiency was less than 50%. Moreover, all oxidants required high dosage which consequently caused numerous problems, such as increases in chlorine and hardness when using, respectively chlorine gas (Cl2). With regard to the utilization of ozone, no residual compound problem was observed, but it was not possible to obtain more than 50% COD removal (Chian and DeWalle, 1976). (d) Reverse Osmosis Of all the physical-chemical processes evaluated for leachate treatment, reverse osmosis was found most effective for removal of COD. Chian and DeWalle (1977) reported between 56-70% removals of TOC with the conventional cellulose acetate membrane, while the removal increased to 88% with the polyethyleamine membranes. Since low rejection of undisassociated fatty acids by membranes was responsible for the leakage of TOC into the permeate, the performance of the membrane process was improved to 94% when the pH of the leachate was increased from 5.5 to 8.0 (Chian and Fang, 1973). In addition to efficient TOC removal, total dissolved solids removal was as high as 99%. In most studies, severe membrane fouling was experienced, and biological pretreatment of leachate prior to membrane processes was necessary. Lu et al. (1984) suggested that reverse osmosis is perhaps most effective as a post biological treatment step for removal of residual COD and dissolved solids. Chian and DeWalle (1977) also noted that membranes are sensitive to pH. Table 2.3 and Table 2.4 showed the summary of biological and physical-chemical treatment processes applied to leachate treatment. 21 Table 2.3 : Physical, chemical and biological treatment processes applicable to process trains for leachate treatment (Qasim and Chiang, 1994) Process Physical Processes Equalization Description Flow and mass loadings are equalized by means of utilizing inline or off-line equalization chambers. Screening Suspended and floating debris are removed. Removal is by straining action. Flocculation Fine particles are aggregated. Gentle stirring is utilized. Sedimentation Settleable solids and floc are removed by gravity. Flotation Solids are floated by fine air bubbles and skimmed from the surface. Dissolved air flotation (DAF) is commonly used. Air Stripping Air and liquid are contacted in countercurrent flow in a stripping tower. Ammonia, other gases and volatile organics are removed. Filtration Suspended solids and turbidity are removed in a filter bed or micro screen. Membrane Processes These are demineralization processes. Dissolved solids are removed by membrane separation. Ultrafiltration, reverse osmosis and electrodialysis are the most common systems. Natural Evaporation The waste is impounded in basins that have an impervious liner. Liquid is evaporated. The rate of evaporation depends upon temperature, wind velocity, humidity, and natural precipitation. Chemical Processes Coagulation Colloidal particles are destabilized by rapid dispersion of chemicals. Organics, suspended solids, phosphorus, some metals, and turbidity are removed. Alum, iron salts and polymers are commonly used coagulation chemicals. Precipitation Solubility is reduced by chemical reaction. Hardness, phosphorus, and many heavy metals are removed. Gas Transfer Gases are added or removed by mixing, air diffusion and change in pressure. Chemical Oxidation Oxidizing chemicals such as chlorine, ozone, potassium permanganate, hydrogen peroxide and oxygen are used to oxidize organics, hydrogen sulfide, ferrous, and other metal ions. Ammonia and cyanide are oxidized by strong oxidizing chemicals. Chemical Reduction Many metals are removed. Common reducing chemicals are sulfur dioxide, sodium bisulfite and ferrous sulfate. 22 Table 2.3 (Continued) Process Description Disinfection Destruction of pathogens is achieved by using oxidizing chemicals or ultraviolet light. Ion Exchange Removal of inorganic species is achieved from liquid. Ammonia is selectively removed by clinoptilite resin. This process is used for mineralization. Carbon Adsorption Used for reduction of residual BOD, COD, toxic and refractory organics. Some heavy metals are also removed. Carbon is used in powdered form or in a granular bed. Biological Processes Aerobic Microorganisms are cultivated in the presence of molecule oxygen. Solids are recirculated. The end product is carbon dioxide. Suspended Growth The wastewater containing BOD, solids, and nutrients are mixed with a large population of active microorganisms suspended in an aeration basin. Activated Sludge In the activated sludge process the food and sludge microorganisms are aerated. The microorganisms are settled and recirculated. Common process modifications are conventional, completely mixed, pure oxygen, extended aeration and contact stabilization. Nitrification Ammonia nitrogen is oxidized to nitrate. BOD removal can also be achieved in a single aeration basin, or in a separate basin. Aerated Lagoon Large aeration basins with several days of detention period are used. Sequencing Batch Reactor (SBR) A SBR is a fill-and-draw activated sludge treatment systems. Food and microorganisms contact, organics stabilization, sedimentation and discharge of clarified effluent occur in a single basin. Attached Growth Trickling Filters Rotating Biological Contactor (RBC) Anaerobic The population of active microorganisms is supported over solid media. The solid media may be of rocks or synthetic material. Water is applied over a bed of rocks or synthetic media. Trickling filters are slow rate, high rate, and two stage filters. Aeration is by natural draft or forced draft. Consists of a series of closely spaced circular contactor disks of synthetic material. The disks are partly submerged in the wastewater. The microorganisms are cultivated in the absence of oxygen. The complex organics are solubilized and stabilized. Carbon dioxide, methane and other organic compounds are the end products. 23 Table 2.3 (Continued) Process Suspended Growth Description The waste is mixed with biological solids in a digester, and the contents are commonly stirred, and heated to an optimum temperature. Conventional High organic strength waste or sludge is stabilized in a digester. The digesters are standard rate, high rate, one-stage, or two stages. Denitrification Nitrite and nitrate are reduced to gaseous nitrogen in an anaerobic environment. A suitable organic carbon source (acetic acid, methanol, sugar etc.) is required. Combine Anoxic, Anaerobic and Aerobic System Nitrogen and phosphorus are removed along with BOD in an anoxic, anaerobic and aerobic treatment system. Nitrate is converted to gaseous nitrogen in the anoxic reactor. Phosphorus is released in anoxic and anaerobic reactors. Uptake of released phosphorus, BOD stabilization, and nitrification of ammonia occurs in the aerobic reactor. Attached Growth The microbiological film is supported over a solid media. The organic matter is stabilized as the waste comes in contact with the attached growth. Anaerobic Filter The reactor is filled with the solid media, and the waste flows upward. Expended Bed or Fluidized Bed The reactor is filled with media such as sand, coal and gravel. The influent and recycled effluents are pumped from the bottom. The bed is kept in an expanded condition. Combined Suspended and Attached growth The attached and suspended microbiological growth in an anaerobic environment consumes the organic matter. Aerobic-anaerobic Stabilization Ponds Stabilization ponds are earthen basins with impervious liner. The basins may be aerobic, facultative, or anaerobic depending upon the depth and strength of waste. Source of oxygen is natural aeration. Land Treatment The waste is applied over land to utilize plants, soil matrix and natural phenomena to treat waste by a combination of physical, chemical and biological means. The methods of land application are slow-rate irrigation, rapid infiltration-percolation, and overland flow. 24 Table 2.4 : Summary of biological and physical-chemical treatment processes applied to leachate treatment Type of Treatment Results References Activated Sludge The removal efficiency for BOD and COD removal was 90-99%, metal removal 80-99% and operational range (MLVSS concentration of 5000-10,000 mg/L, food to microorganisms ratio 0.02-0.06 per day, hydraulic retention time 1-10 days and solids retention time 15-60 days). The operational parameters clearly indicate that large amounts of organic matter in leachate were not readily oxidized and required extensive biological activity for stabilization. Chian and DeWalle (1976); Palit and Qasim (1977); Uloth and Mavinec (1977); and Christensen et al. (1992) Aerobic/Anaerobic Activated Sludge (A/A Process) The A/A process removed up to 70% of the nitrogen contained in leachate, compared to 20% nitrogen removal by a conventional activated sludge system, when the leachate BOD5:TKN ratios exceeded 10. The A/A process achieved greater nitrification removals than aerobic system with no loss in BOD removal efficiency, while using 50% less aeration energy than the fully aerobic system. Manganese removal was greater than 50% with effluent concentrations of 4-5 mg/L. Christensen et al. (1992) Aerated Lagoon The COD removal was achieved 22-99% have reported by using aerated lagoon. The range of BOD/COD, and TOD/TOC ratios fed to aerated lagoon varied from 0.03 to 0.08, and 1.56 to 3.45 respectively. It is clearly noted that COD removal decreases for lower ratios. Removal efficiencies achieved were: 97% organics, over 99% irons, zinc, and calcium, and 76% magnesium. Chian and DeWalle (1977) Rotating Biological Reactor (RBC) This report was investigated the comparative performance of activated sludge and RBC in treating leachate from existing landfill. Bench scale and pilot plant studies indicated that BOD5 removal rates in RBC were 95-97%, and soluble COD removal rates were 80-90%. The RBC unit after an aeration basin provided additional removal and nitrification was 98-99%. Lugowski et al. (1989) Biological Process 25 Table 2.4 (Continued) Type of Treatment Results References This report investigated the use of subsurface flow rock-reed filters for treatment of leachate from a solid waste landfill. The results showed BOD removal 7694% with greatest removal occurring in gravel mini beds. Removals of heavy metals, nitrogen and phosphorus also high. Sanford et al.. (1990) Precipitation and Coagulation These researchers demonstrated that BOD and COD removal by lime precipitation is small, but removal of color, iron and other multivalent cations was excellent at higher lime doses (300-400 mg/L). Coagulation with alum and ferric chloride was also not very effective in removing BOD and COD. High chemical doses were needed and the process was sensitive to pH. Also production of large quantities of sludge was reported. Thornton and Blanc (1973) and Ho et al. (1974) Ion Exchange This researcher utilized combination of cation and anion exchange resins to improve the quality of biologically treated leachate. The process was effective in removing dissolved salt, and nutrients. Very little removal of residual organics was reported. However, the use of mixed resins was considered a promising approach for the removal of the non-organic fraction of leachate. Pohland (1975) Carbon Adsorption These researchers reported that leachate having COD/TOC ratio of 2.9, showed an initial TOC removal of 70%, which decreased to 13% after 140 bed volumes. These clearly indicate that treatment of leachate by activated carbon is not feasible due to the large quantities of activated carbon required. However, also reported up to 70% COD removal by activated carbon with stabilized leachate having a BOD/COD ratio of less than 0.1. Chian and DeWalle (1977) Fixed Film Reactor Physical-chemical process 26 Table 2.4 (Continued) Type of Treatment Results References Chemical Oxidation Chian and DeWalle suggested that calcium hypochlorite produced the best results as chemical oxidant, especially in removing COD, iron and color in leachate treatment. But, the COD removal efficiency was less than 50%. Chian and DeWalle (1977) and Ho et al. (1974) Reverse Osmosis This study reported between 56-70% removals of TOC with the conventional cellulose acetate membrane, while the removal increased to 88% with the polyethyleamine membranes. However, this study showed high COD removal (more than 80%), although some operating problems, such as membrane fouling were observed. Chian and DeWalle (1976) 27 2.4 Problem in Leachate Treatment There are various options to treat landfill leachates. The identification of the preferred option in specific circumstances is a function of the costs, both operating and capital, and the limitation impose on the quality and quantity of discharge. Selection and design of a leachate treatment process is not simple. Important factors that govern the selection and design of treatment facilities include leachate characteristics, effluent discharge alternatives, technological alternatives, costs and permit requirements (Qasim and Chiang, 1994). Specific problems inherent with treatment of landfill leachate are: (i) The high strength of waste and magnitude of pollution potential dictates the selection and use of reliable treatment processes; (ii) The changes encountered from landfill to landfill are such that waste treatment techniques applicable at one site may not be directly transferable to other locations. It may be necessary that each instance be separately engineered for proper treatment; (iii) The source of leachate is primarily percolating water that may be seasonal depending on hydrologic and climatic factors; (iv) The chemical nature of the solid wastes accepted at a landfill has a marked effect on the composition of the leachate; and (v) The fluctuations in the leachate quantity and quality, which occur over both short and long time intervals, must be considered in the treatment plant design. The process designed to efficiently treat the leachates from a young landfill should be modified in the future to treat the leachate adequately as the landfill ages, or effluent standards change. 28 2.5 Wetland A wetland can be many things to many people. Generally, the word “wetland” conjures an image of a river or pond surrounded by cattails, alive with ducks, fish, frogs and the like paddling about. Identification and delineation of wetlands has become an important topic. This is partly due to the variety of groups that have interest in wetlands (Navid, 1989). Wetlands are defined by The International Union for the Conservation of Nature and Natural Resources (IUCN) at the Convention on Wetlands of International importance especially as Waterfowl Habitat, better known as the Ramsar Convention adopted the following definition of wetlands (Navid, 1989; Finlayson and Moser, 1991): "Areas of marsh, fen, peat land or water, whether natural or artificial, permanent or temporary, with water that is static or flowing, fresh, brackish, or salt including areas of marine water, the depth of which at low tide does not exceed six meters" and also defined as "Land inundated with permanent or temporary water that is usually slow moving or stationary, shallow, either fresh, brackish or saline, where the inundation determines the type and productivity of soils and the plant and animal communities". Both natural and constructed wetlands have been used as wastewater treatment system; it is found that both systems may act as efficient water purification systems and nutrient sinks (Brix, 1997). Natural wetlands are characterized by extreme variability in functional components, making it virtually impossible to predict responses to wastewater application and to translate results from one geographical area to another. Although significant improvement in the quality of the wastewater is generally observed as a result of flow through natural wetlands, the extent of their treatment capability is largely unknown. The performance may change over time as a consequence of changes in species composition and accumulation of pollutants in the wetlands (Aeslina, 2004). Therefore, the treatment capacity of natural wetlands is unpredictable, and design criteria for constructed wetlands cannot be extracted from results obtained in natural wetlands. 29 2.6 Constructed Wetland Constructed wetlands represent an emerging ecotechnological treatment system, which are designed to overcome the disadvantages of natural wetlands. Constructed wetland treatment systems are human-made, engineered wetland areas specifically designed for water quality improvement by optimizing physical, chemical and biological processes that occur in natural aquatic wetland ecosystems. Constructed wetlands have been demonstrated to immobilize and remove metals contained in wastewater very effectively (Kadlec and Knight, 1996; Lytle et al., 1998; Polonsky and Clements, 1999; Zhu et al., 1999; Vesk et al., 1999). According to Hammer and Bastian (1989), a constructed wetland is a “designed and man-made complex of saturated substrates, emergent and submergent vegetation, animal life, and water that simulates natural wetlands for human use and benefits”. A constructed wetland is an ecological system that combines physical, chemical and biological treatment mechanisms in removing pollutants from wastewater as it flows throught the wetland. The use of constructed wetlands has several advantages over conventional wastewater treatment methods. The initial cost of constructed wetlands is considerably lower than conventional treatments in treating wastewater discharged from municipal, agriculture and industrial sources (Kadlec and Knight, 1996). Annual cost of operation is also considerably less due to its relatively simple design. While constructed wetlands efficiently remove many pollutants from wastewater streams, constructed wetlands also enhance the environment by providing a habitat for vegetation, fish, birds, and other wildlife (Mashhor et al., 2002; Jin et al., 2003). Among the aquatic treatment systems, constructed wetlands have a greater potential because they can tolerate higher organic loading rate and shorter hydraulic retention time. Consequently, land requirement for construction wetland is less than that for other aquatic treatment systems. In addition, these systems have the capability of treating more than one type of pollutants simultaneously to some satisfactory levels. This can rarely be achieved by other treatment systems (Mashhor et al., 2002). 30 Constructed wetland system are designed, built and operated to emulate the functions of natural wetlands especially marshes in the treatment of wastewater and urban runoff water. According to Brix (1994), constructed wetlands are suitable for wastewater treatment especially for post treatment, because the wetland vegetation and organisms can adapt to the wastewater inflow and utilize the various organic and inorganic pollutants during the metabolic and other life processes. Constructed wetland are designed to maximize the physical, chemical and biological abilities of natural wetlands to reduce BOD, total suspended solid (TSS), total nitrogen (TN), phosphorus, and pathogens as wastewater flows slowly through the vegetated subsurface (Masud et al., 2004). Precipitation and uptake of metals are also possible along with biodegradation and bioaccumulation. The mechanisms of pollutant removal in wetlands include both aerobic and anaerobic microbiological conversions, sorption, sedimentation, volatilization and chemical transformations (Nancy, 2004; Masud et al., 2004). 2.7 Types of Constructed Wetland There are several types of constructed wetlands and the main are classified as either FWS systems or SSF systems. Any wetland, in which the surface of the water flowing through the system is exposed to the atmosphere, is classified as an FWS system (Lim, 2002; Lee, 2004). It has a natural or constructed clay layer or impervious liner made of geotechnical material as bottom to prevent seepage. Above the layer is the soil or other suitable medium to support the growth of emergent plants (Lim, 2002; Lee, 2004). In SSF systems water is designed to flow through a granular media, without coming into contact with the atmosphere. It is basically consists the same components as the FWS systems but the water level is maintained below the top of media and the media supporting plant growth normally consist of gravel to ensure better bed porosity (Lim, 2002; Lee, 2004; Paquiz, 2004). Free water surface wetlands can be sub-classified according to their dominant type of vegetation; 31 emergent macrophyte, free floating macrophyte, or submerged macrophyte (Le, 2003). Subsurface flow wetlands (which by definition must be planted with emergent macrophytes) can best be sub-classified according to their flow patterns: Horizontal flow or Vertical flow. A classification system is shown in Figure 2.3. Free Water Surface (FWS) Subsurface Flow (SSF) Emergent Macrophyte based Horizontal Free Floating Macrophyte based Vertical Submerged Macrophyte based Figure 2.3 : Wetland design categories (Le, 2003) 2.7.1 Free Water Surface Wetlands Based on the ecological engineering of natural wetlands, the constructed free water surface (FWS) wetlands were build for wastewater treatment purposes mainly (Mashhor et al., 2002; Le, 2003). FWS wetlands consist of a shallow basin, soil or other medium to support the roots of vegetation and a water control structure that maintains a shallow depth of water. The water surface is above the substrate. FWS wetlands look much like natural marshes and can provide wildlife habitat and aesthetic benefits as well as water treatment (Mashhor et al., 2002; Le, 2003). In FWS wetlands, the near surface layer is aerobic while the deeper waters and substrate are usually anaerobic. Stormwater wetlands and wetlands built to treat mine drainage and agricultural runoff are usually FWS wetlands. Emergent macrophytes based wetlands are the most common type of FWS. They consist of a series of channels or basins which are lined with an impermeable material (such as clay) in order to limit infiltration. A layer of soil is provided on top of the impervious material in which emergent macrophytes are planted. The macrophytes supply oxygen to the sludge zone through their roots, thereby 32 promoting aerobic digestion of the pollutants by microorganisms. Macrophytes also act as physical supports for microorganisms that help remove pollutants (Le, 2003). As the name implies, free floating macrophytes based wetlands make use of floating plants, such as duckweed and water hyacinth, to remove nutrients and control algae in wastewater. A floating barrier grid is used to support the growth of floating macrophytes and to reduce wind effects, which would otherwise cause the plants to drift. It has been claimed that the floating plant mat blocks out sunlight, thereby preventing photosynthesis and inhibiting algae growth (Lemna Corporation, 1994). The plant mat and barrier grid reduce turbulence, allowing suspended solids to settle out more readily. The advantages of FWS wetlands are that their capital and operating costs are low, and their construction, operation, and maintenance are straight forward. The main disadvantage of FWS systems is that they generally require a larger land area and other systems (Le, 2003; Galbrand, 2003; Aeslina, 2004). Table 2.5 showed the advantages and disadvantage of Free Water Surface Flow Wetlands. And, Figure 2.4 shows the different types of FWS wetlands. Table 2.5 : Advantages and disadvantages of Free Water Surface Flow wetlands (Nancy, 2004) Advantages Disadvantages Less expensive to construct (on a cost per acre basis) and operate and simpler to design than SSF wetlands and conventional treatment methods. Lower rates of contaminant removal per unit of land than SSF wetlands, thus they require more land to achieve a particular level of treatment than SSF wetlands Can be used for higher suspended solids wastewaters Requires more land than conventional treatment methods. Offer greater flow control than SSF wetlands. Risk of ecological or human exposure to surface-flowing wastewater. Offer more diverse wildlife habitat May be slower to provide treatment than conventional treatment. Provides habitat for plants and wildlife Odors and insects may be a problem due to free water surface. 33 Inlet pipe Outlet weir/pipe Low-permeability soil (a) FWS wetland with emergent macrophytes Inlet pipe Outlet weir/pipe Lined basin (b) FWS wetland with floating plants Inlet pipe Outlet weir/pipe Low-permeability soil (c) FWS wetland with submerged macrophytes Figure 2.4 : Types of Free Water Surface (FWS) treatment wetlands (Brix, 1993) 34 2.7.2 Subsurface Flow Wetlands The Subsurface Flow (SSF) wetland basically consists of the same components as the FWS systems, but the wastewater is confined to the substratum (Freeman, 1993). The SSF wetlands are designed as a basin or channel with a boundary to prevent seepage and a suitable depth bed of porous media that support the emergent plants (Le, 2003). The wastewater will flow in a high level site of the wetland and then flow through the porous media of sand soil and plant rhizosphere (Le, 2003). Subsurface flow type wetlands make use of the same removal mechanisms as FWS wetlands; sedimentation, filtration and microbiological degradation. When the wastewater flows through the media, it is being purified through contact with the surface of the media and the root zone of the plants (Lim and Polparasert, 1996). However, since the wastewater flow is below the surface, it is in continuous contact with the filter media, which in turn provides more surface area for bacterial growth, therefore allowing for higher organic loading rates (Le, 2003). The media supporting plant growth normally consist of soil, sand, gravels and rocks in that order downwards to provide better bed porosity (Mashhor et al., 2002). The SSF wetland types have several advantages if compared with the FWS wetland types. It is found that in the constructed SSF wetland, the available of wastewater treatment is better than the constructed FWS one. SSF are more effective than FWS system at removing pollutants at high application rate (Aeslina, 2004). Wastewater flowing subsurface media may also avoid of the little risk of heavy odors, dark-color exposure and insect vectors effects (Kowalk, 2002). The area application for SSF wetland can be smaller than a FWS system with the same wastewater withdrawing conditions (Le, 2003; Galbrand, 2003). The disadvantages of SSF wetlands are that they are more expensive to construct, on a unit basis than FWS wetlands. Because of cost, SSF wetlands are often used for small flows. SSF wetlands may be more difficult to regulate than FWS wetlands, and maintenance and repair costs are generally higher than for FWS wetlands. A number of systems have had problems with clogging and unintended 35 surface flows (Galbrand, 2003; Nancy, 2004). Table 2.6 shows the advantages and disadvantages of SSF Wetlands. Table 2.6 : Advantages and disadvantages of Subsurface Flow wetlands (Nancy, 2004) Advantages Disadvantages Higher rates of contaminant removal per unit of land than FWS wetlands, thus they require less land to achieve a particular level of treatment than FWS wetlands. Requires more land than conventional treatment methods. Lower total lifetime costs and capital costs than conventional treatment systems. May be slower to provide treatment than conventional treatment Minimal ecological risk due to absence of an exposure pathway. Waters containing high suspended solids may cause plugging More accessible for maintenance because there is no standing water. More expensive to construct than SF wetlands on a cost per acre basis. Odors and insects not a problem because the water level is below the media surface. There are two types of constructed SSF wetlands, which are horizontal flow systems and vertical flow systems (Liu, 2002; Mashhor et al., 2002). As their names, this classification is based on the flow direction to the soil and gravel layers. This technology is generally limited to systems with low flow rates and can be used with less than secondary pretreatment (Kadlec, 1999). (a) Horizontal Flow System In Horizontal Subsurface Flow (HF-SSF) wetlands, the medium is kept saturated under a continuous wastewater flow. Wastewater is fed in at the inlet and flows slowly through the porous medium under the surface of the outlet zone, where it is collected and discharged at the outlet. During this passage, the wastewater will into contact with a network of aerobic, anoxic and anaerobic zones. The aerobic zones occur around roots and rhizomes that leak oxygen into the substrate. When the 36 wastewater passes through the rhizosphere, the wastewater is cleaned by microbiological degradation and by physical and chemical process (Cooper et al., 1996). Oxygen is then transferred from the atmosphere into the wetland through the emergent plants (Galbrand, 2003). Figure 2.5 shows a typical arrangement for the constructed wetland with HF-SSF. Figure 2.5 : Typical arrangement of horizontal subsurface flow constructed wetland system (Le, 2003) (b) Vertical Flow System Vertical Subsurface Flow (VF-SSF) wetlands are operated as a batch process rather than in continuous flow mode. Wastewater is dosed at timed intervals so that the filter is allowed to drain. Consequently, the system is not always saturated and oxygen is more easily transferred from the atmosphere through diffusion. Therefore, this system tends to be less anoxic compared to horizontal flow system and it is suitable for treatment of wastewater that has a relatively high oxygen demand (Liu, 2002). In general, vertical flow SSF wetlands are less common and not as well documented as horizontal flow systems. VF-SSF treatment wetlands are frequently planted with common reed. Other emergent wetlands plants such as cattails or bulrush can also be used. They are composed of a flat bed of gravel topped with sand. The liquid or wastewater then gradually drains vertically down through the bed and is collected by a drainage 37 network at the base. The bed drains completely free, allowing air to refill the bed. The next dose of liquid traps this air and this together with 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 (Cooper et al., 1996). Figure 2.6 shows a typical arrangement for the constructed wetlands with a VF-SSF. Figure 2.6 : Typical arrangement of vertical subsurface flow constructed wetland system (Cooper et al., 1996) 2.7.3 Combine FWS-SSF Constructed Wetland System in Wastewater Treatment Integrated constructed wetland comprised of a FWS-SSF systems have introduced as alternative to enhance the potential of constructed wetland in wastewater treatment. Several researchers were involved in this treatment system (Eckhardt et al., 1999; Lin et al. 2002, 2005) In the paper by Eckhardt et al. (1999), results of dual system involving a FWS-SSF constructed wetland to treat landfill leachate in Munroe Country, New York are presented. Both contained Phragmites australis reeds and were designed for leachate application at a rate of 1.8 m3/day. The FWS wetland provided an effective pretreatment site for certain constituents, while the SSF wetland functioned as an environment for plant uptake, microbial 38 activity and geochemical processes, all of which assisted in contaminant removal. In this study, the data demonstrated that removal rates for 14 constituents ranged from 49% to 100%. The removal efficiencies exceeded 90% for most metals species, total phosphorus, ammonium, BOD and volatile organic compound (VOC). Removal rates were lowest for the major inorganic ions and barium. The results indicate the (1) total iron removal was 98%, and load reduction for most metals species was facilitated by oxygen from rainfall, aeration, plant input, especially in the SSF bed; (2) nitrogen removal (mostly as ammonium) was 91%; and (3) total phosphorus removal was 99% and was mainly through plant uptake and concentration in plant tissues, especially the rhizomes. Figure 2.7 shows the plan view of constructed wetland at Munroe Country wastewater treatment. Figure 2.7 : Plan view of constructed wetland at Munroe Country wastewater treatment , New York (Eckhardt et al., 1999) Lin et al. (2002) were developed a pilot-scale wastewater treatment system consisting of FWS and SSF constructed wetlands to evaluate the performance of nutrient removal from aquaculture wastewater under various hydraulic loading rate (HLR) of 1.8 to 13.5 cm/day. By observation the performance transitions and growth of wetland plants, the result demonstrated that FWS and SSF constructed wetlands showed quick start-up behaviors for treating aquaculture wastewater, with the SSF wetland achieving stable performance more rapidly than the FWS wetland. 39 The result showed that nitrogen removals were excellent, with efficiencies of 86% to 98% for ammonia nitrogen (NH4-N) and 95% to 98% for total inorganic nitrogen (TIN). Phosphorus removal of 32% to 71% occurred, with the efficiencies being inversely related to hydraulic loading. The study was concluded that the FWS wetland removed most inorganic nitrogen, whereas the SSF wetland removed phosphate at a rate equal to or even greater than the FWS. Figure 2.8 shows the pilot-scale system consisted of a FWS and a SSF constructed wetlands arranged in series. Earthen fishpond A Effluent to fish B FWS wetland Influent from fishpond Perforated distribution pipeTrough-shaped colletor SSF wetland C Perforated collection pipe Figure 2.8 : Layout of the pilot-scale FWS-SSF series constructed wetlands system for treating fishpond water. (A) Sampling location for the influent; (B) sampling location for the FWS effluent; (C) sampling location for the SSF effluent (Lin et al., 2002) Beside, a study conducted by Lin et al. (2005) were investigated the performance of the treatment wetlands for controlling water quality. The results showed that the FWS-SSF constructed wetlands effectively removed BOD5 (3754%), SS (55-66%) and NO2-N (83-94%), total ammonia (64-66%) from recirculating water under high hydraulic loading rate, HLR in range 1.57 to 1.95 m/day. However, NO3-N was removed poorly as the nitrate level increased from influent to effluent. The high HLR applied in this study affected the performance of pollutants removal. The study also showed that high HLR diminished the contact time for nitrate and denitrifying bacteria, thus decreasing the performance of wetland 40 for denitrification. Figure 2.9 shows a schematic diagram of the recirculating aquaculture system. SF wetland Compressor FWS wetland Culture Tank Sump Settling cell Recirculation Water Indoor Outdoor Figure 2.9 : Schematic diagram of the recirculating aquaculture system (Lin et al., 2005) 2.8 Pollutants Removal Process Mechanisms Constructed wetlands consist of channels and basins in which aquatic plants are planted. Wastewater is discharged into the wetland system by either pumping or gravity. Several physical, chemical and biological processes take place in a wetland system. On average, wetlands are capable of providing removal rates ranging anywhere from 60% to over 95% for many pollutants (Mashhor et al., 2002). There are six major biological reactions of interest in the performance of constructed wetlands; photosynthesis, respiration, fermentation, nitrification, denitrification and microbiological phosphorus removal (Hammer, 1990; Mashhor et al., 2002; Nancy, 2004). The principal pollutant removal mechanisms operative in wetland systems are includes sedimentation, chemical precipitation and adsorption, microbial metabolic activity and plant uptake. Chemical reactions between certain substances, especially 41 metals, can lead to their precipitation from the water column as insoluble compounds. The following Table 2.7 provides an overview of pollutant removal mechanisms. And, Figure 2.10 shows mechanisms treating inorganic compounds in wetland treatment systems. Table 2.7 : Overview of pollutant removal process (Watson et al., 1989) Pollutant Removal Process Organic Material (measured as BOD) biological degradation, sedimentation, microbial uptake Organic Contaminants (e.g. pesticides) adsorption, volatilization, photolysis, biotic or abiotic degradation Suspended solids sedimentation, filtration Nitrogen sedimentation, nitrification/denitrification, microbial uptake, plant uptake, volatilization Phosphorus sedimentation, filtration, adsorption, plant & microbial uptake Heavy metals sedimentation, adsorption, plant uptake Figure 2.10 : Major pollutants uptake and release pathway in wetland system (Nancy, 2004) 42 (a) Suspended Solids Removal Most of the solids are removed through sedimentation and filtration, as vegetation obstructs the flow and reduces velocities. Settleable solids are removed easily by sedimentation since wetland systems generally have long hydraulic retention times (Lim, 2002). Non-settling or colloidal solids are removed by processes which include; straining (sand media), adsorption on plants and wetland media and biodegradation. The types of removal mechanism at work are very dependent on the size and nature of solids present in the wastewater and the types of filter media used (Lim, 2002). In all cases, wetland vegetation has a negligible role to play. In most applications, a sedimentation pond is added upstream of the wetland cells to promote the removal of larger sediment particles and minimize the chance of clogging the wetland cells. These processes remove a significant portion of the BOD, nutrients (mostly nitrogen and phosphorus) and pathogens (Watson et al., 1989; Lim, 2002). (b) Biochemical Oxygen Demand Removal Microbial degradation plays a dominant role in the removal of soluble or colloidal biodegradable organic matter (BOD) in wastewater (Lim et al., 2001). Both the FWS and SSF system essentially function as attached growth biological reactors. The remaining soluble organic material, left over after sedimentation, is aerobically degraded by the bacterial biofilm that is attached to the plants. In the wetland the aquatic plants supply oxygen to the wetland floor through their roots, thereby promoting the aerobic digestion of organic material (Lim, 2002). Some anaerobic degradation of organic material also occurs in the bottom sediments. Various processes occur within the water column, on the plants, in the wetland substrate and in concentrated areas of microbial activity known as biofilms. Biofilms are formed as bacteria and microorganisms attach themselves to the plant stems, the plant roots and the substrate matrix to form a biological filter from the water surface to the wetland floor. As water passes through the thick growth of plants, it is exposed to this living biofilm, which provides a treatment process similar to that found in conventional treatment plants (Watson et al., 1989). 43 (c) Nitrogen Removal Nitrogen (N) can exist in various forms, namely ammoniacal nitrogen (NH3 and NH4+), organic nitrogen and oxidized nitrogen (NO2- and NO3-). There are several possible mechanisms for nitrogen removal such as plant uptake, nitrification, denitrification, soil adsorption and volatilization (Watson et al., 1989; Lim et al., 2002 and Paredes, 2003). It is clear that the main role for nitrogen removal is played not by plants but microorganisms. Wetlands promote the process of nitrification or denitrification which removes nitrogen from the water. Organic Nitrogen is mineralized to NH4+-N in both oxidized and reduced soil layers. The oxidized layer and the submerged portions of plants are important sites for nitrification in which NH4+ is converted to NO2--N by Nitrosomonas and eventually to NO3--N by Nitrobacter bacteria. Figure 2.11 depicts nitrogen transformation in wetland system. At higher pH, some NH4+ exists in the form of NH3 and it lost to the atmosphere by the volatilization process. NH3 Atmosphere Water N2, N2O Volatilization Influent NH4+-N Aerobic sediment (Oxidized Org.N zone) (a) NH4+-N (b) Nitrification NO2--N NO3--N (a) NH4+-N Plant uptake Sorption Plant Plant uptake (b) Anaerobic sediment (reduced zone) Effluent uptake Plant uptake Sedimentation Org.N Nitrification NO2--N NO3--N - NO3 -N Microbial assimilation Cation exchange complex Leaching Denitrification N2 N2O Note: (a) Decomposition or Ammonification (b) Microbial uptake Figure 2.11 : Nitrogen transformation in wetland system (Lim and Polpraset, 1996) 44 Nitrate nitrogen (NO3--N) in the reduced zone is removed through denitrification, leaching and some plant uptake. It is however replenished by NO3from the oxidized zone by diffusion. At the root soil interface, atmospheric oxygen diffuses into the rhizosphere through the leaves, stems, rhizomes and roots of the wetland plants thus creating an aerobic layer similar to that existed at the media water or media air interface. Nitrification takes place in the aerobic rhizosphere where NH4+ is oxidized to NO3- which is either taken up by the plants or diffuses into the reduced zone where it is converted to N2 and N2O by the denitrification process (Lim, 2002). This reaction is catalyzed by the denitrifying bacteria Pseudomonas spp. and other bacterias (Mashhor et al., 2002). (d) Phosphorus Removal Many treatment wetlands have been shown to be successful at retaining phosphorus (Kadlec and Knight, 1996; Reddy et al., 1983). Phosphorus removal in wetlands is based mainly on the phosphorus cycle and can involve a number of processes such as adsorption onto soil and organic matter, filtration, sedimentation, assimilation or plant uptake, complexation or precipitation reactions with calcium, Ca2-, magnesium, Mg2+, Fe3+ and Mn2+ (Renee, 2001; Fraser et al., 2004; Huett et al., 2005). Plant uptake may be significant in systems where the area specific loading rate is low. Therefore, phosphorus removal in wetlands is less effective than nitrogen. Phosphorus removal in many wetlands and aquatic plant systems is not very effective because of the limited contact opportunities between the wastewater and the soil (Aeslina, 2004). Adsorption and precipitation are the major removal pathways when the hydraulic retention times are longer and finer-textured soils are being used. Adsorbed phosphorus can be held tightly and is generally resistant to leaching (Lim, 2002). (e) Heavy metal Removal Heavy metals are common environmental pollutants. Metal contamination of soils and waters has a severe impact on the environment and human health. Kadlec and Knight (1996) report the removal of several metals in treatment wetlands, including aluminium, arsenic, cadmium, copper, iron, manganese, mercury, nickel, 45 silver and zinc. Metals are removed in treatment wetlands by three major mechanisms (Kadlec and Knight, 1996); binding to soils, sediments, particulates, and soluble organics by cation exchange and chelation; precipitation as insoluble salts, principally sulfides and oxyhydroxides and uptake by plants, including algae and by bacteria. Removals of heavy metal occur mainly through adsorption and precipitation and to a minor extent through plant uptake for some metals. Metals are retained in the soil profile or the sediments or substratum. Metals can precipitate out as sulfides and carbonates, or get taken up by plants (Renee, 2001). Figure 2.12 shows the summary the major physical, chemical and biological processes controlling contaminant removal in wetlands. Figure 2.12 : Summary of the major physical, chemical and biological processes controlling contaminant removal in wetlands (Lim, 2002) 2.9 Wetland Plant In selecting plants for use in a constructed wetland it is necessary to consider the factors that affect their natural distribution both overall within the state and locally, as these will have a major impact on the success of the plants that are used for wetland planting. Wetland vascular plants are generally categorized based on 46 their growth form. Types of wetland plants can be classified into three broad types as shown in Figure 2.13. These broad types are; floating, submerged and emergent plants (Mashhor et al., 2002). Figure 2.13 : Types of wetland plants (Mashhor et al., 2002) The floating plants that are free floating and not attached to any substrate. A widespread family of free-floating plants is the Lemnaceae, which includes the genera Lemna (duckweed), Wolffiella and Wolffia (water meal). Also included in the floating plants are larger species, such as Eichhornia crassipes (water hyacinth) and Pistia stratiotes (water lettuce) (Cronk and Fennessy, 2001). Both have extensive branching roots that hang down into the water column. Besides the roots role in absorbing nutrients, they also serve as a weight that helps stabilize the plant on the water. The submerged plans that are attached to the substrate or free floating but whose leaves and stems are permanently submerged. It includes plants whose flowers may be emergent. In submerged species, all photosynthetic tissues are normally underwater. Examples of submerged species include Hydrilla verticillata (hydrilla) and Ceratophyllum demursum (coontail) (Cronk and Fennessy, 2001). Submerged plants take up dissolved oxygen and carbon dioxide from water column and many are able to use dissolved bicarbonate (HCO3-) in photosynthesis as well. Rooted submerged species acquire the majority of their nutrients from the sediment, although some nutrients, particularly micronutrients, may be absorbed from the water column (Cronk and Fennessy, 2001). 47 The emergent plants, those rooted in the soil and emerge the water surface have a higher potential in wastewater treatment because they can serve as microbial habitat and as a filtering media (Mashhor et al., 2002). An example of emergent plants includes Scirpus longii (bulrush), Typha latifolia (cattail) and Pragmites communis (reeds) (Kadlec, 1999). Recent research in use of constructed wetlands that water hyacinth (Eichhornia crassipes) is also useful for metals uptake. Study by Thien (2005), water hyacinth had higher capacity to accumulate heavy metals in roots than leaves. 2.10 Role of Wetland Vegetation Plants are an integral part of the effluent treatment processes in constructed wetlands (Brix, 1997). The plant transfer oxygen through their root and rhizome systems to the bottom of treatment basins and providing a medium beneath the water surface for attachment of microorganisms that perform most of biological treatment (Mashhor et al., 2002). Several processes are envisioned as being effective in pollutant reduction; phytoextraction, phytostabilization, transpiration stripping, and rhizofiltration (Kadlec, 1999). In particular, for leachate context, vegetation fosters and provide several storage and reduction mechanisms. Phytoextraction refers to plant uptake of toxicants, which is known to occur and has been studies in the storm water and mine water wetland context (Kadlec, 1999). However, in many cases the contaminant is selectively bound up in below ground tissues, roots and rhizomes, and is not readily harvested. For example, metals are taken up by plants, and in many cases stored preferentially in the roots and rhizomes (Sinicrope et al., 1992). Phytostabilization refers to the use of plants as a physical means of holding soils and treated matrices in place. This process is also one of the chief underpinnings of treatment wetlands, as it relates to sediment trapping and erosion prevention in those systems (Kadlec, 1999). Wetland plants possess the ability to transfer significant quantities of gases to and from their root zone and the atmosphere 48 (Brix, 1997). Rhizofiltration refers to a set of processes that occur in the root zone, resulting in the transformation and immobilization of some contaminants. The macrophytes growing in constructed wetlands have several properties in relation to the treatment processes that make them an essential component of the design. The most important effects of macrophytes in relation to the wastewater treatment processes are the physical effects that the plant tissues give rise to (such as erosion control, filtration effect and the provision of surface area for attached micro organisms). The metabolism of the macrophytes (such as plant uptake and oxygen release) affects the treatment processes to different extents depending on design. The macrophytes have other site specific valuable function, such as providing a suitable habitat for wildlife and giving systems an aesthetic appearance. The major roles of macrophytes in constructed wetlands are summarized in Table 2.8. Table 2.8 : Roles of macrophytes in constructed wetlands (Mashhor et al., 2002) Macrophyte Property Role in treatment process Aerial plant tissue Light attenuation: reduce growth of phytoplankton Reduce wind velocity: reduces risk of resuspension Aesthetically pleasing appearance of system Storage of nutrients Plant tissue in water Filtering effect: filter out large debris Reduce current velocity: increases rate of sedimentation, Reduces risk of resuspension Provide surface area for attached biofilms Excretion of photosynthetic oxygen: increases aerobic degradation Uptake of nutrients Roots and rhizomes in the sediment Provide surface for attached bacteria and micro-organisms Stabilizing the sediment surface: less erosion Prevents the medium from clogging Release of oxygen increase degradation and nitrification Uptake of nutrients Release of antibiotics 49 2.11 Application of Constructed Wetlands in Treating Landfill Leachate Leachate composition depends on the type and quantity of materials placed in the landfill and on the time since placement (Crites, 2005). Thus, characterization of the leachate is essential for proper wetland design because it can contain high concentrations of BOD, ammonia, metals, high or low pH, and possibly priority pollutants of concern. In addition, the nutrient balance in the leachate may be inadequate to support vigorous plant growth in the wetland and supplemental potassium, phosphorus, and other micronutrients may be necessary (Crites, 2005). Many researchers are involved in treating landfill leachate using constructed wetland. A study by Rafidah (2003) reported that the pollutants removal efficiency for S. sumantrensis was BOD (94%), COD (92%), Fe (89%), Zn (90%), Mn (89%) compared to S.mucronatus that removed BOD (98%), COD (95%), Fe (95%), Zn (90%), Mn (91%) by using FWS constructed wetland system. In this study, the author was remarked that the removal rate for nutrient and heavy metal depends directly with time. The more the contact time between leachate and vegetation in the wetland system, was better the removal rate. El-Gendy (2003) reported on landfill leachate treatment by a FWS constructed wetland with water hyacinth (E.crassipes) and salvinia. From this study, the removal efficiency of pollutants in leachate using water hyacinth was more 80% in TKN (91%), total ammonia (100%), total reactive phosphorus (97%) and total iron (84%). Salvinia plants died after the first day of experiments. Ammonia was removed completely from the system incorporating water hyacinth after 21 days of experiment. Water hyacinth therefore out performed salvinia in leachate treatment. A study by Lee (2004) was reported that horizontal SSF constructed wetland with T.angustifolia has high performance in treating ammonical nitrogen with 80% removal efficiency compare to phosphorus with about 65% removal. The plant uptake of Chromium, Cr and cadmium, Cd was 91.7% and 81.8% respectively with more than 80% Cd retained in plant leaves. Vegetation played an important role in nutrient removal. Beside that, Lee (2004) also concluded that the nutrient removal 50 efficiency could be affected by process variables such as HLR, HRT and mass loading rate. Recently, study by Thien (2005) clearly demonstrates the FWS constructed wetland system was proven effective in pollutants removal in leachate treatment. In her study, she was mentioned that wetland of 100% and 50% leachate concentration showed high removal efficiency for BOD, NO3-N, Fe and Mn compared to 25% leachate concentration wetland. In FWS constructed wetland with 100% leachate concentration, the removal efficiency of BOD (74.07%) and Fe (100%) respectively. While, in FWS constructed wetland with 50% leachate concentration, the removal efficiency of NO3-N and Mn were 64.51% and 53.13% respectively. Beside, the study showed Eichhornia crassipes had higher capacity to accumulate heavy metals in roots than leaves. Table 2.9 and Table 2.10 showed the summary of wastewater pollutants removal in constructed wetland and leachate pollutants removal in constructed wetland, respectively. 51 Table 2.9 : Wastewater pollutants removal in constructed wetland System Type Constructed wetlands systems under different seasons. Horizontal sub-surface flow (HFCWs) and hybrid constructed wetlands systems FWS and SSF constructed wetlands under under high HLR in range 1.57 to 1.95 m/day. Type of Influent Finding References Domestic wastewater Comparisonof mean inlet and outlet concentrations showed that the constructed wetland system could effectively reduce the output of SS (71.8%), BOD5 (70.4%), COD (62.2%), total coliform (99.7%) and fecal coliform (99.6%). However, the percent reduction of ammonia nitrogen was relatively low (40.6%), and total phosphorus showed the least efficient reduction (29.6%). BOD5 and COD removal was more efficient in spring and summer than in autumn and winter whereas ammonia nitrogen and total phosphorus removal was more efficient in summer and autumn than in spring and winter. Song et al. (2006) Municipal sewage HFCWs provide high removal of organics and suspended solids but removal of nutrients is low. Removal of nitrogen is limited by anoxic/anaerobic conditions in filtration beds which do not allow for ammonia nitrification. Phosphorus removal is restricted by the use of filter materials (pea gravel, crushed rock) with low sorption capacity. However, hybrid systems are comprised most frequently of vertical flow (VF) and HF systems arranged in a staged manner. HF systems cannot provide nitrification because of their limited oxygen transfer capacity. VF systems, on the other hand, do provide a good conditions for nitrification but no denitrification occurs in these systems. Vymazal (2005) Shrimp aquaculture wastewater The results showed that the FWS-SSF constructed wetlands effectively Lin et al. (2005) removed BOD5 (37-54%), SS (55-66%) and NO2-N (83-94%), total ammonia (64-66%) under high HLR. The high HLR affected the performance of pollutants removal. The study also showed that high HLR diminished the contact time for nitrate and denitrifying bacteria, thus decreasing the performance of wetland for denitrification. 52 Table 2.9 (Continued) System Type Type of Influent Finding References Two combined systems composed of a vertical flow bed planted with Phragmites and a horizontal flow bed planted with Typha. Domestic Wastewater he system shows a good performance in the bacterial removal (90%) as well for planted and unplanted system. Nitrogen removal in planted system was greater than in unplanted one especially for nitrogen Kjeldahl (27 and 5%) and nitrogen ammonia (19 and 6%). Whereas, removal of nitrate-nitrite in planted system is less than in unplanted one (4 and 13%). Keffala and Ghrabi (2005) constructed wetlands with Cyperus papyrus (papyrus) and Miscanthidium violaceum (K.Schum.) in tropical climate Domestic sewage wastewater Papyrus root structures provided more microbial attachment sites, sufficient wastewater residence time, trapping and settlement of suspended particles, surface area for pollutant adsorption, uptake, assimilation in plant tissues and oxygen for organic and inorganic matter oxidation in the rhizosphere, accounting for its high treatment efficiency. Papyrus showed higher ammonium-nitrogen and total reactive phosphorus (TRP) removal (75.3% and 83.2%) than Miscanthidium (61.5% and 48.4%). Plant uptake and storage was the major factor responsible for N and P removal in treatment Kyambadde et al. (2004) Small-scale wetland mesocosms (400L each) containing two treatment designs (a mixture of Typha, Scirpus, and Juncus species; Domestic wastewater Significant differences between influent and effluent water quality for the vegetated wetlands (p>05) were observed in TSS, BOD and TKN. Increased DO and reduction in fecal coliform, enterococcus, Salmonella, Shigella, Yersinia, and coliphage populations also were observed in vegetated wetlands. Greatest microbial reductions were observed in the planted mesocosms compared to those lacking vegetation. Hencha et al. (2003) 53 Table 2.9 (Continued) System Type Type of Influent Finding References Cameron et al. (2003) FWS with Typha latifolia and Scirpus acutis Municipal sewage lagoon The FWS cells achieved removals as follows: BOD (34%), ammonia and ammonium (52%), TKN (37%), TSS (93%), TP (90%), ortho-P04 (82%) and E. coli (58%). The vegetated filter strip treating the effluents from the wetland cells achieved removals as follows: biochemical oxygen demand (18%), ammonia and ammonium (28%), TKN (11%), TSS (22%), TP (5%) and F. coli (22%). It may therefore serve as an additional treatment stage further. Horizontal SSF with Phragmites australis Domestic Sewage Mantovi et al. (2003) Removal of suspended solids and organic load was above 90%, while those of the nutrients N and P were about 50% and 60%, respectively. Nitrogen removal is usually not very efficient in horizontal SSF wetlands, due to insufficient oxygen supply. The role of plants in the CWs is limited but essential. Absorption by plants was not the main route through which the contaminants were removed or transformed, but certainly the presence of plants was fundamental for establishing a heterogeneous environment. FWS and SSF constructed wetlands under various HLR (1.8 to 13.5 cm/day) Fishpond water (shrimp aquaculture wastewater) The result showed that nitrogen removals were excellent, with efficiencies of 86% to 98% for ammonia nitrogen (NH4-N) and 95% to 98% for total inorganic nitrogen (TIN). Phosphorus removal of 32% to 71% occurred, with the efficiencies being inversely related to hydraulic loading. The study was concluded that the FWS wetland removed most inorganic nitrogen, whereas the SSF wetland removed phosphate at a rate equal to or even greater than the FWS. Lin et al., (2002) 54 Table 2.10 : Leachate pollutants removal in constructed wetland System Type Type of Influent Findings References FWS constructed wetland with magnetic field and Eichhornia crassipes. Treated leachate The results showed continuous circulation magnetic field with wetland (CRM-W) systems can reduce up to 60% of ammonia nitrogen removal, 68.7 % of ferum and 60% of manganese after 6 hours of treatment. Wetland was able to remove 99% of nitrate nitrogen, 96% of ammonia nitrogen and 83% of BOD after end of experiment. Noor Ida Amalina (2006) Horizontal SSF constructed wetland with Typha angustifolio Treated leachate The study was conducted to determine removal of nutrient treated by SSF with different concentration, HRT and sand ratios. Removal efficiency of AN and nitrate by Typha angustifolio ranges from 42.6-88.9%. Removal of BOD and COD by horizontal SSF constructed wetland ranges from 62.6-72.8% and 64.5-85.7%, respectively. The HRT was found to affect the results, about 10-30% of differences in removal efficiency for longer HRT compare to shorter HRT. Chew (2006) Constructed wetland with floating plant (E.crassipes) Treated leachate This study demonstrates the FWS constructed wetland system with 100% and 50% leachate concentration showed high removal efficiency for BOD, NO3-N, Fe and Mn compared to 25% leachate concentration wetland. In FWS constructed wetland with 100% leachate concentration, the removal efficiency of BOD (74.07%) and Fe (100%) respectively. While, in FWS constructed wetland with 50% leachate concentration, the removal efficiency of NO3-N and Mn were 64.51% and 53.13% respectively. The study showed E.crassipes had higher capacity to accumulate heavy metals in roots than leaves. Thien (2005) FWS with Typha latifolia, Phragmites australis and Elodea canadensis Leachate Submerged plant E.canadensis had a greater capacity for denitrification, because it offered higher carbon availability or other species-specific advantages, such as suitable attachment surfaces. The potential denitrification rates were more than three times higher in the cores containing E. canadensis than in the cores with T.latifolia and P.australis Bastviken et al. (2005) 55 Table 2.10 (Continued) System Type Type of Influent Findings References Horizontal SSF constructed wetland with T.angustifolia Treated leachate A study was reported that horizontal SSF constructed wetland with T.angustifolia has high performance in treating AN with 80% removal efficiency compare to phosphorus with about 65% removal. The plant uptake of Chromium, Cr and cadmium, Cd was 91.7% and 81.8% respectively with more than 80% Cd retained in plant leaves. Vegetation played an important role in nutrient removal. Beside that, Lee (2004) also concluded that the nutrient removal efficiency could be affected by process variables such as HLR, HRT and mass loading rate. Lee (2004) FWS constructed wetland with water hyacinth (E.crassipes) and salvinia. Landfill leachate This study reported on landfill leachate treatment by a FWS constructed wetland with water hyacinth (E.crassipes ) and salvinia. From this study, the removal efficiency of pollutants in leachate using water hyacinth was more 80% in TKN (91%), total ammonia (100%), total reactive phosphorus (97%) and total iron (84%). Salvinia plants died after the first day of experiments. Ammonia was removed completely from the system incorporating water hyacinth after 21 days of experiment. Water hyacinth therefore out performed salvinia in leachate treatment. El-Gendy (2003) FWS constructed wetland with S. sumantrensis Landfill leachate A study reported that the pollutants removal efficiency for S. sumantrensis was BOD (94%), COD (92%), Fe (89%), Zn (90%), Mn (89%) compared to S.mucronatus that removed BOD5 (98%), COD (95%), Fe (95%), Zn (90%), Mn (91%) by using FWS constructed wetland system. In this study, the author was remarked that the removal rate for nutrient and heavy metal depends directly with time. The more the contact time between leachate and vegetation in the wetland system, was better the removal rate. Rafidah (2003) 56 Table 2.10 (Continued) System Type Type of Influent Findings References Dual system (FWS-SSF) constructed wetland with Phragmites australis reeds. Municipal landfill leachate The data demonstrated that removal rates for 14 constituents ranged from 49% to 100%. The removal efficiencies exceeded 90% for most metals species, total phosphorus, ammonium, BOD and volatile organic compound (VOCs). Removal rates were lowest for the major inorganic ions and barium. The results indicate the (1) total iron removal was 98% (2) nitrogen removal (mostly as ammonium) was 91%; and (3) total phosphorus removal was 99% and was mainly through plant uptake and concentration in plant tissues, especially the rhizomes. Eckhardt et al. (1999) SF with Scleria sumantrensis Retz. and Scirpus mucronatus Treated leachate S.mucronatus accumulated more Zn, Mn, and Fe in the roots than S.sumantrensis Retz. S.mucronatus had higher metal absorption compared to S.sumantrensis Retz.. The heavy metal concentration was higher in the root zones compared to the stem zones for Fe, Zn and Mn. The high accumulation of heavy metal in S.mucronatus was due to the plant that had many shorter roots that were able to create aeration zones for heavy metal uptake. Krishnan (2002) Pre-treatment using FWS constructed wetland Municipal landfill leachate The treatment wetland consists of a primary treatment lagoon and ten FWS wetlands cells. Chemical and biological data indicated that the wetland treatment system has provided a high level of landfill treatment. For example, BOD was reduced by an average of 96%, while TSS, iron and TKN concentration were decreased by more than 95%, on average. The FWS constructed wetland has proved to be sustainability means for removal metals from leachate during an operational period over 5 years. Debusk, W.F. (1999) 57 2.12 Conclusion Leachates from landfill vary in their hazardous characteristics and include numerous pollutants and phenolics. Leachates are well known as a particular sort of problematic wastewater both from the viewpoint of eco-toxicity and the treatment technique. Methods developed for treatment of landfill leachates can be classified as physical, chemical and biological, which are usually, used as a combination in order to improve the treatment efficiency. The treatment of leachates by natural systems seems to be environmentally sustainable for the treatment of many constituents. The high productivity and nutrient removal capability of wetlands has created substantial interest in their potential use for improving leachate water quality. It is probable that they would be part of an integrated natural system, comprised of aquatic and terrestrial components together with wetlands. Constructed wetlands can be built with a much greater degree of control, thus allowing the establishment of experimental treatment facilities with well-defined composition of substrate, type of vegetation and flow pattern (Moshiri, 1993). Constructed wetlands for leachate treatment have several advantages compared to conventional secondary and advanced leachate treatment systems. Some of these advantages are; low cost of construction and maintenance; low energy requirements; being a “low technology” system, they can established and run by relatively untrained personnel; and the systems are usually more flexible and less susceptible to variations in loading rate than conventional treatment systems (Moshiri, 1993). A constructed wetland was an ecological system that combines physical, chemical and biological treatment mechanisms in removing pollutants from leachate wastewater as it flows through the wetland (Kadlec and Knight, 1996; Lim, 2002). These systems effectively reduce total suspended solids, BOD, nitrogen (ammonia and total nitrogen), phosphorus (P) and fecal coliform (Neralla et al., 2000). However, the major disadvantages of constructed wetland treatment systems are the increased land area required, compared to conventional systems and the possible decreased performance during winter in temperate regions (Moshiri, 1993). But, the use of constructed wetlands has considerable promise for the control of a 58 large number of organic compounds, which are the subject of landfill leachate regulation. Therefore, the disposal of wastewater especially landfill leachate into constructed wetlands is an especially attractive alternative to conventional wastewater treatment technologies for small to medium sized communities, in sparsely populated areas and in developing countries. Treatment wetlands are either natural or constructed wetlands almost completely covered with emerging macrophytes or they are being managed as water quality improving systems. Several studies also have shown the important role played by macrophytes in constructed wetlands (Brix, 1997). Macrophytes enriched their substrate with oxygen and reduce filter erosion. In this study, Limnocharis flava and Eichhornia crassipes were used as aquatic plants. These plants were selected as the wetland plants because of their local availability (available at nearest study area), easy to control and maintain, and have capability to survive with leachate constituents. The functions and ability of these plants were proved, as it is one of the plants used in Putrajaya wetlands. Its ecological function is to reduce suspended solids and chemical pollution; biodegradable organic pollutants in water which is in need in leachate treatment. The increasing application of treatment wetlands coupled with increasingly strict water quality standards has been an incentive for the development of better design tools. This study reviews the application of constructed wetland on leachate treatment using combined SSF and FWS constructed wetland system and planted with Limnocharis flava and Eichhornia crassipes. The focus of this study is on the removal efficiency of constructed wetlands as well as standard water variables such as SS, turbidity, nutrients and heavy metals. CHAPTER 3 METHODOLOGY 3.1 Introduction This chapter describes several research design, operational framework, method and experimental procedure used in this study. The activity such as in engineering approach (basic knowledge and understanding activities, design parameters or verification, and process design and set-up the configuration) and mathematical analysis are the main approach to be involved simultaneously. 3.2 Research Design and Operational Framework The research methodology was divided into 6 phases as shown in Figure 3.1. This study was focussed on the ability of SSF-FWS constructed wetland systems in removing nutrients and heavy metals in leachate. Control was set up which was the constructed wetland. The control system is important to carry out to compare the effectiveness between constructed wetland with plants and without plants. The wetlands systems are constructed using fiber glass tank. The experiments were carried out at Environmental Engineering Laboratory, Faculty of Civil Engineering, Universiti Teknologi Malaysia. 60 Phase 1: Literature Review Determine objectives and scope of study Theoretical approach and literatures Types of constructed wetland Wetland plants Phase 2: Process Design and Set up the Experiment Set up of experimental scale SSF-FWS constructed wetland systems Phase 3: Experimental Works Control System Planted System Without plant HLR = 0.13 m/cycle/day Leachate (50% concentration) Constructed wetland (Planted) HLR = 0.13 m/cycle/day Leachate (50% concentration) Phase 4: Sampling and Preservation Phase 5: Data analysis Based on the parameter observed in the experiment Removal efficiency of pollutants Phase 6: Recommendation and Conclusion Figure 3.1 : Frameworks and experimental design 61 3.3 Leachate Sample Collection and Preparation Before any experiment can be run in the constructed wetlands, leachate sample need to be collected. For this study, raw leachate (without treatment) sample was taken from Pasir Gudang Sanitary Landfill. Some equipment needs to be prepared and 4 containers (750 liter) of leachates were collected in every collection trips. Once the leachate sample arrives at the laboratory, the leachate was stored at 4°C to minimize any further change that might occur in its physiochemical and biological properties until the experiments analyses were carried out within a week. Before run the experiments, the characterizations of the raw leachate samples in this study were analysed. 3.4 Experiment Set up The experiments were conducted using two lab-scale constructed wetland systems. Planted system was set-up a two-stage lab-scaled system comprised of a SSF and FWS constructed wetland plants, while the Control system is without plants. The equipment consists of 4 tanks which are storage tank, SSF tank, FWS tank and settling tank. Each tank was fabricated in trapezoidal shape with dimension of 0.23 m width, 0.43 m length and 0.3 m depth. SSF and FWS constructed wetland systems were arranged in series and operated for around 3 weeks (18 days). Before leachate sample were poured in storage tanks, the sample was diluted to the concentration of 50% leachate and 50% tap water. After that, diluted leachate was poured into storage tank of about 18 liter before flow into the SSF tank. The plastic valve installed at storage tank was adjusted to control the flow rate of the leachate and to make sure the entire tank were fed with leachate effluent at a constant flow rate which is designed accordingly the HLR (0.13 m/cycle/day) and to obtain a hydraulic retention time (HRT) of 7 hours per cycle for SSF tank and 10 hours per cycle for FWS tank. The daily HLR was adjusted and checked manually using a measuring cylinder and a stopwatch to obtain and maintain a continuous flow rate. The HRT of each bed was regulated throughout 62 the time that the valves remained opened during irrigation. Leachate wastewater was continuously daily return feed (around 3 weeks) into the SSF wetland directly from the storage tank and then passed through the FWS wetland and settling tank via gravity flow. The elevation level of the SSF wetland was higher than the FWS wetland, to allow gravity flow. The schematic plans of laboratory equipments for SSF and FWS constructed wetland are shown in the Figure 3.2. Control Planted 1 1 A A 2 4 Daily Return Daily Return B B 3 5 C C 6 6 Figure 3.2 : Schematic diagram of SSF-FWS constructed wetland used in experiment. (1) Storage tank; (2) Media without plant; (3) water tank without plant; (4) SSF tank with Limnocharis flava (5) FWS tank with Eichhornia crassipes; (6) Settling tank; and (A) Sampling location for the influent; (B) sampling location for the SSF effluent; (C) sampling location for the FWS effluent. 63 Control Planted STORAGE TANK SSF B Limnocharis flava SSF B FWS C SETTLING TANK Eichhornia crassipes FWS C SETTLING TANK Figure 3.3 : Arrangement of SSF-FWS constructed wetland systems Figure 3.3 shows the leachate was treated in SSF-FWS constructed wetland systems. Sampling ports were set up at the inlet and outlet of the SSF wetland and at the outlet of the FWS wetland as illustrated above in Figure 3.3. The SSF and FWS tanks were contained with the same quantity of leachates and the experiments were conducted under natural environmental conditions which were exposed to sunlight as shown in Figure 3.4. Detail of experimental design in this study is summarized in Table 3.1. 64 Table 3.1 Summary of experimental design System : 50% Leachate + 50% Tap water Type of flow Q (m3/day) HLR (m/day) HRT (hours) Duration Type of plants Continues flow (SSF constructed wetland system) 0.014 (per cycle) 0.13 (per cycle) 7 (per cycle) 18 days Limnocharis flava Continues flow (FWS constructed wetland system) 0.014 (per cycle) 0.13 (per cycle) 10 (per cycle) 18 days Eichhornia crassipes Figure 3.4 : Two-stage lab-scaled system comprised of a SSF and FWS constructed wetland located outside of the building in an open area 3.5 Plants In this study, yellow bur-head (Limnocharis flava) and water hyacinth (Eichhornia crassipes) were used as aquatic plants. The SSF wetland was planted with Limnocharis flava. And, the FWS wetland was planted with floating Eichhornia crassipes plants. SSF wetlands are planted by hand. The planting 65 densities were 10 plants of Limnocharis flava for the SSF tank and 7 plants of Eichhornia crassipes for the FWS tank. These plants were selected as the wetland plants because of their local availability (available at nearest study area), easy to control and maintain, and have capability to survive with leachate constituents. A short description about Limnocharis flava and Eichhornia crassipes are shown in Figure 3.5 and Figure 3.6. Scientific Name : Limnocharis flava Local names : Yellow bur-head (English), Yellow sawah lettuce, Sawah flowering rush, Paku rawan (Malay) Family : Limnocharitaceae Synonyms : Limnocharis emarginata, Alisma flava, Damasonium flavum Limnocharis laforesti, and Limnocharis plumieri . Description : Perennial herb to 1 m high and rooting in mud. Leaves broadovate, 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, horseshoeshaped, to 1.5 mm long with obvious ridges. Dispersal by production of numerous seeds. Habitat : Emergent, L. flava inhabits shallow swamps, ditches, pools and wet rice fields, occurring usually in stagnant fresh water. Figure 3.5 : Short description of Limnocharis flava (Waterhouse and Mitchell, 1998) 66 Scientific Name : Eichhornia crassipes Local names : Water hyacinth (English), Keladi bunting (Malay) Family : Pontederiaceae Synonyms : Eichhornia speciosa, Heteranthera formosa, Piaropus crassipes Piaropus mesomelas and Pontederia crassipes Description : E. crassipes is a free-floating aquatic macrophyte growing generally to 0.5 m in height. The individual plants consist of several leaves in rosettes and are connected by stolons. The leaf petiole is usually inflated, spongy, and up to 20 cm long. The leaf blades are thickened, leathery, 2 to 15 cm long and 2 to 10 cm wide, sub orbicular, ovate or broadly elliptic with parallel veins. Their roots are long, fibrous, branched root stocks hang from the underside of the plant. Habitat : Grow in a wide variety of aquatic habitats including lakes, ponds, rivers, wetlands and marshes. It will grow most prolifically in water of high nutrient content; it has been used in wastewater treatment facilities. Figure 3.6 : Short description of Eichhornia crassipes (Waterhouse and Mitchell, 1998) 67 3.6 Media In this study, the media used in the SSF constructed wetlands consists of a layer of coarse stone with 15-20 mm diameter (2 cm), followed by a layer of fine stone with 5-10 mm diameter (1 cm), a mixture of sand and soil with ratio (2:1) (5 cm), a layer of soil at the surface (2 cm) and providing a porosity of 45%. According to Pant et al. (2001), inexpensive materials such as sand for example, can effectively removed phosphorus through sorption and their usage as root bed media can increasing the efficiency of phosphorus removal in constructed wetland. The gravels were cleaned first by washing with tap water before putting into the SSF tank to free from debris which can block the flow of leachate through the media. The water table in the bed was controlled and maintained 1 cm under the media surface by an adjustable outflow pipe leading into a storage tank. 3.7 Sampling and Analysis Water samples were taken two times each week for the duration of the study from the influent and effluent of SSF wetland and at the effluent FWS wetland. Such sampling was usually carried out at around 9 a.m. in each sampling date. After termination of the each different concentration of leachate, the plants leaves and roots were harvested for each constructed wetland and were analysed for heavy metal (Fe and Mn). For roots and leaves, analysis samplings were carried out during initial and after 3 weeks of treatment. 3.8 Analysis Procedure All the laboratory analysis was done in Environmental Engineering Laboratory of Faculty of Civil Engineering, UTM. The samples were analyzed for SS, turbidity, NH4-N, NO3-N, PO43- and heavy metal (Fe and Mn). All the analytical measurements were carried out according to DR/4000 Procedures and Standard 68 Methods (APHA, 2002). A table described the analytical method is shown in Table 3.2. Analysis procedures are described briefly as below: Table 3.2 : The parameter observed in leachate analysis Parameter Method/Equipment Method code Source NH4- N Nessler Method 8038 DR/4000 NO3- N Cadmium Reduction Method 8039 DR/4000 PO43- Molybdovanadate Method 8114 DR/4000 Fe FerroVer Method 8008 DR/4000 Mn PAN Method 8149 DR/4000 Turbidity Attenuated Radiation Method 10047 DR/4000 SS Total Suspended Solids Dried at APHA 2450-B *SA o 103-105 C *SA = Standard Method 3.8.1 Analysis of Heavy Metals in Plant Tissues After termination of the experiments, the plant’s leaves and roots were harvested for each constructed wetland. Then, the leaves and the roots were washed with tap water and distilled water. After that, the plant samples were dried in oven at 105˚C for 24 hour, and the dry weight of each component was measured. The samples were then ground with mortar and pestle to a fine powder. And 0.5 - 3.0 g of the ground plant sample was put inside the conical flask 250 ml and 50 ml of 2 M hydrochloric acid was added in for plant digestion. The sample mixture was then shaken overnight with orbital shaker. After that, the mixture was centrifuged for 20 minutes and filtered with cellulose acetate membrane 0.45 µm (Markert, 1994). The filtrate was then analyzed for heavy metal (total iron and manganese) according to the method mentioned above in Table 3.2. Figure 3.7 shows plant digestion for analysis of heavy metal in plant tissues. 69 Figure 3.7 : Plants digestion for root and leaves. 3.9 Performance Evaluation Pollutant loading rate (g/m2.day) was calculated by multiplying the hydraulic loading rate (m/day) by the influent pollutant concentration (mg/L). Pollutant 2 removal rate (g/m .day) was defined as hydraulic loading rate times the difference in concentration between the influent and the effluent. The first-order plug flow kinetic reaction was applied accordingly: Ci Co = k t) e (- Where, Ci = effluent pollutant concentration, mg/L Co = influent pollutant concentration, mg/L k = first-order removal rate constant, day-1 t = nominal hydraulic retention time, day (3.1) CHAPTER 4 RESULTS AND DISCUSSIONS 4.1 Introduction In this chapter, the results obtained from the two lab-scales of SSF-FWS constructed wetland systems observation and experiment will be discussed in details. The experiments were done two times and run for 18 days to get the data. The entire results were analysed and plotted from the average data. The experiments period were from July to end of August 2006. Water samples were taken two times each week for the duration of the study and were analysed immediately. In this study, the leachate analysis consists of nutrients, SS, turbidity, heavy metals removal. All data will be carried out in graphical approach to evaluate the specific analysis processes. Thus, an extensive discussion had been concluded in the behaviour obtained. The analysis considers the removal efficiency and performance of the planted and unplanted system as the control in landfill leachate treatment. Analysis of variance (ANOVA) has been used to reveal significant differences between Control and Planted system. Statistical significance differences were tested at p≤0.05 (95% levels of significance). Individual system was analysed to discover the common trends for individual wetlands. Removal efficiency from all SSF-FWS constructed wetland was compared to evaluate overall performance trends representative of this SSF-FWS constructed wetlands system design. 71 4.2 Basic Characteristics of the Landfill Leachate The characterizations of the raw leachate samples in this study were analysed before run the experiments. Basic characteristics of the influent landfill leachate from the Pasir Gudang Landfill site are shown in Table 4.1. The inlet concentration of NH4-N, NO3-N, PO43-, Fe, Mn, turbidity and SS were very high. All the nutrients, SS, turbidity and heavy metals analysed are above the water quality standard. The constituents in the leachate may vary depending on waste composition and weather. Table 4.1 : Influent characteristics of the Pasir Gudang leachate Parameter Value (mg/L) Ammonia Nitrogen (NH4-N) 84.5 Nitrate Nitrogen (NO3-N) 35.0 Orthophosphate (PO43-) 87.5 Suspended Solid (SS) Turbidity Ferum (Fe) Manganese (Mn) 160 450 33.68 0.48 4.3 Nutrients Removal Landfill leachate contained high concentration of nutrients as shown in Table 4.1. Therefore, the performance of SSF-FWS constructed wetland system was investigated to determine removal efficiency of nutrients from landfill leachate. Three types of nutrients were studied in this study which was Ammonia nitrogen (NH4-N), Nitrate nitrogen (NO3-N) and Orthophosphate (PO43-). 4.3.1 Ammonia Nitrogen Ammonia nitrogen (NH4-N) is an undesirable constituent of many wastewater discharges because of its toxicity to fish and considerable microbial oxygen demand on receiving waters. NH4-N concentration is considered high in landfill leachate. In 72 this study, the system consisting of SSF-FWS constructed wetland vegetated with Limnocharis flava and Eichhornia crassipes were effective for 18 days in reduction high level of NH4-N. Significant reduction in concentration of NH4-N through the SSF and FWS wetland was achieved after approximately 3 days of operation as NH4-N Co ncentratio n (m g/L) shown in Figure 4.1 and Figure 4.2. 100 Control 90 Planted 80 70 60 50 40 30 20 10 0 0 3 6 9 12 15 18 Time (days) Figure 4.1 : NH4-N concentration profile in Control and Planted system through NH4-N Concentration (mg/L) SSF constructed wetland within 18 days of treatment 100 Control 90 Planted 80 70 60 50 40 30 20 10 0 0 3 6 9 12 15 18 Time (days ) Figure 4.2 : NH4-N concentration in profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 73 All the systems show the high reduction of NH4-N concentration as the time increased. Concentrations of NH4-N through the SSF-FWS wetland were decreased steadily from day 3 to day 18 of operations. Figure 4.3 illustrated that Planted systems have the ability to removed NH4-N faster than Control system. After 18 days of treatment, the removal efficiencies for overall performance in Control and Planted system for the SSF-FWS wetlands were achieved 78.1% and 93.1% respectively. NH4-N removal followed the first order removal model, with rate constants of 0.075 day-1 and 0.137 day-1 in Control and Planted systems. A higher value of removal rate constant, k in Planted system would indicate a better NH4-N removal mechanism compared than in Control system. The ANOVA test did reveal a significant differences p≤0.05 between Control and Planted systems (Refer to Appendix B). It can be concluded that NH4-N level were reduced more efficiently in wetlands containing plants. Control Planted 1.00 0.80 C = 1 . 02 e − 0 .075 t Co C/Co 0.60 0.40 C = 1 . 03 e − 0 .137 t Co 0.20 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.3: Comparison of NH4-N concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland There are several mechanisms for the reduction of NH4-N, which are volatilization, soil adsorption, plant uptake and nitrification (Watson et al., 1989; IWA, 2000; Lim et al., 2002 and Paredes, 2003). Nitrogen transformation takes place in the oxidized and reduced layers of media, the root-media interface and the submerged portion of the emergent plants. At higher pH, some NH4-N which exists 74 in form of NH3 is lost to the atmosphere by the volatilization process (Lim, 2002). NH4-N may be taken up in biota or transformed into nitrate. In addition, because of it’s positively charge, NH4-N can be absorbed onto negatively charged soil particles that can be deposited as sediment (Cronk and Fennessy, 2001). So, this fact was supported the high removal efficiency in Control system. However, such removal is not considered to be a long-term sink because the adsorbed NH4-N is released easily when water chemistry conditions change (Kadlec and Knight, 1996). Wetland plants will assimilate nitrogen as an important part of their metabolism. Limnocharis flava and Eichhornia crassipes have high nutrient assimilative capacity and this mechanism was increased the NH4-N removal. From the observation, the percentage of NH4-N removal in FWS wetland was higher than in SSF wetland. This was because the floating plants tend to diffuse more oxygen through their roots than emergent plants (Cronk and Fennessy, 2001). However, plant uptake rates were only about one third of those reported for this species in experimental systems where plants still in actively spreading (Tanner, 1996). This concluded that plant uptake rates in the systems were almost moderately, but not excessively, above normal levels likely to occur in treatment wetlands. The major pathway for removal of ammonia nitrogen in constructed wetlands is nitrification. Both systems had capability in NH4-N reductions as previously shown in Figure 4.3. This was because the nitrification process was taking place actively in both Control and Planted system. Nitrification process occurs in the oxidized areas of substrate or water column, where NH4-N is oxidized to nitrite nitrogen (NO2-N) by Nitrosomonas and eventually to NO3-N by Nitrobacter bacteria (Cronk and Fennessy, 2001; Lim, 2002). Because the transformation of NH4-N involves microbial processes, NH4-N removal is enhanced during the growing season when high temperature stimulates microbial population growth (Cronk and Fennessy, 2001). However, nitrification processes were controlled by many factors, including temperature, dissolved oxygen, pH, and alkalinity of the water, inorganic source, microbial population and NH4-N concentration (Vymazal, 2005). It is clear that the main role for NH4-N removal is played not by plants but microorganisms. The substrate media such as gravel, soil and sand also support vegetation, provided surface area and retain nutrient for microb. 75 However, the Planted system has greater removal efficiency compared to Control because of the plants uptake and the root of the plants provided aerobic zone for nitrification to be occurred (Lim and Polprasert, 1996). The plants also provided surface areas for microbial attachment (Hammer, 1990). At the root-soil interface, atmospheric oxygen diffuses into the rhizosphere through the leaves, stems, rhizomes and roots of the wetland plants thus creating an aerobic layer. For these reason, vegetated treatment wetlands are more efficient at removing ammonia than unvegetated wetlands. A review by Brix (1997) describes macrophytes plants encourage the assimilation and breakdown of nutrients within a wetlands system. They have the ability not only to bind high amounts of nutrients within their system, but also to create an environment conducive to decreasing nutrients. Macrophytes provide surface area on their stems and leaves, which is necessary for microbial growth. The roots provide a structure for microorganisms to perform the processes necessary for transformation of nutrients. Moreover, roots not only provide a place for microbes but also serve to decrease erosion and increase the levels of oxygen, which provides for the oxidation of toxic substances like ammonia and nitrites. 4.3.2 Nitrate Nitrogen In this study the system consisting of SSF-FWS constructed wetland vegetated with Limnocharis flava and Eichhornia crassipes were effective for 18 days in reduction high level of NO3-N constituents in landfill leachate. During initial stage, reduction of NO3-N concentration through the SSF wetland in Planted system was negligible. NO3-N concentration in the effluent of the SSF wetland was higher than influent concentration as shown in Figure 4.4, resulting in negative removal efficiencies. Reduction of NO3-N concentration through the SSF wetland in Planted system did not occur until around day 3 of operation. However, after approximately 6 days of operation SSF wetland show the improvement in NO3-N removal. Conversely, significant reductions in concentration of NO3-N through the FWS wetland for both systems were achieved after approximately 3 days of operation. 76 Subsequently, the FWS wetland showed consistently low nitrate concentration in its effluent as shown in Figure 4.5. NO3-N concentration in SSF effluent was higher than its influent due to both of systems were not stable at early stage. This is because it begins to acclimatize with its environment (Lin et al., 2002). 45 Control Planted NO3-N Concentration (mg/L) 40 35 30 25 20 15 10 5 0 0 3 6 9 12 15 18 Time (days) Figure 4.4 : NO3-N concentration profile in Control and Planted system through NO3-N Concentration (mg/L) SSF constructed wetland within 18 days of treatment 45 Control 40 Planted 35 30 25 20 15 10 5 0 0 3 6 9 12 15 18 Time (days) Figure 4.5 : NO3-N concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 77 Figure 4.6 shows trend of NO3-N reduction over time. After 18 days of experiment, both systems show higher performance in NO3-N removal. From the graph it can be seen that concentration of NO3-N through the SSF-FWS wetland in both systems decreased steadily from day 3 to day 18 of operations. After 18 days of treatment, the removal efficiencies for overall performance in Control and Planted systems were 77.1% and 96.4% respectively. As depicted in Figure 4.6, the reductions of NO3-N in Planted systems were significantly (p≤0.05) higher than in Control. The removal rate constant (k) for planted constructed wetland are 0.135 day-1 while for Control 0.07 day-1. This study of SSF-FWS wetlands demonstrated that Planted system consistently exhibited greater NO3-N removal than did unplanted Control system. The ANOVA test did reveal a significant differences p≤0.05 between Control and Planted systems as shown in Appendix B. Control 1.00 Planted 0.90 0.80 0.70 C = 1 . 0 e − 0 . 07 t Co C/Co 0.60 0.50 0.40 C = 1 . 05 e − 0 .135 t Co 0.30 0.20 0.10 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.6 : Comparison of NO3-N concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland Studies have shown that NO3-N concentration levels were reduced more efficient in wetlands containing plants. This was because NO3-N is not immobilized by soil minerals and remains in the water column or pore water of the sediments. Previous studies (Ingersoll and Baker, 1998; Baker, 1998) showed that NO3-N removal in wetlands occurred through plant uptake and denitrification. However, 78 denitrification is only one mechanism for NO3-N removal in the FWS wetland. And also, with high NO3-N loading rates typical in treatment wetlands, denitrification is generally considered the dominant mechanism of NO3-N loss. Denitrification is carried out by microorganisms under anaerobic i.e. anoxic conditions, with NO3-N as the terminal electron acceptor and organic carbon as the electron donor (EPA, 1993). That is to say, the reaction occurs in the absence of oxygen and requires an organic carbon source. Also, the low NO3-N levels in planted constructed wetlands can be explained by heterotrophic competition with nitrificants for oxygen (Focht and Verstraete, 1977). Experiments with plants such as Limnocharis flava and Eichhornia crassipes also demonstrated that NO3-N removal from sediments is enhanced in the presence of macrophytes. Gersberg (1986) contends that the high NO3-N removal is due to a stimulation of denitrification by the supply of organic material from the macrophytes. In wetlands, the organic carbon was supplied mainly by the vegetation and it was used as a carbon and energy sources for heterotrophic bacteria, such as the denitrifying bacteria (Bastviken et al., 2005). When sufficient carbon is available for microbial metabolisms, denitrification is enhanced (Watson et al., 1989; EPA, 1993; Cronk and Fennessy, 2001; Lim, 2002). Decomposing wetland plants and plant root exudates are potential sources of biodegradable organic carbon for denitrification (EPA, 1993). This link between vegetation and carbon availability is one of the ecologically critical features of effective treatment of high nitrogen loadings. Consequently, NO3-N later which is either taken up by the plants or diffuses into the reduced zone where it is converted to nitrogen gases, N2 and nitrogen oxide, N2O by the denitrification process (Watson et al., 1989; IWA, 2000; Lim et al., 2002 and Paredes, 2003). Both N2 and N2O are released to the atmosphere. 4.3.3 Orthophosphate Orthophosphate (PO43-) concentration was high in the initial leachate landfill as previously shown in Table 4.1. In this study, the system consisting of SSF-FWS constructed wetland vegetated with Limnocharis flava and Eichhornia crassipes 79 were effective for 18 days in reduction high level of PO43-. From the observation, PO43- concentration reduction in the SSF effluent were stable and consistently lower than in the FWS effluent, and it followed the trend of the FWS effluent. Figure 4.7 and Figure 4.8 shows PO43- concentration in Control and Planted system through the SSF and FWS constructed wetland. Respectively, both systems show the significant reductions in concentration of PO43- through the SSF-FWS wetland. Control Planted 100 3- PO4 Concentration (mg/L) 90 80 70 60 50 40 30 20 10 0 0 3 6 9 12 15 18 Time (days) Figure 4.7 : PO43- concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment Control Planted 30 20 15 10 3- PO4 Concentration (mg/L) 25 5 0 0 3 6 9 12 15 18 Time (days) Figure 4.8 : PO43- concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 80 Figure 4.9 represents overall performance of Control and Planted through SSF-FWS constructed wetland systems in removing of PO43-. After 18 days of operation, both systems had the capability to reduce PO43- concentration in leachate. From the graph it can be seen that concentration of Fe decreased more rapidly after 3 days of operation and decreased steadily from day 3 to day 12 and then stay constant after that. The PO43- removal efficiency can be considered high for the entire systems, more than 90%. The removal efficiencies of PO43- for overall performance in Control and Planted system through the SSF-FWS constructed wetland systems were achieved 92.4% (k = 0.236 day-1) and 95.9% (k = 0.337 day-1), respectively. Based on removal rate constant, k value for Planted system was slightly higher than Control in removing of PO43-.. From analysis ANOVA, there was significant different (p≤0.05) between Control and Planted systems in PO43- removal as shown in Appendix B. Control 1.00 Planted 0.80 C/Co 0.60 C = 0 .94 e − 0.236 t Co 0.40 0.20 C = 0 .97 e − 0 .337 t Co 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.9 : Comparison of PO43- concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland The PO43- removal capacity of constructed wetlands depends on the physical, chemical and microbiological processes, which influence PO43- incorporation in both inorganic and organic forms in wetland sediments. PO43- removal in wetlands takes place by plant uptake, accretion of wetland soils, microbial immobilization, retention by root bed media, and precipitation in the water column (Pant et al., 2001). PO43- 81 may be deposited onto the wetland system sediment by sedimentation or entrapped within the emergent macrophytes stem matrix and attached onto biofilms (EPA, 1993). Sand that was used as the media is a better system to remove PO43- from wastewater. Sand can effectively remove PO43- through sorption and its use as root bed media could enhance the efficiency of constructed wetlands to remove PO43from effluents (Aeslina, 2004). As suspended solid settle, the sorbed PO43- is removed from water column. PO43- also sorbs to oxides and hydroxyoxides of iron and aluminium and to calcium carbonate. There is a finite supply of these minerals in the sediments, and inorganic phosphorus must come in direct contact with the sediments before it can retained there (Cronk and Fennessy, 2001). Under reduced conditions, PO43- is released the reduction of ferric, Fe3+ phosphate compounds to more soluble ferrous, Fe2+ forms. If the soil is not vegetated such as in Control system, this released PO43diffuses back to surface waters. However, when plants are present, such as in Planted system, the wetland plants were assimilated the released PO43- and prevent its movement out of the sediments (Cronk and Fennessy, 2001). PO43- may be broken down to inorganic forms such as HPO42- through microbial enzyme activity. Dissolved organic PO43- and insoluble inorganic and organic PO43- are not usually available to plants until transformed to a soluble inorganic form. These transformations may take place in the water column by way of suspended microbes and in the biofilms on the emergent plant surfaces and in the sediments (EPA, 1993). Finally, floating and emergent macrophytes, as well as algae take up varying amounts of PO43- (Debusk, 1999). Uptake by the macrophytes occurs in the sediment pore water by the plant root system. 4.4 Suspended Solid Removal Suspended solid (SS) concentration was high in the initial leachate landfill as previously shown in Table 4.1. High SS will put a greater stress on the water body because too much SS in water can adversely affect the light penetration and photosynthetic activity and hence fish and other aquatic life would be intolerant 82 adaptation. As depicted in Figure 4.10 and Figure 4.11, both systems show the concentration of SS through the SSF and FWS wetland in both systems decreased steadily from day 3 to day 18 of operations. Control 200 Planted 180 SS Concentration (mg/L) 160 140 120 100 80 60 40 20 0 0 3 6 9 12 15 18 Time (days) Figure 4.10 : SS concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 200 Control Planted 180 SS Concentration (mg/L) 160 140 120 100 80 60 40 20 0 0 3 6 9 12 15 18 Time (days) Figure 4.11 : SS concentration in profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 83 Figure 4.12 represents overall performance of Control and Planted system through the SSF-FWS constructed wetland in removing of SS. After 18 days of operation, both systems had the capability to reduce SS concentration in leachate. The removal efficiencies of SS for overall performance in Control and Planted system through SSF-FWS constructed wetland were achieved 75.9% (k = 0.076 day-1) and 87.3% (k = 0.106 day-1), respectively at the end of operations. As depicted in Figure 4.12, the reductions of SS in Planted systems were significantly (p≤0.05) higher than in the Control as shown in Appendix B. 1.00 Control Planted 0.80 C = 1 .04 e − 0 .076 t Co C/Co 0.60 0.40 C = 1 .03 e − 0 .106 t Co 0.20 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.12 : Comparison of SS concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland system The removal of SS in constructed wetlands is achieved through several mechanisms. Settleable solids are removed easily by sedimentation since wetland systems generally have long HRT. Nonsettling or colloidal solids are removed by processes which include; straining of sand media, adsorption on plants and wetland media and biodegradation. The types of removal mechanism at work are very dependent on the size and nature of solids present in the wastewater and the types of filter media used (Lim, 2002). Control and Planted systems shows the significant different in SS removal. Therefore, studies have shown that SS concentration levels were reduced more efficient in wetlands containing plants especially in SSF-FWS wetland. This was because the presence of macrophytes stands reduces water 84 velocity and allows for the filtering and settling of organic particulate matter; other suspended solids, and associated nutrients. With decreased water velocity, the contact time between the wastewater and the sediments and plant surface area is increased, thus adding to the potential treatment of the waste by adsorption or microbial processes (Carpenter and Lodge, 1986; Cronk and Fennessy, 2001). Most of the solids are removed through sedimentation and filtration in SSF wetland and settling process in FWS wetland, and all the processes are based on velocities of flow (Lim, 2002). In this case, wetland plants which were planted in both wetlands were obstructed the flow and reduces the influent velocity. Once the velocity was reduce, sedimentation, filtration and settling processes of wetlands effectively removed SS. This was because the influent moves slowly, SS settle out and creating sediment at the bottom of the wetlands. Besides, sand and soil in SSF wetland helps to settle out the solids and effluents slowly filters before the end product is released into FWS wetland (Cronk and Fennessy, 2001; Mashhor et al., 2002). In Control system, SS reduction is attributed to filtering action as wastewater passes through the bed media. SS are removed by wetlands due to the filtering action of the bed media. Microorganisms are removed by die-off, straining, sedimentation, entrapment and adsorption (Metcalf and Eddy, 1991). Besides, plant surfaces in the water column are coated with an active biofilm of periphyton. This biofilm can adsorb colloidal and supracolloidal particles as well as absorb soluble molecules (EPA, 1993). 4.5 Turbidity Turbidity is a measure of the cloudiness of the water. Sediment, algae, bacteria and zooplankton all contribute to what is technically known as the TSS that increases the turbidity. As turbidity increases, the degree to which sunlight penetrates the water column declines (EPA, 1993). In this study, the system consisting of SSF-FWS constructed wetland vegetated with Limnocharis flava and 85 Eichhornia crassipes were effective for 18 days in reduction high level of turbidity. As shows in Figure 4.13 and Figure 4.14 respectively, turbidity value reductions in the FWS effluent were stable and consistently lower than in the SSF effluent. 500 Control 450 Planted Turbidity (NTU) 400 350 300 250 200 150 100 50 0 0 3 6 9 12 15 18 Time (days) Figure 4.13 : Turbidity measure in Control and Planted system through SSF constructed wetland within 18 days of treatment 250 Control Planted Turbidity (NTU) 200 150 100 50 0 0 3 6 9 12 15 18 Time (days) Figure 4.14 : Turbidity measure in Control and Planted system through FWS constructed wetland within 18 days of treatment 86 From the graph it can be seen that turbidity decreased more rapidly after 3 days of operation and decreased steadily from day 3 to day 18 of operations. Turbidity value more rapidly decreased for all the wetlands due to the sorption on the new sand and soil media. During the next 15 days of operation, the turbidity value decreased gradually at the outlet due to the sand and soil already saturated with solids particles. Figure 4.15 shows the trend of turbidity reduction over time. Control 1.00 Planted C/Co 0.80 0.60 0.40 0.20 C = 0 .97 e − 0 .251 t Co C = 0 .98 e − 0 .306 t Co 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.15 : Comparison of turbidity value (C/CO) for overall performance in Control and Planted system through SSF-FWS constructed wetland system Due to good removal efficiency of SS in both systems, reductions of turbidity in both systems after FWS wetland is also high. The removal efficiencies of turbidity for overall performance in Control and Planted system through SSF-FWS constructed wetland were achieved 98% (k = 0.251 day-1) and 99.6% (k = 0.306 day-1), respectively after 18 days of operation. As depicted above in Figure 4.15, the reductions of turbidity in Planted systems were significantly (p≤0.05) higher than in the Control as shown in Appendix B. However, turbidity removal rate constants for Control and Planted system in this study were high. This result might be caused by the high turbidity removal efficiency in both systems. After 18 days of operation, both systems had the capability to reduce turbidity value in landfill leachate. This was subsequently affected from the highest SS removal as shown previously in Figure 4.12. As previously mention, SS concentration was contributed the turbidity 87 value. In this study, the reduction of SS was high and this result was influence the removal of turbidity. That means the removal of turbidity in constructed wetlands is achieved through several mechanisms which is similar like SS removal. Turbidity reduction in constructed wetlands is best facilitated through the encouragement of settling. Densely vegetated wetland facilitate the settling of suspended matter by obstructing water flows, stabilizing bottom sediments and physically filtering and trapping the matter (Galbrand, 2003). Sedimentation and filtration mechanisms of constructed wetlands effectively removed fine particle of organic and inorganic matter, and at the same time reduced turbidity (Lin et al., 2005). In this study, treatment wetlands that use emergent and floating plants such as Limnocharis flava and Eichhornia crassipes, the plants act as a filter, straining wastewater and retaining solids in their dense roots. It’s so obvious that by comparing Limnocharis flava and Eichhornia crassipes bed to unplanted bed, turbidity decreased up to 6 % after 5 days of treatment. With a decreased in turbidity came a reduction in suspended organic matter, which resulted in a decreased in BOD (Reddy et al., 1983). 4.6 Heavy Metals Removal Iron and manganese were present at relatively high concentrations in the leachate, but were efficiently removed by the wetland treatment system. Probable removal mechanisms are plant uptake and probably more importantly, precipitation and sedimentation of Fe and Mn oxide (Debusk, 1999). 4.6.1 Ferum Heavy metals concentrations is of great concern due to their serious effects on food chain and furthermore on animal and human health (EPA, 1993). Ferum (Fe) reduction during experiments for both SSF and FWS constructed wetland were 88 shown in Figure 4.16 and Figure 4.17. Respectively, both systems show the significant reductions in concentration of Fe through the SSF-FWS wetland. The results also show that effluent concentration was decreasing after 18 days in all systems. 40 Control Planted Fe Concentration (mg/L) 35 30 25 20 15 10 5 0 0 3 6 9 12 15 18 Time (days) Figure 4.16 : Fe concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment 16 Control Planted Fe Concentration (mg/L) 14 12 10 8 6 4 2 0 0 3 6 9 12 15 18 Time (days) Figure 4.17 : Fe concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 89 Fe was efficiently removed in both wetlands systems as illustrated in Figure 4.18. From the graph it can be seen that concentration of Fe decreased more rapidly after 3 days of operation and decreased steadily from day 3 to day 12 and then stay constant after that. The removal efficiencies of Fe for overall performance in Control and Planted were 97.2% and 99.5%, respectively after 18 days of operation. Fe removal followed the first order removal model, with rate constants of 0.286 day-1 and 0.43 day-1 in Control and Planted systems. In this study, Fe removal rate constants for both Control and Planted systems were high. This result might be caused by the high Fe removal efficiency in both systems. In this study, the reductions of Fe in Planted systems were slightly higher (p≤0.05) than in the Control. Control 1.00 Planted 0.80 C/Co 0.60 0.40 C = 0 . 97 e − 0 .286 t Co C = 0 . 99 e − 0 .43 t Co 0.20 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.18 : Comparison of Fe concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS wetland From the results, this phenomenon might be explained. Emergent plants and floating plants help in reducing heavy metals by retaining it either in the root or in the leaves. Plants species have variety of capacity in accumulating and removing heavy metals. Uptake and accumulation of elements by plants may follow two different paths, i.e., the root system and foliar surface (Sawidis et al., 2001). The results indicated that Limnocharis flava and Eichhornia crassipes could accumulate significant amount of Fe concentration. Wetland plants, however, can influence metals removal and storage indirectly through their effects on hydrology, sediment 90 chemistry and microbial activity. However, it is important to know that although plants uptake is a direct way to remove heavy metal by vegetation, the amount of heavy metal removed by uptake is not significant comparing to other removal mechanisms. It’s so obvious that by comparing Limnocharis flava and Eichhornia crassipes bed to unplanted bed, both of Planted and Control system were achieved high Fe removal percentage at the end of operations. The greater heavy metals removal in the Control system maybe was due to clogging of the substrate in soil sediment. So it can be concluded that, reduction of heavy metal concentration in the Planted and Control system were most likely due to chemical precipitation and sorption on sediment, and aided by the macrophytes. Other possible removal processes include precipitation as metal hydroxides in the aerobic zone. It is also believed that an external aerobic microzone can be established around parts of the growing roots (Armstrong and Armstrong, 1990). As a result, iron is precipitated. It is suggested Fe precipitated as a result of oxygen release from the roots (Peverly et al., 1995). In this study, the reduction of nitrate was high and this result was influence the removal of Fe. The reasons are because some of the microorganisms involved in Fe reduction can also reduce nitrate. They favor nitrate, so the reduction of Fe starts once nitrate has been depleted (Cronk and Fennessy, 2001). 4.6.2 Manganese Manganese (Mn) which is most commonly present in landfill leachate at high concentration and present in it reduced forms (Mn2+), which is one of the heavy metals concern in this study. In this study, the system consisting of SSF-FWS constructed wetland vegetated with Limnocharis flava and Eichhornia crassipes were effective for 3 weeks in reduction high level of manganese from landfill leachate. As depicted in Figure 4.19 and Figure 4.20, both systems show the significant reductions in concentration of Mn through the SSF-FWS wetland. The 91 results also show that effluent concentration was decreasing after 18 days in all reactors. From the graph it can be seen that concentration of Mn through the SSFFWS wetland in both systems decreased steadily from day 3 to day 18 of operations. Control 0.60 Planted Mn Concentration (mg/L) 0.50 0.40 0.30 0.20 0.10 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.19 : Mn concentration profile in Control and Planted system through SSF constructed wetland within 18 days of treatment Control Planted 0.50 0.45 Mn Concentration (mg/L) 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.20 : Mn concentration profile in Control and Planted system through FWS constructed wetland within 18 days of treatment 92 Mn was also decreasing significantly in Control and Planted systems as shown in Figure 4.21. From the graph it can be seen that concentration of Mn decreased more rapidly after 3 days of operation and decreased steadily from day 3 to day 12 and then stay constant after that. The removal efficiency which was more than 90% was achieved for all the treatment systems after 18 days of treatment. It shown the highest removal of Mn determined by Planted system (97.7%), followed by Control (95.6%). The removal rate constant (k) for Mn is slightly higher in Planted (k= 0.16 day-1) compared to Control system (k= 0.137 day-1). It shows that Mn concentration is only slightly decreased in Planted system compared than in Control system. The ANOVA test did reveal a significant differences p≤0.05 between Control and Planted systems as shown in Appendix B. Control 1.00 Planted 0.80 C/Co 0.60 0.40 0.20 C = 1 .03 e − 0 .137 t Co C =1 . 02 e − 0 .16 t Co 0.00 0 3 6 9 12 15 18 Time (days) Figure 4.21 : Comparison of Mn concentration (C/CO) for overall performance in Control and Planted system through SSF-FWS wetland In this study, the unplanted system also demonstrated high reduction of Mn. This results shows that the amount of heavy metal removed by Limnocharis flava and Eichhornia crassipes plants uptake is not significant comparing to other removal mechanisms. The reduction of Mn in SSF wetland system maybe was due to settling and sedimentation, uptake by algae and bacteria, precipitation as insoluble salts, and binding to soil, sediments and particulate (Kadlec and Knight, 1996; Lim, 2002). Sedimentation has long been recognized as the principle process in removal of heavy 93 metals from waste water in natural and constructed wetlands. It is not a simple straightforward physical reaction. Other chemical processes like precipitation and co-precipitation have to occur first. Precipitation and co-precipitation in the removal of heavy metals is an important adsorptive mechanism in wetland sediments. Meanwhile, in sediments heavy metals are adsorbed to the soil particles by either cation exchange or chemisorptions (Sheoran and Sheoran, 2005). However, the reduction of Mn in Control system still showed lower Mn removal if compared with performance of Planted system. This result suggests that macrophytes could induce higher Mn removal in wetland. It can be concluded that wetland plants are an integral part of the Mn removal in SSF-FWS wetlands. Plants mechanisms for metals removal in wetlands include adsorption, chemical precipitation and plant uptake (Reed et al., 1995). Several processes are envisioned as being effective in pollutant reduction; for example metals are taken up by plants, and in many cases stored preferentially in the roots and rhizomes (Kadlec, 1999). Manganese, a micronutrient is reduced from Mn4+ to Mn2+ at a redox potential. The transformation is a microbial process. The reason is in the reduced form, Mn2+ is slightly more available to plants than in the oxidized form Mn4+ (Cronk and Fennessy, 2001). 4.7 Heavy Metal in Plant’s Tissues Biological removal is perhaps the most important pathway for heavy metal removal in the wetlands. Probably the most widely recognized biological processes for metal removal in wetlands is plant uptake (Sheoran and Sheoran, 2005). Therefore, analysis of the roots and leaves were done at the beginning of experiment before the plants planted in the constructed wetland and at the end of experiment. As the results, concentration of Fe was significantly greater in roots compared to in leaves with the highest accumulation by Limnocharis flava in SSF wetlands system, followed by Eichhornia crassipes in FWS wetlands, which were 209.5 μg/g dry weight, and 102.2 μg/g dry weight, respectively. While, Fe uptake in 94 the leaves of the Limnocharis flava and Eichhornia crassipes were 29 μg/g dry weight and 58.4 μg/g dry weight, respectively. From the study, it shows that heavy metal uptake is more significant in roots compare to leaves as illustrated in Figure 4.22. The highest total accumulation of Fe was achieved by Limnocharis flava in SSF wetlands system which was 238.5 μg/g dry weight followed by Eichhornia crassipes in FWS wetlands, 160.6 μg/g dry weight in roots and leaves. 500 Limnocharis flava Limnoclaris flava Fe conc. (ug/g dry weight) 450 Eichhornia Eichhorniacrassipes crassipes 400 350 300 250 200 150 100 50 0 Initial Root Final Root Initial Final Leaves Leaves Initial Final Root Leaves Initial Final Leaves Leaves Plants Tissues Figure 4.22 : Heavy metal (Fe) accumulation by Limnocharis flava and Eichhornia crassipes in SSF-FWS wetland systems Figure 4.23 shows that concentration of Mn was significantly greater in root compared to in leaves with the highest accumulation by Limnocharis flava in SSF wetlands system, followed by Eichhornia crassipes in FWS wetlands, which were 6.52 μg/g dry weight, and 4.8 μg/g dry weight, respectively. While, Mn uptake in the leaves of the Limnocharis flava and Eichhornia crassipes were 1.18 μg/g dry weight and 1.48 μg/g dry weight, respectively. The highest total accumulation of Mn was achieved by Limnocharis flava in SSF wetlands system which was 7.7 μg/g dry weight followed by Eichhornia crassipes in FWS wetlands, 6.28 μg/g dry weight in roots and leaves. The results proved that leaves of Limnocharis flava and Eichhornia 95 crassipes have less ability for metal accumulation than roots. The study also demonstrated that the uptake of Fe by plants was higher compared to Mn. 9 Limnocharis flava Limnoclaris flava Mn conc. (ug/g dary weight) 8 Eichhorniacrassipes crassipes Eichhornia 7 6 5 4 3 2 1 0 Initial Root Final Root Initial Final Leaves Leaves Initial Root Final Leaves Initial Final Leaves Leaves Plants Tissues Figure 4.23 : Heavy metal (Mn) accumulation by Limnocharis flava and Eichhornia crassipes in SSF-FWS wetland systems One of the major mechanisms of heavy metal removal is due to plants uptake. Plants have the ability to accumulate nutrient including heavy metals from soil and wastewater (Cronk and Fennessy, 2001; Aeslina, 2004; Thien, 2005). Emergent plants and floating plants help in reducing heavy metals by retaining it either in the root or in the leaves. The high accumulation of heavy metal in Limnocharis flava was due to the plant that had many shorter roots that were able to create aeration zones for heavy metal uptake (Krishnan, 2002). Study by Soltan and Rashed (2001) reported that Eichhornia crassipes only effectively removes appreciable quantities of heavy metals, especially at low concentrations, whilst it releases small quantities of heavy metals at wilting. This fact supported low concentration of heavy metals accumulates in roots and leaves of Eichhornia crassipes because at the end of experiments, Eichhornia crassipes cannot survive in leachate constituents and begin to wilt. The study also observed that 96 Limnocharis flava had capability to survive with leachate constituents compared than Eichnornia crassipes. According to previous study, it shows that heavy metal uptake is more significant in roots compare to the leaves (Cooly and Martin, 1979; Peverly et al., 1995; Pant et al., 2001; Thien, 2005; Noor Ida Amalina, 2006). These roots have been reported to be the most beneficial for phytostabilisation of the metal contaminants. Denny (1987) and Greenway (1997) also reported that the main route of heavy metal uptake in wetland plants was through roots in emergent and surfacefloating. Greenway and Simpson (1996); Polprasert et al. (1996); Greenway (1997); and Scholes et al. (1998) reported that roots of the wetlands play very important role in wastewater purification followed by stem and leaves. A limited uptake or translocation of metals is suggested by higher concentrations of roots than leaves. Meanwhile, plaques of iron and manganese oxyhydroxides often form on waterlogged roots (Vest and Allaway, 1997), and co-precipitation of other metals in these plaques is one process to explain the elevated concentrations found in roots. As depicted previously in Figure 4.22 and Figure 4.23, the result shows that Mn uptake by plants was less than Fe. Recently, study by Thien (2005) and Noor Ida Amalina (2006) also reported that the amount of Fe uptake by plants was higher compared to Mn in plants tissues. Fe2+ was the micronutrient for plants that was required in higher concentration than Mn2+ (Kamal et al., 2004). Additionally, plants require a small amount of Mn, high level of Mn interfere with enzyme structure and nutrient consumption. Actually the role and potential importance of plants uptake and storage of heavy metals are poorly understood in wetland treatment system. The rate of heavy metal uptake is controlled by the plants growth rate and the accumulation of heavy metals in the plants tissues (Cronk and Fennessy, 2001). 4.8 Comparison with Other Researchers The results of several studies on constructed wetlands of leachate treatment are presented in Table 4.2. This table shows the comparison between this study and 97 the other researchers. It shows that leachate treatment using combine SSF-FWS constructed wetlands (CWs) have better performance in nutrient and heavy metals removal compare than by using one-single type of constructed wetlands system. Table 4.2 : Comparison of different models of constructed wetlands for landfill leachate treatment Type of CWs and Plants NH4-N (%) NO3-N (%) PO43(%) SS (%) Fe (%) Mn (%) UTM, Malaysia Ain Nihla (2006) SSF-FWS CWs with L.flava and E.crassipes >93% >96% >95% >87% >99% >97% UTM, Malaysia Noor Ida Amalina (2006) FWS CWs with magnetic field and E. crassipes >64% >90% >59% - >100% >87% UTM,Malaysia Thien (2005) FWS CWs with E.crassipes >25% >60% >15% - >60% >50% UTM, Malaysia Aeslina (2004) Horizontal (SSF) Thypa Angustifolia Safety Flow® >90% >60% >80% - - - University of Windsor, ElGendy (2003) FWS CWs with E.crassipes and salvinia >100% - >97% - >84% - UTM, Malaysia Rafidah (2003) Vertical (SSF) S.Sumatrensis And S.Mucronatus - - - - >95% >91% Norway, Maehlum (1995) Horizontal (SSF) P. Australis And T.Latifolia >70% - >70% - - - Site and Researchers 98 However, study by Noor Ida Amalina (2006) also show high heavy metals removal efficiency compared to others system. This was due to the effects of magnetic field in treating landfill leachate. Rafidah (2003) also reported high heavy metals (Fe and Mn) removal by using vertical (SSF) planted with S.sumatrensis and S.mucronatus. The reason might be because the effect on using two types of plants such as S.sumatrensis and S.mucronatus in one constructed wetland system which is can increased the removal of heavy metals in landfill leachate. In this study, Rafidah (2003) was also remarked that the removal rate for nutrient and heavy metal depends directly with time. The more the contact time between leachate and vegetation in the wetland system, was better the removal rate. Meanwhile, the treatment systems of El-Gendy (2003) showed the best performance in removal of NH4-N and PO43- from landfill leachate which is achieved 100% and 97% respectively. El-Gendy (2003) also reported that by using two types of plants such as E.crassipes and salvinia in FWS constructed wetland system can enhanced the removal efficiency of nutrients from landfill leachate. So, it can be concluded that use of multi-types of plants rather than mono-types of plants in wetland systems also gives higher removal either in nutrient or heavy metals removal. 4.9 Conclusion As the conclusion, the SSF-FWS wetland system was proven effective in pollutants removal in leachate. From the results, this study has demonstrated that both systems (i.e. Planted and Control) of the experiments had the ability to reduce all the parameters measured. However, the removal efficiency obtained from this study indicated that Planted system with Limnocharis flava and Eichhornia crassipes had the highest percentage of removal compared to unplanted Control system. Significant differences were revealed by ANOVA between systems at p≤0.05 for NH4-N, NO3-N, PO43-, SS, turbidity and heavy metals (Fe and Mn) removal. Overall, Planted system had shown the best operating system for removal of measured parameters during this study. 99 According to the study, removal efficiency of nutrients from landfill leachate in the form of NH4-N, NO3-N and PO43- by Planted system through the SSF-FWS constructed wetland were achieved 93.1%, 96.4% and 95.9% respectively after 18 days of operations. Removal of heavy metals by SSF-FWS constructed wetland with Limnocharis flava and Eichhornia crassipes were achieved Fe (99.5%) and Mn (97.7%) after end of treatment. And, also removal efficiency of SS and turbidity were achieved 87.3% and 99.6% respectively. While, removals of nutrients by unplanted system were achieved 78.1% of NH4-N, 77.1% of NO3-N and 92.4% of PO43-. Removals of heavy metals by unplanted system were achieved 97.2% of Fe and 95.6% of Mn. In unplanted Control system also shows removal 75.9% of SS and 98% of turbidity. In this study, gravel, sand and soil that were used as the media are also an effective combination to remove pollutants. However, it was observed that Limnocharis flava and Eichhornia crassipes did attribute to nutrients and heavy metals removal. It is because macrophytes in leachate treatment play an important role in constructed wetlands by providing microbial attachments, sufficient leachate residence time, trapping and settlement of suspended leachate components. These were results of resistance to hydraulic flow, surface area for pollutant adsorption, uptake and storage in plant tissues, roots or leaves and diffusion of oxygen from aerial parts to the rhizosphere. The study showed Limnocharis flava and Eichhornia crassipes had higher capacity to accumulate heavy metals (Fe and Mn) in roots compared than in leaves. Fe uptake in the root and leaves of the Limnocharis flava were 209.5 μg/g dry weight and 29 μg/g dry weight, and by Eichnornia crassipes were 102.2 μg/g dry weight and 58.4 μg/g dry weight respectively. While, Mn uptake in the root and leaves of the Limnocharis flava were 6.52 μg/g dry weight and 1.18 μg/g dry weight, and by Eichnornia crassipes were 4.8 μg/g dry weight and 1.48 μg/g dry weight, respectively. CHAPTER 5 CONCLUSION 5.1 Conclusion Constructed wetland is one of approaches that can promotes the best achievement in nutrient and heavy metal removal and also enhance landfill leachate water quality. In this study, a combination system utilizing a SSF-FWS constructed wetland systems have shown higher performance in treating landfill leachate. The results demonstrated that nutrients and heavy metals removal can be increased up to 90% by applying SSF-FWS constructed wetland systems. The performance of SSFFWS constructed wetland was evaluated with comparison to Control systems (without plants). The SSF-FWS constructed wetland planted with Limnocharis flava and Eichhornia crassipes shows the higher performance than unplanted constructed wetlands for all parameters evaluated. The results indicated that the removal efficiency of nutrients, and heavy metals in leachate using Limnocharis flava and Eichhornia crassipes were achieved NH4-N (93.1%), NO3-N (96.4%), PO43- (95.9%), Fe (99.5%) and Mn (97.7%) after end of the treatment. And, also removal efficiency of SS and turbidity were achieved 87.3% and 99.56% respectively. While, in Control system shows removal of nutrients, SS, turbidity and heavy metals (Fe and Mn) were NH4-N (78.1%), NO3-N (77.1%), PO43- (92.4%), SS (75.9%), turbidity (98% ), Fe (97.2%) and Mn (95.6%). 101 Control system has almost the same performance with the Planted systems in PO43-, turbidity and heavy metals removal. Difference between the performances of both systems was less than 5% in these parameters removal. Therefore, it can be concluded that Limnocharis flava and Eichhornia crassipes have little enhancement in PO43-, turbidity and heavy metals removal. The role of the plant was more obvious in NH4-N, NO3-N and SS removal with 15%, 19% and 11% better than the Control system, respectively. Limnocharis flava had higher capacity to accumulate heavy metals (Fe and Mn) in leachate constituents compared than Eichhornia crassipes. From the analysis, it shows that Fe and Mn uptake by Limnocharis flava and Eichhornia crassipes is more significant in roots compare to leaves. The study also observed that Eichhornia crassipes planted in the FWS beds were notable less vigorous and healthy than Limnocharis flava in the SSF beds. So, it can be concluded that Limnocharis flava had capability to survive with leachate constituents compared than Eichhornia crassipes. 5.2 Recommendations Recommendation will be given in order to further enhance the applicability of the findings in this study, the soundness of which has been well demonstrated in this study: (i) Further studies should vary the flow rates, HLR, retention time, type of plants and size of constructed wetlands system in order to determine the efficient of pollutants removal; (ii) Further studies are recommended to analyse accumulation of nutrients and heavy metals in the soil sediment adjacent to the plants roots. The measurement of soil sediment near the plants wetland will give an indication of nutrient and heavy metals removal performance. REFERENCES Aeslina Abdul Kadir (2004). Landfill Leachate Treatment Performance in SSF Constructed Wetlands using Safety Flow System. Universiti Teknologi Malaysia: Master Thesis. th APHA (2002). Standard Methods for Examination of Water and Wastewater. 21 Edition. Washington : American Public Health Association. Armstrong, J. and Armstrong, W. (1990). Light-enhanced convective through flow increases oxygenation in rhizomes and rhizosphere of Phragrnites australis. Trin ex Steud. New Phytol. 114: 121-128. Bagghi, A. (1994). Design, Construction and Monitoring of Sanitary Landfill. New York: John Wiley & Sons. Baker, L.A. (1998). Design constructed considerations and applications for wetland treatment of high-nitrate waters. Water Science and Technology. 38(1): 389395. Bastviken, S.K., Eriksson, P.G., Premrov, P. and Tonderski, K. (2005). Potential Denitrification in Wetland Sediments with Different Plant Species Detritus. Ecological Engineering. 25: 183 – 190. Boyle, W.C. and Ham, H.B. (1974). Biological Treatability of Landfill Leachate. Journal of the Water Pollution Control Federation. 46(5): 860-872. Britz, T.J. (1995). Landfill Leachate Treatment. In: Senior, E. Microbiology of Landfill Sites. Boca Raton, Florida: CRC Press. 131-164. Brix, H. (1993). Wastewater Treatment in Constructed Wetlands: System Design, Removal Processes and Treatment Performance. In: Galbrand, C.C. Naturalized Treatment Wetlands for Contaminant Removal: A Case Study of the Burnside Engineered Wetland for Treatment of Landfill Leachate. Dalhousie. 103 Brix, H. (1994). Use of constructed wetlands in water pollution control: historical development, present status, and future perspectives. Water Science Technology. 30(11): 209-223. Brix, H. (1997). Do macrophytes play a role in constructed treatment wetlands?. Water Science and Technology. 35:11-17. Cameron, K., Madramootoo, C., Crolla, A. and Kinsley, C. (2003). Pollutant Removal from Municipal Sewage Lagoon Effluents with a Free-Surface Wetland. Water Research. 37: 2803–2812. CAP (2001). Waste Not Asia. Malaysia Country Report, Consumers Association of Penang. Taipei, Taiwan. unpublished. Carpenter, S.R. and Lodge, D.M. (1986). Effects of Submersed Macrophytes on Ecosystem Processes. Aquatic Botany. 26: 341-370. Chew, A.L. (2006). Nutrient Removal from Leachate using Horizontal Subsurface Constructed Wetlands. Universiti Teknologi Malaysia: Master Thesis. Chian, E.S. (1977). Stability of Organic Matter in Landfill Leachates. Water Research, Pergamon Press. 11(2) : 225-232. Chian, E.S.K. and Fang, H.H.P. (1973). Evaluation of New Reverse Osmosis Membranes for the Separation of Toxic Compounds from Water. American Institute of Chemical Engineers Symposium Series. 71(145): 497-507. Chian, E.S. and DeWalle, F.B. (1976). Sanitary Landfill Leachates and Their Treatments. Journal of the Environmental Protection Agency, Ohio. 125. Chian, E.S. and DeWalle, F.B. (1977). Evaluation of Landfill Leachates Treatments, Characteristion of Leachate. Journal of the Environmental Protection Agency, Ohio. unpublished. Christensen, T.H., Cossu, R. and Stegmann, R. (1992). Landfilling of Waste: Leachate. London: Elsevier Applied Science. Cooly, T.N., Martin, D.F. (1979). Cadmium in naturally occurring water hyacinth. Chemosphere. 8: 75–79. Cooper, P. F., Job, G. D., Green, M. B. and Shutes, R. B. E. (1996). Reed Beds and Constructed Wetlands for Wastewater Treatment. Medmenham, Marlow: WRC Publications. Crites, R.W. (2005). Constructed Wetland for Landfill Leachate Treatment. Southwest Hydrology. 29. 104 Cronk, J.K. and Fennessy, M.S. (2001). Wetland Plants, Biology and Ecology. Bota Raton: Lewis Publishers. Debusk, W.F. (1999). Evaluation of a Constructed Wetland for the Treatment of Leachate at a Municipal Landfill in Northwest Florida. In: Mulamoottil, G., McBean, E.A., and Rovers, F. Constructed Wetlands for the Treatment of Landfill Leachates. United States: Lewis Publishers. 175-185. Denny, P. (1987). Mineral cycling by wetland plants—a review. Hydrobiologie Beih. 27: 1–25. Eckhardt, D.A.V., Surface, J.M. and Peverly, J.H. (1999). A Constructed Wetlands System for Treatment of Landfill Leachate, Monroe Country, New York. In: Mulamoottil, G., McBean, E.A., and Rovers, F.. Constructed Wetlands for the Treatment of Landfill Leachates. United States: Lewis Publishers. 205-220. El-Fadel, M., Findikakis, A.N., and Leckie, J.O. (1997). Environmental Impacts of Solid Waste Landfilling. Journal of Environmental Management. 50: 1-25. El-Gendy, A. (2003). Leachate Treatment Using Natural Systems. University of Windsor: Ph.D. Thesis. EPA (1993). Manual—Nitrogen control EPA/626/R-93/010. Environmental Protection Agency Office of Research and Development, Washington. Finlayson, M. and Moser, M. (1991). Wetland. Fact on File, Oxford, UK. unpublished. Focht, D.D. and Verstraete, W. (1977). Biochemical ecology of nitrification and denitrification. Advance Microb Ecology. 1: 135-214. Fraser, L.H., Carty, S.M. and Steer, D. (2004). A Test of Four Plant Species to Reduce Total Nitrogen and Total Phosphorus from Soil Leachate in Subsurface Wetland Microcosms. Bioresource Technology. 2: 185-192. Freeman, R.J. (1993). Constructed Wetlands Experience in the Southeast. In: Moshiri, G.A., Ed. Constructed Wetlands for Water Quality and Improvement, Chapter 6. Boca Raton: CRC Press. Fungaroli, A.A. and Steiner, R.L. (1979). Investigation of Sanitary Landfill Behaviou. Final Report Environmental Protection Agency, Ohio. unpublished. Galbrand, C.C. (2003). Naturalized Treatment Wetlands for Contaminant Removal: A Case Study of the Burnside Engineered Wetland for Treatment of Landfill Leachate. Dalhousie University: Master Thesis. 105 Gersberg, R.M (1986). Role of aquatic plants in wastewater treatment by artificial Wetlands. Water Research. 20: 363. Greenway, M. and Simpson, J.S. (1996). Artificial wetlands for wastewater treatment, water reuse and wildlife in Queens Land, Australia. Water Science and Technology. 33: 221–229. Greenway, M. (1997). Nutrient content of wetland plants in constructed wetlands receiving municipal effluent in tropical Australia. Water Science and Technology. 35: 135–142. Hammer, D.A. and Bastian, R.K. (1989). Wetland Ecosystems: Natural Water Purifiers?. In: Hammer, D.A. Constructed Wetlands for Wastewater TreatmentMunicipal, Industrial and Agricultural. Chelsea, Ml: Lewis Publishers. Hammer, D.A. (1990). Constructed Wetlands for Wastewater Treatment: Municipal, Industrial and Agricultural. Michigan: Lewis Publishers. Hencha, K.R., Bissonnettea, G.K., Sexstonea, A.J., Colemanb, J.G., Garbuttb, J. and Skousena, J.G. (2003). Fate of Physical, Chemical, and Microbial Contaminants in Domestic Wastewater following Treatment by Small Constructed Wetlands. Water Research. 37: 921–927. Ho, S., Boyle, W.C, and Ham, R.K. (1974). Chemical Treatment of Leachates from Sanitary Landfills. Journal of the Water Pollution Control Federation. 46(7): 1776-1791. Huett D.O., Morris S.G., Smith G and Hunt N. (2005). Nitrogen and Phosphorus Removal from Plant Nursery Runoff in Vegetated and Unvegetated Subsurface Flow Wetlands. Water Research. 39: 3259–3272. Ingersoll, T.L, and Baker, L.A. (1998). Nitrate removal in wetland microcosms. Water Research. 32(3): 677-684. IWA (2000). Constructed Wetlands for Pollutant Control. Scientific and Technical Report No 8. London: International Water Association (IWA) Group Publishing. IWA (2000). Use of Macrophytes in Water Pollution Control Constructed Wetlands for Pollution Control: process, performance, design and operation. London: International Water Association (IWA) Group Publishing. Jin, G., Kelley, T. and Vargas, N. (2003). Preliminary Evaluation of Metals Removal in Three Pilot-Scale Constructed Wetland Systems. Management of Environmental Quality: An International Journal. 14(3): 323-332. 106 Kadlec, R.H. (1999). Constructed Wetlands for Treating Landfill Leachate. In: Mulamoottil, G., McBean, E.A., and Rovers, F., Ed. Constructed Wetlands for the Treatment of Landfill Leachates. United States: Lewis Publishers. Kadlec, R.H. and Knight, R.L. (1996). Treatment Wetlands. Boca Raton: CRC Press. Kamal, M., Ghaly, A.E., Mahmoud, N. and Cote, R. (2004). Phytoaccumulation of Heavy metals by aquatic plants. Environmental International. 29: 1029-1039. Keffala, C. and Ghrabi, A. (2005). Nitrogen and Bacterial Removal in Constructed Wetlands Treating Domestic Wastewater. Desalination. 185: 383–389. Kemper, J.M. and Smith, R.B. (1981). Leachate Production by Landfilled Processed Municipal Wastes. Proceeding of the Sevent Annual Research Symposium. Ohio, U.S.: EE2, 337-355. Kowalk, K.A. (2002). Constructed Wetlands for use as a Part of a Dairy Wastewater Management System. Michigan State University : Master Thesis. Krishnan, V.G. (2002). Kajian Penyerapan Logam-Logam Berat oleh Dua Spesis Tumbuhan Separuh Tenggelam dalam Tanah Bencah Buatan Jenis SubPermukaan bagi Olahan Air Larut Lesap. Universiti Teknologi Malaysia: Master Thesis. Kyambaddea, J., Kansiimea, F., Gumaeliusb, L. and Dalhammarb, G. (2004). A Comparative Study of Cyperus papyrus and Miscanthidium violaceum-based Constructed Wetlands for Wastewater Treatment in a Tropical Climate. Water Research. 38: 475–485. Le, A.T. (2003). Wetland - AN INTRODUCTION. Catholic University of Leuven, Belgium: Master Thesis. Lee, Y.F. (2004). Rainfall Effects to the Performance of Subsurface Flow Constructed Wetland in Leachate Treatment. Universiti Teknologi Malaysia: Master Thesis. Leckie, J.G., Pacey, J.G., and Halvadakis, C. (1979). Landfill Management with Moisture Control. Journal of the Environmental Engineering Division, ASCE. 2: 337-355. Lemna Corporation (1994). Innovations in Lagoon-Based Treatment, Retention Times. unpublished. 107 Lim, P.E. (2002). Constructed Wetland : Mechanisms of Treatment Processes and Design Models. In: Mashhor, M., Lim, P.E. and Shutes, R.B.E. “Constructed Wetlands : Design, Management and Education”. Malaysia: Universiti Sains Malaysia Publisher. Lim, P.E and Polparasert, C. (1996). Constructed Wetland for Wastewater Treatment and Resource Recovery. Environmental Systems Reviews, Thailand. unpublished. Lim, P.E., Wong, T.F. and Lim, D.V. (2001). Oxygen demand, Nitrogen and Copper Removal by Free Water Surface and Subsurface Flow Constructed Wetlands under Tropical Conditions. Environmental International. 26: 425-431. Lim, W.H., Tay, T.H. and Kho, B.L. (2002). Plants Used in the Putrajaya Wetland System and Problems Associated with Their Establishment and Maintenance. In: Mashhor, M., Eng, L.P. and Shutes, R.B.E. “Constructed Wetlands : Design, Management and Education”. Malaysia: Universiti Sains Malaysia Publisher. Lin, Y.F., Jing, S.R., Wang, T.W. and Lee, D.Y. (2002). Effects of macrophytes and external carbon sources on nitrate removal from groundwater in constructed wetlands. Environmental Pollution. 119: 413-420. Lin, Y.F., Jing, S.R., Lee, D.Y. and Chang, Y.F. (2005). Performance of a Constructed Wetland Treating Intensive Shrimp Aquaculture Wastewater under High Hydraulic Loading Rate. Environmental Pollution. 134: 411-421. Lina, V.L. (2004). Case Study on the Management of Waste Materials in Malaysia. Forum GEOOKOL. 15 (2): 7-14. Liu, W. (2002). Subsurface Flow Constructed Wetlands Performance Evaluation, Modeling and Statistical Analysis. University of Nebraska : Ph.D Thesis. Lu, J.S.C., Eichenberger, B. and Stearns, R.L. (1984). Production and Management of Leachate from Municipal Landfills: Summary and Assessment. US EPA Environmental Laboratory, Ohio. unpublished. Lu, J., Eichenberger, B., and Stearns, R. (1985). Leachate from Municipal Landfills, Production and Management. Park Ridge, N.J.: Noyes Publication. Lugowski, A., Haycock D., Poisson, R. and Beszedits, S. (1989). Biological Treatment of Landfill Leachate. Proceeding of the 44th Industrial Waste Conference. Purdue University West Lafayetty, Indiana. 108 Lytle, C.M., Lytle, F.W., Yang, N., Qian, J.H., Hansen, D., Zayed, A. and Terry, N. (1998). Reduction of Cr (VI) to Cr (III) by Wetland Plants – Potential for In Situ Heavy Metal Detoxification. Environmental Science and Technology. 32(20): 3087-3093. Maehlum, T. (1995). Treatment of landfill leachate in on-site lagoons and constructed wetlands. Water Science Technology. 32(3): 129-135. Mantovi, P., Marmiroli, M., Maestri, E., Tagliavini, S., Piccinini, S. and Marmiroli, N. (2003). Application of a Horizontal Subsurface Flow Constructed Wetland on Treatment of Dairy Parlor Wastewater. Bioresource Technology. 88: 85 – 94. Markert, B. (1994). Environmental Sampling for Trace Analysis. In: Muna Mohammad. Pengolahan Air Larut Lesap Melalui Tanah Bencah Buatan Aliran Subpermukaan dengan Scirpus globulosus dan Ericaulon sexangulare bagi Penyingkiran Logam Berat. Universiti Teknologi Malaysia, Malaysia. Mashhor, M., Sofiman, O. and Asyraf, M. (2002). Management of Wetland Weeds in Aquatic Systems. In : Editors : Mashhor, M., Eng, L.P. and Shutes, R.B.E. “Constructed Wetlands : Design, Management and Education”. Malaysia: Universiti Sains Malaysia Publisher. Masud, M.A., Baig, M.A., Malik, M. and Hassan, I. (2004). Constructed Treatment Wetlands : An Option for Wastewater Treatment in Pakistan. Electron. Journal Environmental Agriculture and Food Chemistry,. ISSN: 1579-4377. Matthew, M.C. (2001). Nitrification of Landfill Leachate by Biofilm Columns. Virginia Polytechnic Institute and State University : Master Thesis. Metcalf and Eddy (1991). Wastewater Engineering. 3rd edition. New York: McGraw-Hill. Moshiri, G.A. (1993). Constructed Wetland for Water Quality Improvement. United States: Lewis Publishers. Mulamoottil, G., McBean, E.A., and Rovers, F. (1999). Constructed Wetlands for the Treatment of Landfill Leachates. United States: Lewis Publishers. Nancy, V.H. (2004). Review of Constructed Subsurface Flow vs. Surface Flow Wetlands. U. S. Department of Energy. unpublished. Navid, D. (1989). The International Law of Migratory Species: The Ramsar Convention. Natural Resources Journal. 29: 1001-1016. 109 Neralla, S., Weaver, R. W., Lasikar B. J. and Persyn, R. A. (2000). Improvement of Domestic Wastewater Quality by Subsurface Flow Constructed Wetland. Bioresource Technology. 75: 19-25. Noor Ida Amalina Ahamad Nordin (2006). Leachate Treatment using Constructed Wetland with Magnetic Field. Universiti Teknologi Malaysia: Master Thesis. Palit, T. and Qasim, S.R. (1977). Biological Treatment Kinetics of Landfill Leachate. Journal of the Environmental Engineering Division, ASCE. 103(2): 353-366. Pant, H.K., Reddy, K.R. and Lemon, E. (2001). Phosphorus retention capacity of root bed media of sub-surface flow constructed wetlands. Ecological Engineering. 17: 345–355. Paquiz, M.R. (2004). Constructed Wetlands for Sanitary and Industrial Wastewater Treatment in Developing Communities. Albert Nerken School of Engineering: Master Thesis. Paredes, D. (2003). Landfill Leachate Treatment in Constructed Wetlands: Removal of High Nitrogen Loads. Center of Environmental Research, Germany. Unpublished. Peverly, J.H., Surface, J.M. and Wang, T. (1995). Growth and Trace Metal Adsorption by Phragmites australis in Wetlands Constructed for Landfill Leachate Treatment. Ecological Engineering. 5: 21 – 35. Pohland, F.G. (1975). Sanitary Landfill Stabilization with Leachate Recycle and Residual Treatment. Environmental Protection Agency, Ohio. unpublished. Polonsky, A.P. and Clements, W.H. (1999). Contaminant Assimilation within the Water Column of Two Newly Created Prairie Wetlands. Archives of Environmental Contamination & Toxicology. 36(2): 140-145. Polprasert, C., Dan, N.P. and Thayalakumaran, N. (1996). Application of constructed wetlands to treat some toxic wastewaters under tropical conditions. Water Science and Technology. 34: 165–171. Qasim, S.R. and Burchinal, J.C. (1970). Leaching from Simulated Landfills. Journal of Water Pollution Control Federation. 43(3): 371-379. Qasim, S.R. and Chiang, W. (1994). Sanitary Landfill Leachate: Generation, Control and Treatment. Texas: Technomic Publication. 110 Rafidah Hamdan (2003). Kajian Pengaruh Konfigurasi Tumbuhan di dalam Sistem Tanah Bencah Buatan Jenis Aliran Sub-permukaan terhadap Penyingkiran Bahan Organic dan Logam Berat di dalam Air Larut Lesap. Universiti Teknologi Malaysia: Master Thesis. Reddy, K.R., Sacco, P.D., Graetz, D.A., Campbell, K.L. and Porter, K.M. (1983). Effect of aquatic macrophytes on physico-chemical parameters of agricultural Drainage Water. Journal of Aquatic Plant Mangement. 21: 1-7. Reed, S.C., Crites, R.W. and Middlebrooks, E.J. (1995). Natural Systems for Waste Management and Treatment. 2nd ed. New York: McGraw-Hill. Renee, L. (2001). Constructed Wetlands: Passive Systems for Wastewater Treatment. National Network of Environmental Management Studies. U.S. Environmental Protection Agency. unpublished. Sanford, W.E., Kopka, R.J., Steenhuis, T.J., Surface, J.M. and Lavine, J.M. (1990). An Investigation into the Use of a Subsurface Flow Rock-Reed Filters for the Treatment of Leachate from a Solid Waste Landfill. Proceeding of 1990 WPCF National Specialty Conference on Water Quality Management of Landfill. Chicago. Sawidis, T., Chettri, M. K., Papaionnou, A., Zachariadis, G. and Stratis, J. (2001). A study of metal distribution from lignite fuels using trees as biological monitors. Ecotoxicology Environmental Safety. 48 : 27-35. Scholes, L., Shutes, R.B.E., Revitt, D.M., Forshaw, M. and Purchase, D. (1998). The treatment of metals in urban runoff by constructed wetlands. Science of the Total Environment. 214 (1–3): 211–219. Sheoran, A.S. and Sheoran, V. (2005). Heavy metal removal mechanism of acid mine drainage in wetlands: A critical review. Minerals Engineering. 19: 105– 116. Sinicrope, T.L. and Langis, R., Gersberg, R.M., Busnardo, M.J. and Zedler, J.B. (1992). Metal Removal by Wetland Mesocosms Subjected to Different Hydroperiods. Ecological Engineering. 1: 309-322. Soltan, M.E. and Rashed, M.N. (2001). Laboratory study on the survival of water hyacinth under several conditions of heavy metal concentrations. Advances in Environmental Research. 7: 321–334. 111 Song, Z., Zheng, Z., Li, J., Suna, X., Hana, X., Wang, W. and Xua, M. (2006). Seasonal and Annual Performance of a Full-scale Constructed Wetland System for Sewage Treatment in China. Ecological Engineering. 26: 272–282. Tanner, C. (1996). Plants for constructed wetland treatment systems; A comparison of the growth and nutrient uptake of eight emergent. Ecological Engineering. 7: 59-83. Tchobanoglous, G., Theisen, H., and Vigil, S. (1993). Integrated Solid Waste Management: Engineering Principles and Management Issues. New York: McGraw-Hill. Thien, S.H. (2005). Leachate Treatment by Floating Plants in Constructed Wetland. Universiti Teknologi Malaysia: Master Thesis. Thornton, R.J. and Blanc, J.R. (1973). Leachate Treatment by Coagulation and Precipitation. Journal of the Environmental Engineering Division, ASCE. 99(4): 535-544. Tjasa, B., Ferfila, N. and Vrhovsek, D. (2004). Sustainable Reclamation of Landfill Sites. Management of Environmental Quality: An International Journal. 15(1): 55-61. Uloth, V.C. and Mavinec, D.S. (1977). Aerobic Treatment of a High Strength Leachate. Journal of the Environmental Engineering Division, ASCE. 103(4): 647-745. Vesk, P.A. and Allaway, W.A. (1997). Spatial variation of copper and lead concentrations of water hyacinth plants in a wetland receiving urban run-off. Aquatic Botany. 59: 33-44. Vesk, P.A., Nockolds, C.E. and Allaway, W.G. (1999). Metal Localization in Water Hyacinth Roots from an Urban Wetland. In: Soltan, M.E. and Rashed, M.N. Laboratory Study on the Survival of Water Hyacinth under Several Conditions of Heavy Metal Concentrations. Advances in Environmental Research. 7: 321-334. Vyda, O.M. and Grimm, A. (1977). Country Treats a Shredfill Leachate. Civil Engineering, ASCE. 102: 44-49. Vymazal, J. (2005). Horizontal Sub-surface Flow and Hybrid Constructed Wetlands Systems for Wastewater Treatment. Ecological Engineering. 25: 478–490. Waterhouse, B. and Mitchell, A. (1998). Northern Australia Quarantine Strategy Weeds Target List. AQIS Miscellaneous Publication 6/98. 112 Watson, J.T., Reed, S.C., R.H. Kadlec, R.L. and Knight, A.E. (1989). Performance Expectations and Loading Rates for Constructed Wetlands. In: Hammer, D.A. Constructed Wetlands for Wastewater Treatment-Municipal, Industrial and Agricultural. Chelsea, Ml: Lewis Publishers. 319-351. Zaman, H. Z. (1992). Actual Siltation of Landfill Site and Improvement Design for Sanitary Landfill in Malaysia. Nasional Seminar on Municipal and Industrial Waste. Kuala Lumpur. Zhu, Y.L., Zayed, A.M., Qian, J.H., De Souza, M. and Terrt, N. (1999). Phytoaccumulation of Trace Elements by Wetland plants: Water hyacinth. Journal of Environmental Quality. 28(1): 339-344. APPENDIX 113 APPENDIX A Raw Data Table A1 : Influent characteristics of the Pasir Gudang leachate Parameter Value (mg/L) Ammonia Nitrogen (NH4-N) 84.5 Nitrate Nitrogen (NO3-N) 35.0 Orthophosphate (PO43-) 87.5 Suspended Solid (SS) Turbidity Ferum (Fe) Manganese (Mn) 160 450 33.68 0.48 Table A2 : Quality of leachate after 3 days of treatment NH4-N (mg/L) NO3-N (mg/L) PO4-3 (mg/L) Fe (mg/L) Mn (mg/l) Turbidity SS mg/L Trial 1 Influent Control SSF effluent Control FWS effluent 84.5 94.7 89.9 82.4 76.1 35.0 30.0 37.0 28.0 31.0 87.5 18.2 19.5 31.6 17.0 33.68 15.1 12.5 11.2 9.1 0.48 0.42 0.43 0.35 0.32 450 250 240 200 180 160.0 156.7 130.0 140.0 128.3 Trial 2 Control SSF effluent Control FWS effluent 87.8 62.5 53.2 53.0 30.0 40.0 26.0 25.0 32.0 9.0 16.5 25.5 13.5 11.6 10.1 7.4 0.39 0.41 0.32 0.29 120 118 117 105 181.7 141.7 135.0 126.7 Control SSF effluent Average Control FWS effluent 91.3 76.2 67.8 64.5 30.0 38.5 27.0 28.0 25.1 14.3 24.1 21.3 14.3 12.0 10.7 8.2 0.41 0.42 0.34 0.30 185 179 159 143 169.2 135.8 137.5 127.5 Parameter Trial 114 APPENDIX A Raw Data Table A3 : Quality of leachate after 6 days of treatment NH4-N (mg/L) NO3-N (mg/L) PO4-3 (mg/L) Fe (mg/L) Mn (mg/l) Turbidity SS mg/L Trial 1 Influent Control SSF effluent Control FWS effluent 84.5 74.6 87.9 63.6 40.1 35.0 27.0 25.0 26.0 18.0 87.5 28.4 16.4 26.2 15.8 33.68 10.1 6.9 8.9 3.8 0.48 0.31 0.25 0.27 0.21 450 174 153 125 109 160 128.3 98.3 123.3 75.0 Trial 2 Control SSF effluent Control FWS effluent 52.3 39.9 54.3 32.5 25.0 22.0 24.0 14.0 19.4 17.9 19.3 16.8 8.7 6.4 6.4 4.4 0.27 0.24 0.24 0.22 106 94 99 70 135.0 110.3 115.0 98.7 Control SSF effluent Average Control FWS effluent 63.4 63.9 58.9 36.3 26.0 23.5 25.0 16.0 23.9 17.2 22.7 16.3 9.4 6.7 7.7 4.1 0.29 0.24 0.26 0.21 140 124 112 90 131.7 104.3 119.2 86.8 Parameter Trial Table A4 : Quality of leachate after 9 days of treatment NH4-N (mg/L) NO3-N (mg/L) PO4-3 (mg/L) Fe (mg/L) Mn (mg/l) Turbidity SS mg/L Trial 1 Influent Control SSF effluent Control FWS effluent 84.5 58.7 18.6 48.1 12.5 35.0 23.0 16.0 19.0 15.0 87.5 22.2 14.4 19.5 8.7 33.68 6.7 1.6 5.4 0.7 0.48 0.19 0.18 0.15 0.12 450 114 75 76 50 160.0 100.7 55.0 89.3 45.7 Trial 2 Control SSF effluent Control FWS effluent 49.6 37.2 45.3 35.6 22.0 12.0 19.0 10.0 18.3 15.5 17.5 14.9 4.7 1.3 3.6 0.9 0.19 0.19 0.13 0.11 74 61 69 55 98.3 80.7 87.0 78.3 Control SSF effluent Average Control FWS effluent 54.1 27.9 46.7 24.0 22.5 14.0 19.0 12.5 20.3 15.0 18.5 11.8 5.7 1.4 4.5 0.8 0.19 0.18 0.14 0.11 94 68 73 53 99.5 67.8 88.2 62.0 Parameter Trial 115 APPENDIX A Raw Data Table A5 : Quality of leachate after 12 days of treatment NH4-N (mg/L) NO3-N (mg/L) PO4-3 (mg/L) Fe (mg/L) Mn (mg/l) Turbidity SS mg/L Trial 1 Influent Control SSF effluent Control FWS effluent 84.5 38.6 8.5 35.7 5.7 35.0 17.0 2.0 15.0 6.0 87.5 9.1 13.3 8.8 10.5 33.68 4.4 0.6 2.9 0.4 0.48 0.13 0.10 0.09 0.08 450 45 28 39 25 160.0 60.3 35.7 57.0 33.3 Trial 2 Control SSF effluent Control FWS effluent 39.8 31.5 36.5 28.1 21.0 9.0 18.0 5.0 16.8 14.4 16.2 14.1 2.6 0.8 2.1 0.6 0.09 0.06 0.07 0.04 52 46 47 40 70.7 69.3 68.3 66.0 Control SSF effluent Average Control FWS effluent 39.2 20.0 36.1 16.9 19.0 5.5 16.5 5.5 13.0 13.8 12.5 12.3 3.5 0.7 2.6 0.5 0.11 0.08 0.08 0.06 49 37 43 33 65.5 52.5 62.7 49.7 Parameter Trial Table A6 : Quality of leachate after 15 days of treatment NH4-N (mg/L) NO3-N (mg/L) PO4-3 (mg/L) Fe (mg/L) Mn (mg/l) Turbidity SS mg/L Trial 1 Influent Control SSF effluent Control FWS effluent 84.5 23.5 2.3 21.6 1.3 35.0 12.0 5.0 10.0 3.0 87.5 8.1 7.5 7.6 5.8 33.68 1.9 0.3 1.6 0.3 0.48 0.06 0.05 0.03 0.02 450 37 20 25 11 140.0 55.0 31.7 53.7 30.3 Trial 2 Control SSF effluent Control FWS effluent 34.5 24.5 28.9 20.3 15.0 6.0 13.0 4.0 14.9 13.9 14.4 13.5 0.9 0.4 0.8 0.3 0.06 0.03 0.05 0.03 36 32 34 18 49.7 30.0 45.0 28.7 Control SSF effluent Average Control FWS effluent 29.0 13.4 25.2 10.8 13.5 5.5 11.5 3.5 11.5 10.7 11.0 9.7 1.4 0.4 1.2 0.3 0.06 0.04 0.04 0.02 37 26 30 15 52.3 30.8 49.3 29.5 Parameter Trial 116 APPENDIX A Raw Data Table A7 : Quality of leachate after 18 days of treatment NH4-N (mg/L) NO3-N (mg/L) PO4-3 (mg/L) Fe (mg/L) Mn (mg/l) Turbidity SS mg/L Trial 1 Influent Control SSF effluent Control FWS effluent 84.5 18.4 1.8 14.5 0.2 35.0 9.5 2.0 7.0 1.0 87.5 5.5 4.6 2.1 1.6 33.68 1.3 0.2 1.1 0.1 0.48 0.02 0.02 0.02 0.01 450 18 7 10 1 140.0 51.0 27.0 47.3 23.7 Trial 2 Control SSF effluent Control FWS effluent 25.4 14.2 22.5 11.5 12.0 3.0 9.0 1.5 13.6 9.9 11.2 5.5 1.0 0.2 0.8 0.2 0.04 0.02 0.02 0.01 15 5 8 3 35.3 20.0 29.7 17.0 Control SSF effluent Average Control FWS effluent 21.9 8.0 18.5 5.9 10.8 2.5 8.0 1.3 9.6 7.3 6.7 3.6 1.1 0.2 1.0 0.2 0.03 0.02 0.02 0.01 17 6 9 2 43.2 23.5 38.5 20.3 Parameter Trial 117 APPENDIX B Varian Analysis Calculation (ANOVA) Table B1 : Varian Analysis Calculation (ANOVA) for NH4-N removal (%). Comparison between Control system and Planted system Day 0 3 6 9 12 15 18 Control 0 19.82 30.27 44.74 57.32 70.13 78.11 Planted 0 23.64 57.07 71.57 80.03 87.27 93.08 Anova: Two-Factor without Replication SUMMARY Row 1 Row 2 Row 3 Row 4 Row 5 Row 6 Count Column 1 Column 2 2 2 2 2 2 2 Sum 43.5 87.3 116.3 137.3 157.4 171.2 6 6 300.4 412.7 Average Variance 21.7 7.3 43.7 359.2 58.2 359.9 68.7 9 78.7 146.8 85.6 112.1 50.1 68.8 515.3 648.2 ANOVA Source of Variation Rows Columns Error Total SS df 5624.9 1050.3 192.9 5 1 5 6868.04 11 MS 1124.98 1050.31 38.57 F 29.17 27.23 P-value 0.001 0.003 F crit 5.05 6.61 118 APPENDIX B Varian Analysis Calculation (ANOVA) Table B2 : Varian Analysis Calculation (ANOVA) for NO3-N removal (%). Comparison between Control system and Planted system Day 0 3 6 9 12 15 18 Control 0 22.86 28.57 45.71 52.86 67.14 77.14 Planted 0 20.00 54.29 64.29 84.29 90.00 96.43 Anova: Two-Factor without Replication SUMMARY Row 1 Row 2 Row 3 Row 4 Row 5 Row 6 Column 1 Column 2 Count 2 2 2 2 2 2 Sum 42.86 82.86 110 137.14 157.14 173.57 6 6 294.29 409.29 Average Variance 21.437 4.08 41.43 330.61 55 172.45 68.57 493.88 78.57 261.22 86.79 185.97 49.05 68.21 449.52 812.60 MS 1192.9 1102.08 69.23 F 17.23 15.92 ANOVA Source of Variation Rows Columns Error SS 5964.49 1102.08 346.13 Total 7412.71 df 5 1 5 11 P-value 0.004 0.010 F crit 5.05 6.61 119 APPENDIX B Varian Analysis Calculation (ANOVA) Table B3 : Varian Analysis Calculation (ANOVA) for PO4-3 removal (%). Comparison between Control system and Planted system Day 0 3 6 9 12 15 18 Control 0 72.51 74.01 78.86 85.71 87.43 92.40 Planted 0 75.71 81.38 86.53 85.92 88.97 95.94 Anova: Two-Factor without Replication SUMMARY Row 1 Row 2 Row 3 Row 4 Row 5 Row 6 Column 1 Column 2 Count 2 2 2 2 2 2 Sum 148.23 155.39 165.39 171.63 176.41 188.34 6 6 490.93 514.46 Average Variance 74.11 5.12 77.69 27.21 82.69 29.40 85.82 0.02 88.20 1.18 94.17 6.28 81.82 85.74 63.01 46.94 ANOVA Source of Variation Rows Columns Error Total SS 526.66 46.14 23.07 595.87 df 5 1 5 11 MS 105.33 46.14 4.62 F 22.83 10.00 P-value 0.002 0.025 F crit 5.05 6.61 120 APPENDIX B Varian Analysis Calculation (ANOVA) Table B4 : Varian Analysis Calculation (ANOVA) for SS removal (%). Comparison between Control system and Planted system Day 0 3 6 9 12 15 18 Control 0 14.06 30.52 44.90 60.83 69.17 75.94 Planted 0 20.31 45.73 61.25 68.96 81.56 87.29 Anova: Two-Factor without Replication SUMMARY Row 1 Row 2 Row 3 Row 4 Row 5 Row 6 Column 1 Column 2 Count 2 2 2 2 2 2 Sum 34.38 76.25 106.15 129.79 150.73 163.23 6 6 295.42 365.10 Average Variance 17.19 19.54 38.13 115.62 53.07 133.71 64.89 33.01 75.36 76.84 81.61 64.45 49.24 60.85 570.18 613.18 MS 1175.67 404.67 7.69 F 152.7255 52.5691 ANOVA Source of Variation Rows Columns Error SS 5878.33 404.67 38.49 Total 6321.49 df 5 1 5 11 P-value 1.84E-05 0.001 F crit 5.050329 6.607891 121 APPENDIX B Varian Analysis Calculation (ANOVA) Table B5 : Varian Analysis Calculation (ANOVA) for Turbidity removal (%). Comparison between Control system and Planted system Day 0 3 6 9 12 15 18 Control 0 64.78 75.11 83.89 90.44 93.44 98.00 Planted 0 68.33 80.11 88.33 92.78 96.78 99.56 Anova: Two-Factor without Replication SUMMARY Row 1 Row 2 Row 3 Row 4 Row 5 Row 6 Count Column 1 Column 2 2 2 2 2 2 2 Sum 133.11 155.22 172.22 183.22 190.22 197.56 6 6 505.67 525.89 Average Variance 66.56 6.32 77.61 12.5 86.11 9.88 91.61 2.72 95.11 5.56 98.78 1.21 84.28 87.65 154.96 136.36 ANOVA Source of Variation Rows Columns Error SS 1452.47 34.08 4.1q Total 1490.65 df 5 1 5 11 MS 290.49 34.08 0.82 F 353.66 41.49 P-value 2.29E-06 0.001 F crit 5.050329 6.607891 APPENDIX B Varian Analysis Calculation (ANOVA) 122 Table B6 : Varian Analysis Calculation (ANOVA) for Fe removal (%). Comparison between Control system and Planted system Day 0 3 6 9 12 15 18 Control 0 68.30 77.20 86.54 92.43 96.33 97.18 Planted 0 75.58 87.92 97.67 98.53 99.17 99.52 Anova: Two-Factor without Replication SUMMARY Row 1 Row 2 Row 3 Row 4 Row 5 Row 6 Column 1 Column 2 Count 2 2 2 2 2 2 Sum 143.88 165.11 184.20 190.96 195.50 196.70 6 6 517.98 558.39 Average Variance 71.94 26.46 82.56 57.44 92.10 61.99 95.48 18.61 97.75 4.02 98.35 2.75 86.33 93.06 132.67 92.47 ANOVA Source of Variation Rows Columns Error SS 1090.47 136.08 35.19 Total 1261.74 df 5 1 5 11 MS 218.09 136.08 7.04 F P-value F crit 30.99 0.000908 5.050329 19.33 0.007042 6.607891 123 APPENDIX B Varian Analysis Calculation (ANOVA) Table B7 : Varian Analysis Calculation (ANOVA) for Mn removal (%). Comparison between Control system and Planted system Day 0 3 6 9 12 15 18 Control 0 29.47 45.68 71.05 83.68 91.89 95.58 Planted 0 36.11 55.26 76.32 87.79 95.26 97.68 Anova: Two-Factor without Replication SUMMARY Row 1 Row 2 Row 3 Row 4 Row 5 Row 6 Column 1 Column 2 Count 2 2 2 2 2 2 Sum 65.58 100.95 147.37 171.47 187.16 193.26 6 6 417.37 448.42 Average Variance 32.79 21.98 50.47 45.88 73.68 13.85 85.74 8.43 93.59 5.67 96.63 2.22 69.56 74.74 710.90 598.48 ANOVA Source of Variation Rows Columns Error SS 6529.23 80.36 17.68 Total 6627.27 df 5 1 5 11 MS 1305.85 80.36 3.54 F 369.35 22.73 P-value 2.05E-06 0.005026 F crit 5.050329 6.607891 APPENDIX C Lab Apparatus and Equipments Figure C1 : Leachate pond at Pasir Gudang Sanitary Landfill Figure C2 : Leachate was poured into container 124 APPENDIX C Lab Apparatus and Equipments Figure C3 : Limnocharis flava founded at Pontian Road Figure C4 : Eichhornia crassipes founded at fish pond 125 APPENDIX C Lab Apparatus and Equipments Figure C5 : Limnocharis flava planted in SSF wetland tank Figure C6 : Eichhornia crassipes planted in FWS wetland tank 126 APPENDIX C Lab Apparatus and Equipments 127 Figure C7 : Control and Planted systems for SSF constructed wetland Figure C8 : Control and Planted systems for FWS constructed wetland APPENDIX C Lab Apparatus and Equipments 128 Figure C9 : HACH DR/4000 spectrophotometer machine Figure C10 : Glass microfibre filter disc 5.5m Whatman type GF/C (0.7 µm) APPENDIX C Lab Apparatus and Equipments Figure C11 : Mettler AT261 Delta Range weighing machine Figure C12 : Drying oven for operation at 103˚C to 105˚C 129