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The effectiveness of constructed wetlands for treatment of woodwaste leachate Masbough, Arash 2002

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THE EFFECTIVENESS OF CONSTRUCTED WETLANDS FOR TREATMENT OF WOOD WASTE LEACHATE by ARASH MASBOUGH B.Sc, The University of Tehran, 1995 A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF APPLIED SCIENCE in THE FACULTY OF GRADUATE STUDIES Department of Civil Engineering Environmental Engineering Group Pollution Control and Waste Management Program We accept this thesis as conforming to the required standard: THE UNIVERSITY OF BRITISH COLUMBIA April 2002 © Arash Masbough, 2002 In presenting this thesis in partial fulfilment of the requirements for an advanced degree at the University of British Columbia, I agree that the Library shall make it freely available for reference and study. I further agree that permission for extensive copying of this thesis for scholarly purposes may be granted by the head of my department or by his or her representatives. It is understood that copying or publication of this thesis for financial gain shall not be allowed without my written permission. Department of Civil Engineering The University of British Columbia Vancouver, Canada Date: April 26, 2002 ABSTRACT The forest industry is one of the most important contributors to the economy of the province of British Columbia. This industry supports many wood processing mills located throughout the province. Percolation of the rainfall through woodwaste piles and log storage areas leaches natural chemicals from the wood residuals. A study was performed on a woodwaste storage site near Mission, B.C., where a number of wood processing mills are located adjacent to the Fraser River. The objective of this research was to evaluate the effectiveness of surface flow constructed wetlands for treatment of woodwaste leachate. The leachate was characterized over the period of the study. It had very low pH (-3.5), very high and aggressive oxygen demands (5,000-11,000 mg.L"1 BOD5, and 7,000-18,000 mg.L/1 COD) , very high levels of tannin and lignin (2,800-6,500 mg.L"1) and total VFAs ( 1,800-2,800 mg.L"1), and low levels of nutrients (< 3 mg.L"1 NH3-N, < 0.2 mg.L"1 NOx-N, and < 4 mg.L"1 P04-P). Diluted leachate was directed to six pilot-scale wetland cells, four planted with cattails (Typha latifolia) and two controls, during a total operational period of 34 weeks. As the leachate had a very low nutrient content and pH, nutrient addition and pH adjustments were made to improve contaminant removal. After physical modifications in the site, reductions in pollutants were consistently achieved. The average removals for BOD and COD were in the order of 60% and 50% respectively. On average, up to 69% of VFAs and 42% of tannin and lignin contents were removed. The ThOD comparisons with COD showed that VFAs and tannin and lignin accounted for over 60% of COD in effluent and influent. "Planted and nutrient added" cells were more effective in BOD removal from leachate than the unplanted controls. In addition, the effluent pH values were higher for the planted cells. No significant differences were observed in removal efficiencies of other targeted pollutants between the six cells. Climatic conditions (i.e. precipitation, evaporation and temperature) had a great impact on the performance of the wetlands. In addition, acclimatization of the wetlands increased the treatment ratios. Constructed wetlands proved effective in treatment of woodwaste leachate. Continuous operation of the system will help to elucidate the seasonal fluctuations. Microbiological studies can also shed light on the causes of performance variations. Arash Masbough 11 MASc Thesis (2002) TABLE OF CONTENTS ABSTRACT ii TABLE OF CONTENTS iiList of Tables v List of Figures vii List of Abbreviations ix ACKNOWLEDGEMENTS x 1) INTRODUCTION 1 1-1) B.C.'s Forest Industry 2 1-2) Research Objectives 6 1-3) Project Background 7 1- 4) Research Site Description 8 2) BACKGROUND STUDIES 12 2- 1) Constructed Wetlands 12-1-1) Different Layouts of Constructed Wetlands 14 2-1-1-1) Constructed Surface-Flow (SF) Wetlands.... 16 2-1-1-2) Constructed Subsurface-Flow (SSF) Wetlands2-1-2) The Role of Plants in Constructed Wetlands 18 2- 1-3) Hydraulic Characteristics of Constructed Wetlands 20 2-2) Leachate Control and Treatment 23 2-3) Woodwaste Leachate Characteristics 6 2- 4) Using Constructed Wetlands as an Alternative for Leachate Treatment 31 3) WOODWASTE LEACHATE CHARACTERIZATION 35 3- 1) Methods and Materials 33- 1-1) Sampling Protocols3-1-2) Analytical Protocols 7 3-2) Results and Discussion 40 3-2-1) pH, Temperature, Conductivity, and Solids 4Arash Masbough iii MASc Thesis (2002) 3-2-2) VFAs, Tannin and Lignin, COD, and BOD5, and DO 42 3- 2-3) Nutrients and Other Chemicals 48 3- 3) Conclusions 51 4) PILOT SCALE TREATMENT EVALUATION 53 4- 1) Methods and Materials 54 4- 1-1) System Description4-1-2) Nutrient Addition and pH Adjustment 61 4-1-3) Sampling and Analytical Protocols 2 4-2) Results and Discussion 64-2-1) Characterization of Dilution Water Sources 62 4-2-2) Treatment Performance 4 4-2-2-1) ThOD Comparisons with Measured COD 73 4-2-2-3) Seasonal Effects on Wetlands Performance 80 4-3) Conclusions 85 5) GENERAL CONCLUSIONS AND RECOMMENDATIONS 87 6) REFERENCES 90 APPENDICES 8 APPENDIX A Raw Data 99 APPENDIX B Theoretical Oxygen Demand Calculations 127 APPENDIX C Climatic Data 130 APPENDIX D Seasonal Changes in Wetlands Performance 132 Arash Masbough iv MASc Thesis (2002) List of Tables Page# Table 2-1 Summary of the major roles of macrophytes in constructed treatment wetlands 20 Table 2-2 Chemical composition of leachate from municipal solid waste 25 Table 3-1 Sample collection, preservation and storage 36 Table 3-2 Methods and instruments used for analysis 38 Table 3-3 Frequently measured leachate characteristics (2000 and 2001) 41 Table 3-4 Concentrations of individual volatile fatty acids (2000) 43 Table 3-5 Oxygen demand ratio comparisons 47 Table 3-6 Summary of the measured nutrients in the leachate pool 48 Table 3-7 One-time measured components in the leachate 50 Table 4-1 Characterization of dilution water sources (slough in 2000 and well in 2001) 63 Table 4-2a Field data, pH, and conductivity measurements for influent and effluent, 2000 5 Table 4-2b Field data, pH, and conductivity measurements for influent and effluent, 2001 6Table 4-3a Summary of removal performances for targeted parameters in the pilot-scale constructed wetlands (2000) 68 Table 4-3b Summary of removal performances for targeted parameters in the pilot-scale constructed wetlands (2001) 9 Table 4-4a Summary of removal performance for volatile fatty acids (C2-C6) in the pilot-scale constructed wetlands, 2000 71 Table 4-4b Summary of removal performance for volatile fatty acids (C2-C6) in the pilot-scale constructed wetlands, 2001 71 Table 4-5 Oxygen demand ratio comparisons 3 Table 4-6a Summary of performance for nutrients in pilot-scale constructed wetlands, 2000 76 Table 4-6b Summary of performance for nutrients in pilot-scale constructed wetlands, 2001 7 Arash Masbough V MASc Thesis (2002) Table Al Temperature, pH, DO, and conductivity in constructed Wetland Cells in 2000 99 Table A2 Solids Concentrations in Constructed Wetland Cells in 2000 101 Table A3 BOD, COD, and Tannin and Lignin Raw Data in Constructed Wetland Cells in 2000 110 Table A4 Total Volatile Fatty Acids Raw Data in Constructed Wetland Cells in 2000 113 Table A5 Nutrients Raw Data in Constructed Wetland Cells in 2000 116 Table A6 Temperature, pH, DO, and Conductivity Raw Data in Constructed Wetlands in 2001 117 Table A7 BOD, COD, and Tannin and Lignin Raw Data in Constructed Wetland Cells in 2001 120 Table A8 Total Volatile Fatty Acids Raw Data in Constructed wetland Cells in 2001 122 Table A9 Nutrients in Constructed wetland Cells in 2001 125 Table B1 Total ThOD for VFAs, 2000 128 Table B2 Total ThOD for Tannin and Lignin, 2000 12Table B3 Total ThOD for VFAs, 2001 129 Table B4 Total ThOD for Tannin and Lignin, 2001 12Table Cl Climate Normals, Abbotsford, BC, 1944-1990 131 Arash Masbough VI MASc Thesis (2002) List of Figures Fage Figure 1-1 B.C. exports by product groups, 1999 3 Figure 1-2 General plan of the research site 9 Figure 1-3 Wood-processing shake and shingle mills next to the Fraser River... 10 Figure 1-4 Woodwaste pile as seen from North-South direction 10 Figure 1-5 Leachate pool viewed from top of the pile 11 Figure 2-1 Contaminant removal processes in a constructed wetland 14 Figure 2-2 Types of constructed wetlands 15 Figure 2-3 The three wetland shapes with the best hydraulic efficiencies 22 Figure 3-1 BOD and COD changes in leachate 44 Figure 4-1 Wetland cell cross section 5Figure 4-2 Influent inlet, the replaced spreader pipe, and the influent control valve 55 Figure 4-3 Pilot-scale system site diagram 56 Figure 4-4 General view of the pilot scale wetland cells 57 Figure 4-5 a) The stainless steel electric pump inside the wooden shelter, b) Flow control box: fuses, timers, and switches 58 Figure 4-6 Dosing tank cross-section and details 59 Figure 4-7 a) Drilling a well as the dilution water source replacement, b) Details of the well 60 Figure 4-8 Average pH improvement in pilot scale cells 66 Figure 4-9 pH neutralization measurements during three different time steps using lOg.L"1 limestone and pure leachate 67 Figure 4-10 COD comparisons with ThOD for VFAs and tannin and lignin 75 Figure 4-11 The effect of fertilizer addition on ortho-phosphate concentrations of the cells effluent 78 Figure 4-12 Wetlands seasonal variations for BOD5 and VFAs removal in 2000 79 Figure 4-13 Wetland seasonal variations for COD and tannin and lignin removal in 2000 82 Figure 4-14 Climatic data for year 2000, top: temperature and bottom precipitation 3 Arash Masbough vii MASc Thesis (2002) Figure Cl Temperature Data of Abbotsford, B.C. for 2001 118 Figure C2 Precipitation Data of Abbotsford, B.C. for 2001 11Figure Dl Seasonal Variability in BOD5 in Constructed Wetlands Cells in 2001 120 Figure D2 Seasonal Variability in COD in Constructed Wetlands Cells in 2001 121 Figure D3 Seasonal Variability in Tannin and Lignin in Constructed Wetlands Cells in 2001 122 Figure D4 Seasonal Variability in Volatile fatty Acids in Constructed Wetlands Cells in 2001 123 Figure D5 Seasonal variability in Ammonia in Constructed Wetland Cells in 2000 124 Figure D6 Seasonal variability in Ammonia in Constructed Wetland Cells in 2001Figure D7 Seasonal variability in Nitrate+Nitrite in Constructed Wetland Cells in 2000 125 Figure D8 Seasonal variability in Nitrate+Nitrite in Constructed Wetland Cells in 2001Figure D9 Seasonal Variability in ortho-Phosphate in Constructed Wetland Cells in 2000 126 Figure D9 Seasonal Variability in ortho-Phosphate in Constructed Wetland Cells in 2000Arash Masbough (2002) viii MASc Thesis List of Abbreviations AAS Atomic Absorption Spectrophotometer(y) APHA American Public Health Association BC British Columbia BOD Biochemical Oxygen Demand BOD5 5-Day Biochemical Oxygen Demand COD Chemical Oxygen Demand DO Dissolved Oxygen EPA Environmental Protection Agency FSS Fixed Suspended Solids GC Gas Chromatograph(y) HDPE High Density Polyethylene HRT Hydraulic Retention (Residence) Time LC50 Lethal Concentration: 50% NDIR Non-Depressive Infrared Analyzer PPE Personal Protection Equipments PVC Poly Vinyl Chloride ReCip Reciprocating Bed Wetlands SF Surface Flow Wetlands SSF Sub-surface Flow Wetlands T&L Tannin and Lignin TDS Total Dissolved Solids ThOD Theoretical Oxygen Demand TOC Total Organic Carbon TSS Total Suspended Solids VFAs Volatile Fatty Acids VF Vertical Flow Wetlands VOA Volatile Organic Acids VSS Volatile Suspended Solids Arash Masbough IX MASc Thesis (2002) ACKNOWLEDGEMENTS I have to thank my research advisor, Dr. Ken Hall. He was extremely supportive, patient, and helpful from the first moment that I started in this program. I don't remember a single day going to his office with the most complicated problems, and not leaving without a smile on my face. His knowledge and wisdom were infinitely valuable during the course of this research. I would like to thank Dr. Noboro Yonemitsu in the Environmental Hydraulics Group at UBC. He was always willing to help. It was impossible for me to get to this point without his support. Any student who has been involved in research in Environmental Engineering Group in UBC knows that experiments are not possible without the support of Susan Harper and Paula Parkinson. My research was not an exception. All the instruments and equipment in the Environmental Engineering Laboratory would have been useless without their insight. I am also thankful to the Department of Civil Engineering in UBC for giving me the opportunity. Apart from intensive coarse load, they taught me how to be persistent, examining my knowledge, as well as my endurance. During the period of this research I benefited from the support of a lot of friends. In particular Jody Addah, my friend and officemate. Not only for the fact that he helped me with filed work, but also for his support in the moments that nothing was working. I am also thankful to Wendong Tao. He helped me with the fieldwork and analyses I want to offer my endless thanks to my parents. Their supports during my studies, and life have been unbelievable. And of course it is difficult to say about all of that within these lines. Finally, I should thank my life partner. Parisa always gave me the hope and reason to proceed. She also gave me all the confidence and motivation that I needed. Arash Masbough x MASc Thesis (2002) 1) INTRODUCTION In addition to sunlight and air, water is an indispensable element for most animal and plant life. A casual observation of the world map would suggest that the supply of water is endless, since it covers over 80% of the Earth's surface. Unfortunately, we cannot use it directly; over 95% is in the salty oceans, 2% is tied up in the polar ice caps, and most of the remainder is beneath the Earth's surface. Therefore, there is only a small fraction of the water available for human use, and it is up to humans to maintain access to sustainable sources of clean water. The chemicals present in water affect its quality for the end users. Most industrial activities produce considerable amount of wastewater. Treatment and disposal of industrial wastewater is one of the most challenging fields in environmental engineering practice. Because of the great variety of wastes produced from established industries, and the introduction of wastes from new processes, it is difficult to select a single treatment method for industrial wastewater. Many of the industrial waste problems faced by environmental engineers can be solved by minimizing the quantities of these materials produced and used through product substitution, waste recovery, and recycling. The next step is the introduction of efficient and cost effective treatment processes that are suitable for treating a variety of waste problems. Arash Masbough 1 MASc Thesis (2002) Control and disposal of solid waste are other challenges for environmental engineers. Leachate control and treatment is by far one of the most important aspects in this area. Solid waste composition varies substantially with sources, socio-economic conditions, location, and season. Leachate formation is the result of the removal of soluble compounds by the non-uniform and intermittent percolation of water through the refuse mass. Soluble compounds are generally encountered in the refuse at emplacement or are formed by chemical and biological processes. The sources of percolating water are primarily precipitation, irrigation, runoff, and ground water intrusion and to a lesser extent, initial refuse moisture content. Refuse decomposition due to microbial activity contributes to leachate characteristics and its potential environmental impacts (El-Fadel et al, 1997). The quantity of leachate generated is site-specific. It depends on water availability and weather conditions as well as the characteristics of the solid waste, the landfill surface, and the underlying soil. The quality of leachate is highly dependent upon the stage of fermentation in the solid waste, the composition of the waste, operational procedures, and co-disposal of the wastes (Pohland et al, 1983). 1-1) B. C. 's Forest Industry British Columbia's forest industry is a dominant contributor to the provincial economy. In 1999, it made up over 50.3 percent or $18.6 billion of total manufactured shipments inside the province. Wood products accounted for 33 percent and pulp and paper products Arash Masbough 2 MASc Thesis (2002) for 17.3 percent. B.C. has only 17 percent of Canada's total forestland, but grows almost 40 percent of the nations merchantable timber. In general, B.C. harvests less area annually than Ontario and Quebec, yet plants two to three times more area per year. Almost 50 percent of all silviculture expenditures in Canada occur in B.C. (COFI, 2000). Among the goods-producing industries, the forest industry (a combination of the wood products, paper allied industries and logging) is one of the largest contributors to B.C.'s gross domestic product. The total value of forest products exported from B.C. in 1999 was $15.3 billion. Forest products were counted for 58 percent of the total province's exports (Figure 1-1), (Statistics Canada, 2000). All Other 10% Mineral Products 6% Machinery and Agriculture 4% Fish Products 3% Energy Products 10% 58% (i Figure 1-1 B.C.'s exports byproduct groups, 1999 (Source: B.C. Stats; B.C. Origin Exports, Economics and Trade Branch, Ministry of Forests) The B.C. forest industry accounted for 90,600 direct jobs and a further 181,200 indirect and induced jobs in 1999. The forest industry is a source of livelihood for 271,800 British Arash Masbough 3 MASc Thesis (2002) Columbians and represented 14 percent of total provincial workforce in 1999. (COFI, 2000). B.C. produces 48.8 percent of the total lumber production in Canada. The province's contribution in pulp, paper and plywood are 28.6, 13.7, and 83.0 percent of total production in Canada, respectively. There are close to 500 primary mills located in BC, processing almost all of the wood harvested in the province (65 million m3 in 1998). Considering the size of the industry, it is obvious that the related environmental management measures play a very important role in the province (COFI, 2000). Given the dimensions and importance of the industry, it is necessary to consider a management strategy and appropriate regulations to deal with the waste produced. Woodwaste as defined in British Columbia's Waste Management Act includes hog fuel, mill ends, wood chips, bark, and sawdust. It does not include demolition waste, construction wastes, tree stumps, branches, logs or log ends (Government of B.C., 1996). Collection and disposal of this waste is an immense task. There are about 50 sawmills located in British Columbia (Bailey et al., 1999). The woodwaste from sawmills alone has been estimated at about 2.8 million bone-dry tonnes per year (McCloy, 1997). The woodwaste generated from other sectors of the industry such as chipping, panel, and other type of mills, as well as the pulp and paper mills, must be added to this total. Moreover, a large number of wood product storage locations including log yards and chip piles at barge loading facilities require waste management measures, particularly in connection with leachate runoff control and treatment. Arash Masbough 4 MASc Thesis (2002) Woodwaste is a natural product. However, if rainwater seeps into woodwaste it can pollute the environment. Provincial and Federal guidelines provide information on woodwaste use, storage and the woodwaste leachate control. For example, management practices that are specific to woodwaste use and storage include, but are not limited to, the following (Government of B.C., 1996): Only woodwaste uses that minimize the leachate and prevent water contamination are permitted. Environmental requirements common to all woodwaste uses include: o Woodwaste must not be used as landfill unless a permit or approval has been obtained from B.C. Environment, o Woodwaste deposits must not exceed a total of 30 cm, which should be achieved by applying layers that do not exceed 15 cm per year, o A buffer zone of 30 m is required between woodwaste deposit and domestic water supplies, and other sensitive water bodies, o Woodwaste and woodwaste leachate must not be allowed to contaminate surface or ground water, o Stored woodwaste should be covered to prevent leachate from forming and polluting the environment. Arash Masbough 5 MASc Thesis (2002) A quick look at the existing acts, regulations, and bylaws shows that the environmental hazards of woodwaste and its leachate are more or less addressed. The growth of woodwaste piles demonstrates that the amount of woodwaste production in the province is much more than the demand for its use. Conversely, having a look at the active wood processing mills in the province suggests that not all of the regulations are practically applied. There are numerous woodwaste piles along the lower Fraser River and in the interior of the province without any control of leachate production or discharge. 1-2) Research Objectives The objective of this research was to evaluate the effectiveness of surface flow constructed wetlands for treatment of woodwaste leachate. The research was conducted on six constructed wetland cells located near the city of Mission, B.C., Canada, adjacent to the Fraser River. A leachate pool was formed at the site because of runoff from an active woodwaste pile. Leachate was directed to wetland cells, after dilution. The fieldwork began with hydraulic and mixing improvements. The performance of wetlands on the removal of targeted pollutants was monitored for a total of 34 weeks (from May to September, 2000 and from July to October, 2001). This thesis provides with a brief review of the project background and research site description. In the next section (Chapter 2), a background literature review introduces and assesses the types and performances of constructed wetlands as systems of treatment for diverse wastewaters. The characteristics of woodwaste leachate and a review of the Arash Masbough 6 MASc Thesis (2002) leachate control and treatment measures are presented. There are few literature sources on woodwaste leachate treatment. As a result, the production and treatment mechanisms of landfill leachate, as the most similar wastewater to woodwaste leachate, are discussed. In the following section (Chapter 3), the results on long-term characteristics of woodwaste leachate on the study site are presented. Next is a description of the pilot scale site and the different components of the system. This is followed by presentation and discussion on the results of the removal efficiency for targeted pollutants (Chapter 4). In the last section (Chapter 5), this thesis finishes with the conclusions based on the presented results and recommendations for further possible research. 1-3) Project Background The research site was selected on October 1997 and permission was secured from the landowners and B.C. Shake and Shingle Association to conduct research on the wood-processing site. The agreements were collected from the B.C. Ministry of Environment, Lands and Parks and various other stakeholders. A particular agreement required that the bottom of the experimental wetland cells should be protected with impermeable liners and all of the produced effluent should be collected and pumped back to the woodwaste pile (i.e. generation point) (Frankowski, 2000). Characterization studies were started on the site and nine sampling trials were conducted. In the mean time, bench scale studies were carried out to evaluate the feasibility of constructed wetlands in treatment of the woodwaste leachate. Eight small wetlands were Arash Masbough 1 MASc Thesis (2002) constructed using broad-leaved cattails (Typha latifolia) planted in fish tanks. The microcosm wetlands were placed in a controlled environment room. The results from the bench scale wetlands were promising. The system with 29 days HRT, achieved 93% removal in toxicity and 80% removal in COD. The BOD removal was as high as 94% with a HRT of 25 days. After the successful bench scale trials, the construction of the pilot scale wetlands started in May 1998 at the research site. Six wetland cells were constructed on the site and four of them were randomly selected and planted with cattails (Typha latifolia). Due to necessary adaptation time, Fraser River flooding event, and financial constraints, the field trials were limited to a six-week period (October-December 1999). However, in this period, the wetland system proved to be capable of treating this leachate. There was a need for more research to optimize the performance of the wetlands (Frankowski, 2000). The project was taken over in May 2000. New research activities were started with physical improvement of the treatment system. 1-4) Research Site Description The research site was situated on the west side of the city of Mission, approximately 75 kilometres east of Vancouver, B.C. It was located in the coastal climate region with relatively high mean annual precipitation (1563 mm per year). Daily mean temperatures Arash Masbough 8 MASc Thesis (2002) varied between 2 °C in January to 17 °C in August. Daily minimum and maximum temperatures were reported as low as -1 °C and as high as 24 °C, respectively (Environment Canada, 1999). The west side of Mission is a rural setting with a few agricultural farms (mostly corn farms) and a few wood processing mills. The study site was adjacent to one of the wood-processing mills on the north bank of the Fraser River (Figures 1-2 and 1-3). Figure 1-2 General plan of the research site (not on scale) Arash Masbough 9 MASc Thesis (2002) Figure 1-3 Wood-processing shake and shingle mills next to the Fraser River On the east side of the series of processing mills, there was a pile of miscellaneous woodwaste generated. The pile had a diameter of approximately 200 m and was over 20 m high. Taking into account the significant precipitation and the permeable character of the woodwaste, a considerable amount of leachate was potentially produced (Figure 1-4). Figure 1-4 Woodwaste pile as seen from North-South direction Arash Masbough 10 MASc Thesis (2002) Due to leachate flowing to the adjacent tree farm, a pool was formed on the west side of the pile. The pool was approximately 20 m wide and 70 m long. The leachate had a very dark colour, strong sour smell, and fine bubbles were noticeable on its surface. A number of dead trees were still standing throughout in the pool and the nearby trees were clearly weakened (Figure 1-5). Figure 1-5 Leachate pool viewed from top of the pile Because of the closeness of the pile to the Fraser River (<60 m), there was a concern about the effects of leachate discharge to the river. The Fraser River and its tributaries comprise the world's most productive salmon river system and they have a great environmental, economic and social value in the province of British Columbia (CHRS, 2001). Arash Masbough 1 1 MASc Thesis (2002) 2) BACKGROUND STUDIES 2-1) Constructed Wetlands Natural wetlands have been used as convenient wastewater discharge sites for as long as sewage has been collected (at least 100 years in some locations) (Kadlec and Knight, 1996). Constructed wetlands have been recognized for several years as low cost, minimal maintenance systems that could lower the impact of wastewater drainage on natural water bodies (Mitsch and Wise, 1998). The first scientific research studies and pilot-scale constructed wetland wastewater treatment facilities originated in Germany at the Max Planck Institute, where Kathe Seidel undertook detailed testing of many aquatic plants to determine their ability to absorb and breakdown chemical pollutants. Her research first presented in 1953, proved that particular plant species had the ability to remove some pollutants. In addition, plants grown in wastewater exhibited surprisingly varied physiological and morphological changes that aided their performance (Campbell and Ogden, 1999). In a very general sense, understanding the function of constructed wetlands requires us to step back in time to achieve a more basic understanding that every farmer had: plants require water and fertilizer for their growth. Wastewater essentially consists of water, fertilizer, and organic chemicals. Wetland plants, unlike dryland plants, can grow in Arash Masbough 12 MASc Thesis (2002) saturated soils and standing water, and consume several times the nutrients used by dryland crops (Campbell and Ogden, 1999). Constructed wetlands are a designed and man-made complex of saturated substrates, emergent and submergent vegetation, animal life, and water that simulate natural wetlands for human use and benefits (Hammer and Bastian, 1989). Natural or artificial wetlands such as marshes or swamps, with their vegetation (primarily cattails, reeds, and rushes), provide an ideal microenvironment for the sedimentation, filtration, adsorption, and bacterial decomposition of wastewater constituents. Since natural wetlands are usually considered as receiving waters, discharges must meet applicable regulatory requirements and thus are limited to treatment of secondary or tertiary effluents. Constructed wetlands, however, have a much broader application, having been employed to treat primary effluent, industrial wastewaters, acid mine drainage, landfill leachate, and urban runoff. In a typical design, continuously applied wastewater flows freely through parallel basins or channels with relatively impermeable bottom soil, emergent vegetation, and water depths of 0.1 to 0.6 m (Henry and Heinke, 1996). A combination of biological, physical, and chemical reactions are involved in contaminant removal processes in constructed wetlands (Figure 2-1) (USGS 1996). Arash Masbough 13 MASc Thesis (2002) LEACHATE: ^ £ F £ P/an/s transfer oxygen to the root zone 4 Biological Treated water • .^R-...,-'-Jhl. Chemical Physical Figure 2-1 Contaminant removal processes in a constructed wetland (Source: USGS, 1996) The use of constructed wetlands provides a relatively simple and inexpensive solution for treatment of pollution from small communities, industries, storm water, and agricultural runoff. Experience shows that constructed wetlands provide an effective treatment alteration to conventional treatment systems especially for small communities (Vymazal, 1999). 2-1-1) Different Layouts of Constructed Wetlands Constructed wetland technology has advanced dramatically in the last ten years. New wetland designs have the capability of treating high-strength wastes and functioning even in subfreezing environments. Constructed wetlands usually comprise reeds (Phragmites australis) and/or bulrushes (Schoenoplectus) planted in gravel or sand. Constructed wetlands may use horizontal or vertical flow (see Figure 2-2). Horizontal-flow wetlands Arash Masbough 14 MASc Thesis (2002) may be of two types: surface flow (SF) or subsurface flow (SSF). In the former, the effluent flows freely above the sand/gravel bed in which the reeds etc. are planted, and there may be patches of open water. In the latter type, effluent passes through the sand/gravel bed (Wallace, 2001). A wide selection of design variations exists for each of these alternatives. In addition, these two types of wetlands can be combined with each other or with other conventional, and natural technologies to create hybrid systems that meet specific needs. Each type has advantages and disadvantages for different applications. a) Horizontal Flow b) Vertical Flow Figure 2-2 Types of constructed wetlands: a) Vertical flow b) Horizontal flow (Source: Fujita, 1998) Arash Masbough 15 MASc Thesis (2002) 2-1-1-1) Constructed Surface-Flow (SF) Wetlands Surface-flow constructed wetlands mimic natural wetlands in that water flows principally above the ground surface, as shallow sheet flow, through a more or less dense growth of emergent wetland plants. Four features are common to all constructed SF wetlands: an inlet device, the wetland basin, the wetland plants, and an outlet device (Kadlec and Knight, 1996). A typical constructed SF wetland is a sequence of sealed shallow basins containing 20-30 cm of rooting soil with water depth of 20-40 cm. Dense emergent vegetation covers a significant fraction of the surface, usually more than 50%. Commonly used plants are Typha spp. and Scirpus spp., but natural assemblages of volunteer regrowth from native seed banks are also used. Deep, open areas are added for wildlife, or to function as sedimentation basins. Flow is directed into a cell along a line comprising the inlet, upstream embankment, and is intended to proceed across all portions of the marsh to one or more outlet structures (Kadlec, 1995). Surface flow wetlands are well established, but their use is limited in severely cold-climate applications when year-round treatment is required (Wallace, 2001). 2-1-1-2) Constructed Subsurface-Flow (SSF) Wetlands Constructed, SSF wetland systems treat wastewater by passing it horizontally or vertically through a permeable media planted with wetland plants. Microbial attachment Arash Masbough 16 MASc Thesis (2002) sites are located on the surface of media and on the roots of the wetland plants. Although SSF wetlands have many features in common with SF wetlands, they also have a number of differences that are important during planning. The principal components of a SSF constructed wetland are the inlet distribution system, the basin configuration, the bed media, the plants, and the outlet control system (Kadlec and Knight, 1996). SSF beds are commonly vegetated with Phragmites spp. Submerged beds, populated by plants such as Elodea canadensis or Mariophyllum aquaticum, are seen less frequently. Channels with floating leaved plants, either Eichhornia crassipes or Lemna spp., are also used. The former is used in frost-free climates (Kadlec, 1995). Freezing of the gravel bed could occur in winter if the weather is cold enough. The extent and severity of freezing is strongly influenced by the amount of snow or other insulation present. With cold temperature and no snow resulting in the worst freezing. The year-round use of SSF constructed wetlands has proved feasible in the permafrost zone. Vertical Flow (VF) and Reciprocating Bed (ReCip) wetlands, which are two sub-groups of SSF wetlands, are being successfully used to treat waste previously considered "too strong". In VF wetlands, as the name implies, water flows vertically within the gravel bed. ReCip wetland was originally developed to deal with high-strength agricultural waste. The basic process uses two gravel-filed wetland cells. Wastewater is pumped back and forth between the two cells. The alternative filling and draining of the wetland draws atmospheric oxygen into the gravel pore spaces, enhancing oxygen transfer. Technical Arash Masbough 17 MASc Thesis (2002) developments in constructed wetlands allow for lower treatment costs in a variety of previously unexplored applications (Wallace, 2001). 2-1-2) The Role of Plants in Constructed Wetlands Plants are an integral part of the effluent treatment processes in constructed wetlands (Wetzel, 1993). The presence or absence of wetland plants is one of the characteristics often used to define the boundary of wetlands. In Clean Water Act of the US Government, wetlands are defined as "areas that are inundated or saturated by surface or ground water at a frequency and duration sufficient to support, and that under normal circumstances do support, a prevalence of vegetation typically adapted for life in saturated soil conditions" (Mitsch and Gosselink, 1993). Thus, it is an inherent property of wetlands, including constructed wetlands, that they are vegetated by wetland plants. The most important functions of the macrophytes in relation to the treatment of wastewater are physical effects due to the presence of the plants. The macrophytes stabilize the surface of the beds, provide good conditions for physical filtration, prevent vertical flow system from clogging, insulate the surface against frost during winter, and provide a huge surface area for attached microbial growth (Brix, 1997). Research has shown that the plant canopy captures the contaminants by creating still regions that allow particulate material to accumulate around stems and leaves. Another effect of plant/flow interaction is the creation of small wakes behind plant stems. This bit of turbulence may Arash Masbough 18 MASc Thesis (2002) improve the plants' uptake of elements, or it may accelerate the uptake of chemicals by microbial communities living on the plants' surfaces (Nepf and Koch, 1999). It is well documented that aquatic macrophytes release oxygen from roots into the rhizosphere and that this release influences the biogeochemical cycles in the sediments through the effects on the redox status of the sediments (Sorrel and Boon, 1992). The roots of the wetland plants supply habitat for microorganisms, which are responsible for degradation of many polluting constituents of wastewater. For this reason, recent studies have considered maximizing the contact between wastewater and the rhizosphere (the root zone). Indeed, it is often considered the primary objective in designing these systems, especially in SSF constructed wetlands (Rash and Liehr, 1999). The metabolism of macrophytes affects the treatment process to a different extent depending on the types of the constructed wetland. Plant uptake of nutrients is only of quantitative importance in SF systems. The macrophytes have additional site-specific values by providing habitat for wildlife and making wastewater treatment systems aesthetically pleasing (Brix, 1997). Constructed wetlands can be planted with a number of adapted, emergent wetland plant species. Wetlands created as part of compensatory mitigation, or for wild life habitat, typically include a large number of planted species. Wetland plant species selection should consider the following: expected water quality, normal and extreme water depths, climate and latitude, maintenance requirements, and project goals (Kadlec and Knight, 1996). Table 2-1 summarizes the major roles of macrophytes in constructed treatment wetlands. Arash Masbough 19 MASc Thesis (2002) Table 2-1 Summary of the major roles of macrophytes in constructed treatment wetlands1 Macrophytes Property Role in treatment process Aerial plant tissue Light attenuation => reduced growth of phytoplankton Influence on microclimate => insulation during winter Reduced wind velocity => reduced risk of resuspension Aesthetic pleasing appearance of the system Storage of the nutrients Plant tissue in water Filter effect => filter out large debris Reduced effluent velocity => increase rate of sedimentation, reduces risk of resuspension Provide surface area for attached biofilm Excretion of photosynthetic oxygen => increase aerobic degradation Uptake of contaminants Roots and rhizomes Stabilizing the sediment surface => less erosion Prevents the medium from clogging in vertical flow system Release of oxygen increase degradation and nitrification Uptake of nutrients Release of antibiotics 'Adopted from Brix (1997) 2-1-3) Hydraulic Characteristics of Constructed Wetlands The design of constructed wetlands and ponds requires multi-disciplinary input involving biological and ecological sciences, aquatic chemistry, engineering hydrology, and flow hydraulics. The hydrologic components of the wetland system include inflow, outflow, precipitation, evaporation and transpiration (considered together as evapotranspiration), and infiltration. Inflow and precipitation represent water inputs to the wetland system, and outflow, evapotranspiration, and infiltration represent water outputs from the wetland system. When all water inputs and outputs are measured over a given time period, a water balance can be conducted to test the accuracy of the measurements. If measurements for a single Arash Masbough 20 MASc Thesis (2002) hydrologic component are not available, the water balance can be used to estimate the missing values (SRCD, 1999). Wetland hydrology is a primary driving force influencing wetland ecology, its development and persistent. Increased demand for agricultural and domestic water supplies, the use of wetlands in wastewater treatment, and speculation about the effects of climate change, have raised awareness of the need for accurate estimates of wetland hydrological fluxes. For most wetlands, evapotranspiration is the major component of energy sink (Souch, et al, 1996). Optimal hydrologic effectiveness and hydraulic efficiency provide the most appropriate conditions for promoting the necessary biological and chemical processes for wastewater treatment (Persson, et al, 1999). The hydrologic characteristics of wetlands are usually described through preparation and analysis of a water budget. However, because of the complex nature of wetlands, there is a great deal of uncertainty over the hydrologic budgets and hydrologic functions of different types of wetlands (Arnold et al, 2001). In the highly unsteady conditions to which most real-world constructed wetlands are subjected, constructing a meaningful residence time distribution is difficult. In flow pattern analysis, combining flow rate and concentrations can be useful for observing when masses of tracer leave the wetland. Still, this form of residence time distribution is dependant on the flow conditions the wetland undergoes. High flow rates mask low concentrations. Tracer tests by Rash and Liehr (1999) on free water surface flow wetlands suggested that these wetlands are not subject to short-circuiting, and that the Arash Masbough 21 MASc Thesis (2002) nominal detention time is usually a good estimate of actual detention times in the wetland. In general, SF wetlands are more efficient than SSF wetlands in terms of hydraulic efficiency. Tracer studies also suggest that plug or continuously stirred flow conditions never occur in natural systems and the concentration-time distribution of natural wetland systems lies somewhere between the distributions of plug flow and fully mixed flow conditions (Wood, 1995). Furthermore, the effective volume in constructed wetlands is less than the nominal storage volume. Investigations by Persson et al, (1999) on thirteen wetland configurations and shapes showed that baffled systems (Figure 2-3a) or elongated pond shapes (Figure2-3 b) provided very high hydraulic efficiency. However, care needs to be applied in designing elongated shapes to ensure that increased flow velocity associated with the narrower cross section does not lead to resuspension and remobilization of settled material. Spreading the inflow across the wetland also provided a high hydraulic efficiency (Figure 2-3 c) a) c) b) Figure 2-3 The three wetland configurations with the best hydraulic efficiencies: a) baffled, b) elongated, c) spread inflow (Adopted from Persson et al, 1999) Arash Masbough 22 MASc Thesis (2002) 2-2) Leachate Control and Treatment Leachate occurrence is by far the most significant threat to groundwater. Once leachate reaches the bottom of the landfill or an impermeable layer within the landfill, it either travels laterally to a point where it discharges to the ground's surface as a seep, or it will move through the base of the landfill and into the subsurface formations. Depending upon the nature of these formations and in the absence of a leachate collection system, leachate has reportedly been associated with the contamination of aquifers underlying landfills (Walls, 1975). It is important to locate the landfills in impermeable soils well above the water table, and to prevent it from accumulating in the landfill. Such ideal conditions are not always available, and additional precautions are frequently necessary to protect groundwater supplies from contamination. Landfill leachate control measures include volume and composition control, treatment, and disposal. Hydraulic barriers (e.g., extraction and relief wells, gradient control wells and trenches, and collection systems are commonly used to control leachate problems. Typically, landfill boundaries (bottom, sides, and top) are covered by a clay or synthetic liner to minimize leachate formation through infiltration or groundwater intrusion. The landfill cover is designed with a sloping surface to enhance surface runoff, which is collected via drainage channels constructed at the surrounding edge of the landfill. Water from precipitation or irrigation that may infiltrate past the landfill cover can be collected Arash Masbough 23 MASc Thesis (2002) via a leachate collection and removal system located under the cover and/or above the bottom liner. The collected leachate is generally treated either on-site and disposed of in a nearby sewer system or, recirculated (El-Fadel et al., 1997). Supplementary measures including clay and/or membrane covers, and liners for the landfill, a leachate collection, removal, and treatment facility, and a groundwater monitoring facility are necessary to protect receiving waters from contamination. However, these measures cannot ensure that no seepage will occur. If leakage does occur, attenuation of contaminants as the liquid passes through the soil serves as an additional barrier to surface and mostly groundwater contamination (Henry and Heinke, 1996). The Characteristics of leachate from landfills vary according to site-specific conditions (Table2-2). Leachates from "old" landfills are often rich in ammonia nitrogen due to the hydrolysis and fermentation of the nitrogenous fractions of biodegradable substrates, with decreases in concentrations are mainly attributed to leachate washout. At landfills where leachate containment, collection and recirculation is practiced to accelerate decomposition of readily biodegradable organic constituents, leachate ammonia nitrogen concentrations may accumulate to higher levels than during conventional single pass leaching, thereby creating an ultimate discharge challenge (Onay and Pohland, 1998). Laboratory and field studies have shown that leachate organic content is microbially degradable under either aerobic or anaerobic conditions. However, in light of their very Arash Masbough 24 MASc Thesis (2002) variable nature, leachates may become toxic to microbial communities. For example, leachate with pH values as low as 1.5 and as high as 9.5 have been reported in the literature (El-Fadel et al., 1997). Although a rare occurrence, such extreme pH values could cause a complete inhibition to the growth of microbial communities (e.g. methanogens), which usually grow best at pH values ranging from 6 to 8 (Zehnder et al., 1982). Table 2-2 Chemical composition of leachate from municipal solid waste (Source: El-Fadel et al, 1997) Parameter Concentration Range Parameter Concentration Range (mg.L-1) (mg.L-1) Alkalinity (as CaC03) 0-20,850 Nitrogen (Ammonia) 0-1,250 BOD5' 0 - 195,000 Phosphorus (Total) 0 - 234 Chloride 11,375 pH 1.5-9.5 COD 2 0 - 89,520 TOC 3 335,000 Hardness (as CaC03) 0.1 - 225,000 TVA 4 (as acetic acid) 0 - 19,000 Iron 0 - 42,000 Phenol 0.17-6.6 5-day Biochemical Oxygen Demand, Chemical Oxygen Demand, Total Organic Carbon, Total Volatile acids Analysis of the leachate provides the basic information for selecting the treatment method. The organic strength, the BOD5 to COD ratio, and the type of volatile fatty acids present are all related to the age of landfill. Acceptance of the leachate to the municipal treatment facility is seldom possible and on-site treatment is normally required (Henry andHeinke, 1996). Leachates from "young" landfills (BOD/COD > 0.7) are in the acid fermentation stage with high organic nitrogen. Leachates from "old", stabilized, landfills (BOD/COD -0.1 to 0.3) are in methanogenic stage and contain nitrogen as ammonia. Both leachates, young and old, have been successfully treated in aerobic biological systems. Suspended growth systems, such as activated sludge, are common for BOD removal where as fixed Arash Masbough 25 MASc Thesis (2002) film (attached growth) systems, such as rotating biological contactors are preferred for nitrification (Forgie, 1988). For the treatment of leachate with a BOD/COD ratio between 0.7 and 0.3, anaerobic treatment has advantages over aerobic processes. These advantages include less sludge production, reduced energy needs, and lower costs. To treat well-stabilized leachates (BOD/COD < 0.1) neither aerobic, nor anaerobic treatment is feasible and physical-chemical methods are needed. The variability in leachate characteristics as a landfill ages, requires flexible treatment systems. This means that over time, a combination of aerobic, anaerobic, and physical-chemical processes will be of the most interest (Henry and Heinke, 1996, U.S. EPA, 1995, Forgie, 1988). 2-3) Woodwaste Leachate Characteristics Untreated woodwaste disposal can cause significant pollution problems in the receiving environment, especially in surface water and groundwater systems. The water-soluble material dissolved from the wood is called leachate. The leachate seeps out from piles of stored logs, wood bark, and sawmills. Odour, colour, oxygen demand and high concentrations of metals and tannin (measured as tannic acid) are the typical characteristics of woodwaste leachate (Phipps, 1974). Woodwaste can have a variety of physical and chemical adverse impacts on aquatic life, depending on its form. Woodwaste, like any organic waste, creates a biochemical oxygen demand (BOD) in sediments as it decomposes, and excessive amounts can reduce or eliminate the aerobic zone (Kendall and Michelsen, 1997). Arash Masbough 26 MASc Thesis (2002) Agricultural use, storage, or land disposal of woodwaste have the potential for generating leachate. A study on groundwater contamination by woodwaste disposal in the Mid-Willamette valley region of Oregon-U.S.A has shown that total iron and manganese were found to be far in excess of normal or background concentrations, and were well above recommended local drinking water standards. An initial drop in pH (less than 5.6) and an increase in total acidity of contaminated groundwater were anticipated due to the leaching of volatile organic acids (VOA) (Sweet and Fetrow, 1975). Woodwaste leaches and/or degrades into some compounds that can be toxic to aquatic life, such as phenols and methylated phenols, benzoic acid and benzyl alcohol, terpenes, and tropolones (Kendall and Michelsen, 1997). Woodwaste leachate, in sufficient concentrations, can be toxic to salmonids (Phipps, 1974). Aspen leachate proved toxic to aquatic organisms at dilutions between 1% and 10% (Taylor et al, 1996). It has been characterized by amber colour, low pH (4.0), extremely high BOD (>2600 mg.L"1), and high conductivity (1140 ps.cm"1). In addition, the leachate was rich in phenols (30 mg.L" '), organic carbon (2480 mg.L"1) and organic nitrogen (13 mg.L"1). The aged leachate underwent a transition marked by a rise in pH and dissolved oxygen (DO) concentration, a small decline in conductivity, and a colour change from amber to black. Median acute toxicity concentrations were consistently 1% to 2% of full strength leachate for trout and Daphnia. Inhibition of bacterial metabolism began at concentrations below 0.3%. Leachate was less toxic to plant life but inhibited algal growth at concentrations of 12% to 16%). In this study, toxicity declined abruptly when the supply of labile toxicants was exhausted, but in certain cases, it increased again from the products of microbial Arash Masbough 27 MASc Thesis (2002) metabolism. Oxygen depletion, low pH, and phenolic compounds contributed to the toxicity of aspen leachate, but much of the toxic effect was attributed to other, unidentified constituents. The potential water quality degradation of surface and ground waters from wood bark drainage is significant. It is shown that degradation results from colour, BOD, organic materials potentially toxic to fish, and odour, imparted to the water. Where the bark is stored on the land, rainwater moving through the pile carries out large amounts of pollutant materials. The dissolved oxygen (DO) of a stream would be seriously affected since BOD values as high as 6800 mg.L"1 were noted for hardwood bark when it was stored wet at 37 °C for 48 days. The colour in some cases reached as high as 5500 colour units. Gas chromatographic analysis of the liquid from the aerobic region of the water showed the presence of only a few identifiable simple sugars. The amounts of these sugars were less than 5 ppm (Sproul and Clifford, 1968). Potential contaminants that could contribute to wood leachate toxicity include metals, wood extractives, and chemicals used to control molds and fungi on freshly cut wood. Bailey et al, (1999) have analyzed the acute toxicity of the storm water runoff from sawmills in British Columbia. They have evaluated the potential contribution of metals to toxicity. Concentrations of metals have been compared to available data for rainbow trout toxicity to determine potential causes of toxicity in the samples. They showed that this toxicity is mainly caused by some of the divalent cation species dominated by zinc, Arash Masbough 28 MASc Thesis (2002) which ranged from 0.04 to 0.94 mg.L"1. Other cations were present in the following ranges: aluminium (< 0.01 to 0.04 mg.L"1), copper (<0.01 to 0.02 mg.L"1), cadmium (< 0.025 mg.L"1), manganese (0.006 to 2.12 mg.L"1), lead (< 0.08 mg.L"1), and nickel (< 0.03 mg.L'1). Through the measurements of resin acids, and tannin and lignin, Bailey et al. (1999) concluded that toxicity in samples, not attributed to metals, is likely due to wood extractives, in particular tannin and lignin (53 to 108 mg.L"1), or other organic acid wood extractives that co-varied with tannin and lignin. Total tannin and lignin greater than 10 mg.L"1 were always associated with toxicity. A study by Thurlow et al. (1977) indicates the characteristics of wastewater leached from log storage as follows: the wood and bark wastes generally consisted of tannins, wood sugars, nutrients (nitrogen and phosphorus), and lignin. The quality of organics released into the water is dependent on the wood species, the amount of bark adhering to the wood, the area of the exposed logs, and the circulation flow of the water. Bark contains a higher proportion of extractives than wood and, therefore, the more bark that remained on a log, the more concentrated was the leachate that seeped out. This study also indicated that tannin and lignin often impart a yellowish-brown colour to water and that leaching rates do not differ greatly between saline and fresh water. The constituents of wood extractives and woodwaste leachate vary significantly depending on the kinds of trees. In a study by Bianco and Savolainen (1997) chromatographic analysis was done to identify tannin fractions in hard and soft wood. They showed that oak tannin contains phenolic compounds (i.e. gallic and ellagic acids) Arash Masbough 29 MASc Thesis (2002) while acacia tannins contain vanillic acid and syringaldehyde. Spruce and fir tannin fractions did not contain identifiable major phenolic and their tannin concentrations were an order of magnitude less than the above-mentioned woods. However, identified phenolics accounted for only a part of the total tannins (Bianco and Savolainen, 1997). Abietic and pimaric acids are the most abundant resin acids naturally occurring in wood. The resin acid content of the wood leachate also varies significantly within species according to tree age, tree part, growing environment, and storage conditions (Teschke, et al, 1999). In a gas chromatographic study by Becker et al. (2001) on the leaching extracts from pine wood (Pina nigra) mainly alcohols and ketones were found (C7 ~ C12). These substances originated from the lignite and polyose fraction of the wood. Hemicellulose compounds are among the most dominating extractives in wood leachate (Bertaud et al., 2002, Gabrielii et al., 2000). In a study on hemicellulosic extractions from the poplar wood, xylans were found to be the most predominant component (Sun et al, 2001). Peters et al. (1976) have studied the effect of red cedar leachate on aquatic organisms. The study showed highest concentrations of extractives are found in heartwood. Heartwood extractives can be divided to two main groups, lignans and volatiles. The lignans make up to 8-15% dry weight of the heartwood, and are polyphenolic compounds. Plicatic acid, the major lignan, is a strong organic acid. The volatile fraction, 0.5-2% dry weight of the heartwood, consists mainly of the tropolones, methyl thujate, thujic acid, and neutrals. The tropolones are known for their fungicidal properties. The toxicity data obtained from the laboratory bioassays indicated that under certain Arash Masbough 30 MASc Thesis (2002) conditions western red cedar leachate had a significant effect on the aquatic environment. The static leachate samples had a strong colour with a pH of 4.3 and a BOD5 of 715 mg.L"1. Tropolones were found to be the primary cause of leachate toxicity to fish. In addition, Kiparissis et al. (1996) have documented that natural constituents of wood such as planar terpenoids may contribute to the overall toxicity potential of the wood pulp leachates. Leachate from the softwood pulp appeared to have more toxic effects on fish, than hardwood pulp. 2-4) Using Constructed Wetlands as an Alternative for Leachate Treatment The practice of landfilling results in a number of potentially damaging environmental impacts, one of which is the generation of landfill leachate. In addition to the initial moisture content of the solid waste and any liquid waste inputs, water may enter landfills by the ingress of precipitation, surface water or ground water. Contact between this water and the waste generates a leachate contaminated with a range of soluble organic and inorganic substances (Tyrrel et al, 2002). Treatment wetlands have been successfully used for non-point sources of pollution (i.e. agricultural and urban runoff), municipal wastewater, sludge treatment, pulp mill effluent, acid-mine drainage and mining waste, oil, food and agricultural industry wastewater, coal mining wastewater, and landfill leachate. They have been proved Arash Masbough 31 MASc Thesis (2002) effective on removal of BOD, COD, suspended solids, nutrients, heavy metals, pathogens, disinfection by-products and also increasing pH in highly acidic influents (Rostad et al, 2000, Gerba et al, 1999, Rash and Liehr, 1999, Tarutis et al, 1999, Martin et al, 1999, Mitsch and Wise, 1998, Bulc et al, 1997, Morris and Herbert, 1997, Schreijer et al, 1997, Kadlec and Knight, 1996, Zachritz et al, 1996, Birkbeck et al, 1990, Lienardetfa/, 1990). Landfill leachates are classified as problematic wastewaters and represent a dangerous source of pollution for the environment due to their toxicity. Leachate is most often transported to a wastewater treatment plant, where it is treated along with municipal wastewater. Various hazardous substances in the landfill leachate can affect the biological process of the purification. For this reason and because transport represents a risk, it is best to treat landfill leachate on site (Bulc et al, 1997). Although effective advanced leachate treatment systems exist, some landfill operators seek alternative treatment systems, because of their high capital costs and specialized management requirements. Land-based treatment systems are an attractive alternative for landfill operators as they utilise an existing land resource, are considered cheaper to build and operate, and do not need sophisticated management. Land-based systems may be used in conjunction with a conventional tank-based system to play a polishing role (Tyrrel et al, 2002) Arash Masbough 32 MASc Thesis (2002) The use of constructed wetlands to treat landfill-generated leachate has become a treatment modality, which has received much attention over the past few years. One factor has caused heightened interest in the use of constructed wetlands for landfill leachate treatment is the variations in quality and quantity of leachate that is produced by different landfills. Not only does leachate composition vary day-to-day, it is also affected by regional climatologic patterns and characteristics of the refuse including its depth and permeability. Therefore, attempts to modify traditional treatment modalities to address these variations can prove very costly (Martin et al., 1999). Because of this inherent variability in composition, no two landfills produce the same quality of leachate. This variability presents landfill managers with the problem of providing cost-effective, reliable, flexible, on-site technologies for pre-treatment and on-site disposal, or off-site disposal such as direct discharge of treated effluent into receiving waters. Landfill leachates can contain a large variety of hydrocarbons, including priority pollutants, phenolics, and high BOD of many origins. Reports indicate that significant reductions of BOD and total organic carbon (TOC) can be achieved by constructed wetland treatment systems (Kadlec and Knight, 1996). In a study on low-strength leachate, the removal of BOD5 (from over 50 mg.L"1 to less than 20 mg.L"1) and ammonia nitrogen removal in the order of 5-6 g ammonia N/m2 marsh area/day was achieved (Birkbeck et al., 1990). Another study, also suggested that wetlands have excellent organic carbon and nitrogen treatment capabilities (Kozub and Liehr, 1999). Arash Masbough 33 MASc Thesis (2002) Bulc et ah, (1997) have studied a pilot scale treatment wetland receiving landfill leachate. The influent concentrations in this study were 1264 mg.L"1 for COD, 60 mg.L"1 for BOD5, and 88 mg.L"1 for NH3-N. They showed that the constructed wetlands were efficient achieving reductions in COD (68%), BOD5 (46%), NH3-N (81%), Fe (80%), and bacteria (85%). By studying the ortho-phosphate concentrations, they concluded that low phosphorus levels could limit biomass growth and subsequently the treatment efficiency. They recommended that in spring, when plant growth is accelerated, phosphorous should be added to attain greater biomass. Arash Masbough 34 MASc Thesis (2002) 3) WOODWASTE LEACHATE CHARACTERIZATION As described in section 2-3, woodwaste leachate is considered "harmful" to the environment. In particular, some studies have shown that it can be toxic to aquatic life. Its toxicity was mostly related to oxygen depletion, low pH, tannin, and phenolic compounds (Bailey et al, 1999, Kiparissis et al, 1996, Peters et al, 1976, Phipps, 1974). In order to evaluate the effectiveness of an existing constructed wetlands system for treatment of woodwaste leachate, the long-term characterization of the leachate is necessary. In this study, research was restricted to woodwaste leachate from a single wood-processing site due to limitations in available time and funding. However, the volume of the waste on the site is one of the largest in the lower Fraser Valley. The woodwaste leachate was characterized over 34 weeks in two periods: from May to September 2000, and from June to October 2001. 3-1) Methods and Materials 3-1-1) Sampling Protocols Standard sampling procedures were followed during sampling trips. Surface grab samples were taken from the east bank of the leachate pool. Sufficient sample volumes were collected in pre-washed 1 L bottles to meet the need of analyses. Sample containers were rinsed twice with sample before filling. Headspaces were avoided in the bottles. All Arash Masbough 35 MASc Thesis (2002) samples were preserved according to the Standard Methods (APHA et al., 1998), (Table 3-1) and were carried in coolers and placed in storage room as soon as they were in the laboratory. All samples were labelled. Temperature and dissolved oxygen of the samples were measured in the field at the time of collection. Appropriate PPE (personal protection equipments) were used during sampling procedures. Laboratory storage was at 4 °C, in the dark. All of the analyses were conducted in first opportunity considering the allowable holding times recommended by accepted protocols (Table 3-1). Table 3-1 Sample collection, preservation and storage (Standard Methods, APHA et al, 1998) Analysis Container Min. Sample Vol. Preservation Allowable Holding time Temperature and DO - - - in Situ pH and Conductivity HDPE' - - -Solids HDPE 200 mL refrigerate 7 days Total Metals HDPE 200 mL nitric Acid, <pH2 28 days Ammonia (NH3-N) HDPE 200 mL sulphuric Acid, <pH2 7 days and refrigerate Nitrate + Nitrite (NOx"-N) HDPE 200 mL sulphuric Acid, <pH2 7 days and refrigerate Ortho-phosphate (P043\P) HDPE 200 mL sulphuric Acid, <pH2 28 days and refrigerate Chemical Oxygen Demand HDPE 100 mL refrigerate 7 days (COD) Biochemical Oxygen HDPE IL refrigerate 6 hours Demand (BOD5) Total Volatile Fatty Acids Glass 200 mL 2% Phosphoric acid 7 days (VFAs) and refrigerate Total Tannin & Lignin Glass 200 mL refrigerate 28 days Total Organic Carbon HDPE 25 mL HC1, <pH2 28 days 2-methoxyphenol Glass 200 mL refrigerate 28 days High Density Polyethylene Arash Masbough 36 MASc Thesis (2002) Quality control measures included the use of field and lab blanks. The field blanks were made by filling the sample bottles with distilled water (distilled water was obtained from the Environmental Engineering laboratory, UBC), which was exposed to atmosphere during sampling procedure. Subsequently, the field and lab blanks were pre-treated and analyzed in exactly the same manner as the samples. 3-1-2) Analytical Protocols Except for the dissolved oxygen and temperature (field data), the chemical analyses were carried out in the Environmental Engineering Laboratory of the Department of Civil Engineering at the University of British Columbia. Standard analytical protocols were followed in all of the tests. Filed parameters (DO and temperature) were measured using portable DO meter. All laboratory analyses were conducted following the methods, and using the instruments summarized in Table (3-2). Arash Masbough 37 MASc Thesis (2002) Table 3-2 Methods and instruments used for analyses Analysis Method Instrument Temperature and DO In situ probe YSI Model 75 DO meter pH pH probe Beckman Model O 44 pH meter Specific Conductivity Conductivity probe Radiometer Copenhagen Model CDM3 SCT meter Solids Std. #' 2540C to 2540F Lindberg Furnace (#51828), VWR Scientific 1350FM faced-air oven, and Mettler AC 100 Digital Scale Total Metals Std. #' 3111 B AAS2 Varian Spectr AA220 FS Ammonia (NH3-N) # 10-107-09-01 of Lachat Quick-Chem 8000 Lachat Quick-Chem Nitrate + Nitrite (NOx-N) # 10-107-04-01 of Lachat Quick-Chem 8000 Ortho-phosphate (P043~P) Lachat Quick-Chem # 10-115-01-01 of Lachat Quick-Chem 8000 Lachat Quick-Chem Chemical Oxygen Demand (COD) Std. #' 5220 D (Closed HACH DR/2000 Direct reading reflux) spectrophotometer @ X=600nm Biochemical Oxygen Demand (BOD5) Std. #' 5110 B (Seeded) YSI Model 50 DO meter and Fisher Scientific Model 307 Incubator Total Volatile Fatty Acids (VFAs) Supelco Inc., GC Supelco Gas Chromatograph bulletin 751 G Model HPGC 5880A Total Tannin & Lignin Std. #' 5550 B HACH DR/2000 Direct reading spectrophotometer @ A=700nm Total Organic Carbon (TOC) Std. #' 5310 B Shimadzu NDIR3 (TOC-500) 2 -methoxypheno 1 Method adopted from Hewlett Packard GC Model Prahacs(1986) HP6890 (equipped with mass selector 5973 and HP 7673 auto-sampler) ' Standard Methods (APHA et al. 1998) 2 Atomic Absorption Spectrophotometer 3 Non-Disperssive Infrared Analyzer The BOD bottles were seeded using the forest soil collected from the leachate pool banks. It was assumed that the microbial communities in the forest soil are adapted to wood extractives, including some of the components which might be toxic to other bacteria. Thus, they were the preferred group of microorganisms for seeding. Only 0.1 g (moist weight) of soil was added to each 300 mL BOD bottle. Seeded blanks were used Arash Masbough 38 MASc Thesis (2002) in all BOD tests in order to make corrections for any possible interference due to seeding. The seeded blanks constantly had an oxygen demand of less than 1 mg.L"1 over time. All samples were corrected for this background BOD. BOD samples were also highly diluted (up to 3000 times). Due to this high dilution, there was no concern about the leachate toxicity affecting the results. Total tannin and lignin was measured using colorimetric method (Method 5550 B, APHA et al, 1998). In order to reduce the usage of toxic reagents and to simplify the method with direct preparation of the sample in spectrophotometer tubes, the method was modified using one tenth of the sample volume recommended in Standard Methods (APHA et al, 1998). Considering the high concentration of analyte present in samples, all samples were diluted up to 500 times. Lab blanks were used to make the standard curve and calibrate the instrument. Minimum detectable concentrations for these compounds have been reported as low as 0.025 mg.L"1 for tannic acid and 0.1 mg.L"1 for lignin in a 1 cm cell using a spectrophotometer (APHA et al, 1998). All standards and samples had concentrations higher than these limits. All of the raw data are presented in Appendix A. Considerable dilutions were required in order to bring the values within the measurable ranges for COD and tannin and lignin. Thus, the possibility of the strong leachate colour affecting results was insignificant. Arash Masbough 39 MASc Thesis (2002) 3-2) Results and Discussion 3-2-1) pH, Temperature, Conductivity, and Solids During the two periods of sampling, in spring-summer 2000 and summer-fall 2001, leachate showed consistent pH values. The pH of the leachate had an average of 3.5 during sampling period. This pH is in the lower limit of the range observed in municipal landfill leachates (Table 2-2). The leachate always had comparably higher temperatures than nearby water bodies. Its average temperature was 28.4 °C in 2000 and 20.2 °C in 2001, which was 6 to 7 °C higher than other ponds in the area. The higher temperature can be elucidated by the high chemical and biological activities in the leachate. In addition, composting processes occurring in the woodwaste pile could potentially heat up the leachate pool. Another reason for the higher temperature is related to the dark colour of leachate, which absorbs more solar energy compared to clear water. Arash Masbough 40 MASc Thesis (2002) Table 3-3 Frequently measured leachate characteristics (2000 and 2001) Parameter 2000 Average1 (Std. Dev.) n2 2001 Average (Std. Dev.) n Temperature (°C) (ambient) 28.4 (2.2) 9 20.2 (4.3) 15 Dissolved Oxygen (ambient) 0.3 (0.1) 13 0.4 (0.1) 14 pH 3.4 (0.1) 13 3.62 (0.2) 14 Specific Conductivity (us.cm1) 1930 (122) 8 1466 (73) 15 Biochemical Oxygen Demand (BOD) 7405 (1227) 19 7786 (1559) 15 Chemical Oxygen Demand (COD) 13774 (3398) 19 12806 (1876) 15 Tannin and Lignin (as tannic acid) 4988 (1357) 19 3445 (489) 15 Total Volatile fatty Acids (C2 - C6) 2107 (343) 15 2085 (185) 15 Total Suspended Solids 33.6 (26.3) 17 - -All concentrations are reported in mg.L" , unless otherwise noted 2 n = number of samples The suspended solids determination is one of the important parameters in treatment methods (Sawyer et al, 1994). Solids were measured during the 19 weeks period from May to September 2001. Leachate contained a very high level of TDS (total dissolved solids) and a very low level of TSS (total suspended solids) (Metcalf and Eddy, 1991). Over 99% of the solids present in the leachate were dissolved, and up to 85% were volatile dissolved solids (see Appendix A). Volatile solids are generally a measure of the organic content of the wastewater. Arash Masbough 41 MASc Thesis (2002) Specific conductivity measurements can give a practical estimate of the dissolved solids content of the wastewater (Sawyer et al, 1994). The high level of dissolved solids was also noticeable in specific conductivity measurements in the leachate. The average specific conductivity was 1930 ps.cnf1 in 2000 and 1466 ps.cm-1 in 2001. As mentioned above, the leachate was characterized with low level of suspended solids and high level of dissolved solids. Treatments through settling, flocculation, and sedimentation were not practicable options because of the lack of suspended solids. In other words, the leachate pool itself is acting as a sedimentation basin. 3-2-2) VFAs, Tannin and Lignin, COD, and BOD5, and DO Volatile fatty acids (VFAs) are short chain carboxylic acids. Their size is represented by the number of carbon atoms they contain, where the smallest VFA is acetic acid with two carbon atoms (C2). Several different bacteria hydrolyse polymers such as cellulose to sugars and ferment the sugars to VFAs (Madigan et al, 1997). The leachate contained very high concentration of total VFAs. The average concentration of total VFAs was 2107 mg.L"1 in 2000 and 2085 mg.L"1 in 2001. These VFAs were, to some extent, responsible for the strong smell and acidic nature (pH ~ 3.5) of the leachate. Measurements of individual VFAs showed that more than half of the total concentration was composed of smaller molecules (e.g. acetic and propionic acid) (Table 3-4). Arash Masbough 42 MASc Thesis (2002) Table 3-4 Concentrations of individual volatile fatty acids in mg.L"1 (2000) Volatile Fatty Acid Average Range n1 Total (C2 - C6) 2107 1641-2829 15 Acetic 1073 858-1321 15 Propionic 364 252-460 15 Butyric + Iso-butyric 434 254-594 15 Valeric 275 154-324 15 n-Hexanoic 175 92-382 15 1 n = number of samples VFAs are readily biodegradable and can act as a source of carbon for microbial communities. The concentration of tannin and lignin was very high in the leachate. The average T&L concentration was 4989 mg.L"1 in 2000 and 3447 mg.L"1 in 2001. These levels of tannin and lignin were expected considering the source of leachate. However, they were higher than reported concentrations in other studies (Section 2-3). This class of compounds is highly coloured and is characterized by its recalcitrant nature. They have been reported to be toxic to aquatic life in much lower concentrations (53 to 108 mg.L"1) (Bailey et al, 1999). The COD test is used to measure the total amount of oxygen required for oxidation of organic compounds to carbon dioxide and water regardless of the biological assimilability of the substances. This test cannot differentiate between biologically oxidizable (e.g. VFAs) and biologically inert (e.g. tannin and lignin) organic matter. However, it provides a good approximation of the organic strength of the wastewater (Sawyer et al, 1994). The leachate had an extremely high chemical oxygen demand with the average concentration of 13774 mg.L"1 in 2000 and 12806 mg.L"1 in 2001. These concentrations are comparable with landfill leachate COD concentrations (Table 2-2). Arash Masbough 43 MASc Thesis (2002) The COD concentrations in the leachate were not constant during the sampling period. The changes can be partially related to the amount of rainfall and temperature. As shown in Figure 3-1, the COD concentrations were rising as the temperature increased in the summer of 2000 (see Appendix C, Figure 4-14). 20000 18000 16000 14000 12000 1> 10000 8000 6000 4000 2000 20000 18000 16000 14000 ^ 12000 m 10000 S 8000 6000 4000 2000 33 OTQ CTQ crq T3 13 Date •Biochemical Oxygen Demand {BOD} (mg/L) Chemical Oxygen Demand {COD} (mg/L) Figure 3-1 BOD and COD changes in leachate (Top: 2000- Bottom: 2001) This trend can be explained by the higher rate of chemical and biological activities in warmer temperatures. As the mean temperature raised, the higher activity rate, higher Arash Masbough 44 MASc Thesis (2002) evaporation, and lower precipitation concentrated the leachate. The increase in COD was not significant in 2001. This can be explained by the fact that in 2001, operation was held during cooler and wetter period of the year. Lower temperatures and higher precipitation decreased the strength of the leachate in 2001. A comparison between the changes in leachate strength and climatic data in Appendix C gives a more clear explanation of these changes. The theoretical oxygen demands (ThOD) were calculated for VFAs and tannin and lignin using balanced oxidation reactions (see Appendix B). These values were then compared to the measured COD, which represents the total oxygen demand. This comparison gave an estimation of the fractions of total COD that correspond to these two classes of compounds. After the entire 34 weeks of sampling, the average ThOD to COD ratio was ~ 0.6. The VFAs ThOD to COD ratio was 0.23 and T&L ThOD to COD was 0.37. These numbers meant that about 60% of the total COD was due to T&L and VFAs. The remaining 40% was due to other groups of compounds, which were not measured in this study. Other groups of compounds accountable for COD could be hemicellulosic compounds, pectins and resin acids (Bertaud et al, 2002, Sun et al, 2001, Gabrielii et al, 2000, Teschke et al, 1999). BOD is defined as the amount of oxygen required by bacteria while stabilizing decomposable organic matter under aerobic conditions. The test is widely used to determine the pollutional strength of wastewaters in terms of oxygen that they will require if discharged into natural water courses (Sawyer et al, 1994). Theoretically, non biodegradable compounds would not exert oxygen under test conditions (standard Arash Masbough 45 MASc Thesis (2002) conditions associated with temperature and light, oxygen, nutrients, and microorganisms availability). The woodwaste leachate had an average seeded BOD5 of 7405 mg.L"1 (in 2000) and 7786 mg.L"1 (in 2001). This high level of BOD was expected given the particularly high COD values discussed earlier. Previous study on the same leachate showed that the leachate had a very aggressive oxygen demand (i.e. BOD5 k ratio ~ 0.5 d"1) (Frankowski, 2000). Dissolved oxygen measurements on site supported this idea. DO concentrations were consistently below the reliable measurement limit of the DO meter (i.e. < 1 mg.L"1) During the determination of COD, almost all the organic matter is converted to carbon dioxide and water. For example, VFAs and tannin and lignin are both oxidized completely. As a result, COD values are greater than BOD values especially when significant amounts of biologically resistant organic matter (e.g. tannin and lignin) is present. Wood related wastes are perfect examples for their high lignin content (Sawyer et al., 1994). In comparison over the period of sampling of this leachate, the BOD to COD ratio had an average of 0.50. This ratio implies that nearly half of the COD was ascribed to readily biodegradable material. As discussed before, the VFAs were theoretically accountable for almost 23% of COD or about half of this readily biodegradable portion. (It is possible that the other half of COD consisted of recalcitrant compounds. From the total COD, about 37%> was calculated to be related to tannin and lignin. This was more that 70% of non-biodegradable portion of COD. Table 3-5 summarizes the results of oxygen demand ratios. Arash Masbough 46 MASc Thesis (2002) Table 3-5 Oxygen demand ratio comparisons COD ratio Average n ThOD of VFAs to COD 0.23 30 ThOD of T&L to COD 0.37 34 Total ThOD2 to COD 0.60 30 BOD ratio Average n ThOD of VFAs to BOD 0.46 30 BOD to COD O50 34_ 1 n = number of samples 2 Total ThOD = VFAs ThOD + T&L ThOD In a quick comparison between the results in 2000 and 2001, it can be noticed that, the levels of contaminants were slightly lower in 2001, except for BOD. The greatest decline was in the concentrations of tannin and lignin. The lower concentration of contaminants can also be explained by the general hypothesis that the strength of the leachate reduces as the age of the waste increases (El-Fadel et al., 1999). The other factor affecting the contaminant concentration would be the seasonal changes. In the year 2000, the sampling was done during the warmer and dryer period (May-September). The high level of evaporation and low precipitation raised the strength of the leachate. In 2001, the sampling was done during a relatively cooler and wetter period of the year (June-October), which resulted in a more dilute leachate. In the case of BOD, as the microbial activity breaks down the large molecules, more easily biodegradable compounds become available. The higher level of BOD in the second year can be correlated to the higher level of readily biodegradable compounds (i.e. smaller molecules). Arash Masbough 47 MASc Thesis (2002) 3-2-3) Nutrients and Other Chemicals During the period of this study, concentrations of ammonia, nitrates and ortho-phosphate were consistently measured. Table 3-6 summarises the concentrations of the nutrients during the two sampling periods. This leachate was also very nutrient poor. The levels of ammonia and nitrates were extremely low. The chemical composition of the biota requires continuous source of nutrients to sustained growth and reproduction of microorganisms. The carbon:nitrogen:phosphorous ratio for plants is roughly 40C:7N:1P by weight (Wetzel, 1975). There were some ortho-phosphate, ammonia, and nitrates present in the leachate. However, comparing to the level of the total organic carbon present (TOC ~ 3775 mg.L"1), those levels were very low. The carbon to nutrients ratio for this leachate were as low as 1C:0.0006P:0.0004N. Consequently, there were insufficient nutrients in the leachate for the microorganisms to degrade the carbon load. This is a significant difference between this woodwaste leachate and landfill leachates. There are generally very high loads of soluble nutrients in landfill leachates (Table 2-2). Although these nutrients are a group of primary contaminants of concern in landfill leachates, they also support the microbial degradation of other contaminants. Table 3-6 Summary of the measured nutrients in the leachate pool 2000 2001 Measured Nutrient Average' n' Average n (Std. Dev.) (Std. Dev.) Ammonia (NH 3-N) 2.94 15 2.29 14 (1.16) (0.51) Nitrate + nitrite (NO X"-N) 0.14 15 0.10 14 (0.12) (0.11) Ortho-phosphate (P043"-P) 4.12 15 0.32 14 (0.96) (0.25) n = number of samples Arash Masbough 48 MASc Thesis (2002) Three metals were also measured in the leachate during a one-time trial. The total concentrations of copper, zinc, and chromium were measured in the leachate. Concentrations of chromium and zinc were 41 and 156 pg.L"', respectively. The concentration of copper was below detection limits of the instrument (< 1 pg.L"1). Although zinc does not pose threatening effects on the human body in low concentrations, it can affect aquatic life. In the study by Bailey et al, (1999), the threshold for acute toxicity of rainbow trout has been reported as low as 14 pg.L"1 of zinc. That is much lower than the concentration measured in this study where average of one time sampling trial from different locations in the pool was 156 pg.L"1 (range: 111-218 pg.L"1). The concentrations of theses three metals along with other measured parameters are summarized in Table 3-7. Some of the data are adopted from a previous study by Frankowski (2000) on the same leachate. As shown in Table 3-7, the woodwaste leachate exhibited high acidity, which is not surprising-considering its low pH. On a previous test by Frankowski (2000), this leachate had a LC50 (Lethal Concentration for 50% of organisms) of 1.4% v/v (rainbow trout 96-hour). The toxicity tests were conducted under defined standardized characteristics. The pH was adjusted and sufficient oxygen was supplied. In addition to the toxic effect of some metals, part of the toxicity of leachate is likely due to VFAs, tannin and lignin, and some phenolic compounds (Taylor et al, 1996). Arash Masbough 49 MASc Thesis (2002) Tannin and lignin are considered to be a major toxicant in wood leachate in concentrations as low as 53 mg.L"1 (Bailey et al, 1999). The level of tannin and lignin in this leachate was almost 100 times higher than this value. Lignans, a class of compounds similar to lignin, have been reported to have a toxic threshold of - 60 mg.L"1. Tropolones, an extractive found in heartwood, has a toxic threshold as low as 0.3 mg.L"1 (Peters et al, 1976). The Standard Method analysis used for this leachate (Method # 5550B, APHA et al, 1998) detects aromatic hydroxyl groups and is unable to distinguish between tropolones and the tannin and lignin group of compounds. As a result, tropolones were an unknown fraction of tannin and lignin concentrations. After initial detection of phenolic compounds by gas chromatography, concentration of one of the phenolic compounds (2-methoxyphenol) was measured in a one-time trial in this leachate. The average concentration of 2-methoxyphenol in 10 samples collected from the leachate pool was 225 pg.L"1 (range: 140-270 pg.L"1). In effluent regulations of the Province of B.C. (1988), the allowable concentration for "total phenol" is 200 pg.L"1. The concentration of only one phenolic compound (2-metoxyphenol) in this leachate was higher than that allowed by regulations. Table 3-7 One-time measured components in the leachate Parameter Concentration 1 Total Organic Carbon (mg.L') 3775 Acidity* (mg.L-1 as CaC03) 2651 Copper (total, ug.L"1) <1.0 Zinc (total, ug.L"') 156 Chromium (total, ug.L"1) 41 Toxicity* (%v/v) 1.4 Rainbow trout 96 hr LC502 'Average of one-time sampling trial (except toxicity) 2 "Lethal Concentration" that causes mortality in 50% of the test organisms * Data adopted from Frankowski (2000) Arash Masbough 50 MASc Thesis (2002) 3-3) Conclusions The leachate investigated during this research should be considered an industrial wastewater that in some constituents was comparable to very strong landfill leachates. It was highly acidic, with an average pH as low as 3.5. The temperature of the leachate was higher than other stagnant surrounding water bodies. It was concluded that this higher temperature was due to composting processes in the pile, high chemical/biochemical activities in the leachate pool, and higher solar energy absorbance. The leachate had a very high concentration of dissolved solids. The high concentration of dissolved solids was confirmed by high levels of specific conductivity. However, a very small fraction of total solids (less than 1%) was suspended. This character of leachate made it impossible to consider flocculation, sedimentation, and precipitation as applicable parts of treatment procedure. The concentration of TOC is correlated with both BOD and COD. Levels of TOC, COD and BOD in the leachate were very high. Because of this high oxygen demand, the leachate had a very low concentration of dissolved oxygen. Significant amounts of tannin and lignin and VFAs were present in the leachate. These two compounds accounted for about 60% of the COD. Further analysis will be needed to clarify the remaining constituents of the measured COD. The BOD: COD ratio was -0.5. This suggested that about half of the COD is due to easily biodegradable compounds. Arash Masbough 51 MASc Thesis (2002) In addition to VFAs and tannin and lignin, Leachate contained other potential toxicants. Phenolic compounds and trace metals were identified. To explain the issues surrounding the causes of toxicity, further research in this regard is necessary. The very low levels of nutrients would make the treatment of this leachate rather challenging. The ratios of nutrients to the carbon content of the leachate were too low. Microbial communities need nutrients for the biological degradation of the waste. The levels of contaminants in the leachate were high enough that its release in the environment without proper treatment would prove harmful. In fact, it poses a serious threat to surface and ground water resources, aquatic life, and even the forestry industry. As mentioned before, because of leachate accumulation in the adjacent property on the site of this research, many trees were killed or damaged. The characteristics of different wood leachates vary significantly. Such variations are partly related to the source of the woodwaste (i.e. types and parts of trees). It is desirable to perform case specific characterization studies before recommending any site related treatment and control measures. Arash Masbough 52 MASc Thesis (2002) 4) PILOT SCALE TREATMENT EVALUATION The study by Frankowski (2000) demonstrated that under optimal laboratory conditions, constructed wetlands are capable of providing efficient treatment of woodwaste leachate. However, assessment of the long-term performance of a pilot scale system under external and internal variations was necessary. To this end, Frankowski (2000) designed, constructed, and used six pilot scale treatment wetlands for treatment of leachate in a three-month period. During the period of pilot scale trials, the possibility of the treatment was established. Constructed wetlands were capable of providing efficient treatment of the leachate including substantial reductions in BOD, COD and acute toxicity (Frankowski, 2000). The pilot scale treatment research re-started on May 2000. The research activities were continued with physical improvement of the system, including hydraulic and mixing modifications. The chemical improvement of the system was also considered. The chemical improvement measures included pH neutralization and nutrients addition. The experimental cells allowed a controlled evaluation of this technology under "real world" operating conditions. Moreover, they gave the potential for a range of concurrent manipulations to be executed during performance optimization. Arash Masbough 53 MASc Thesis (2002) 4-1) Methods and Materials 4-1-1) System Description Each of the wetland cells were a mixture of three parts: a small front bay, a planted surface flow (SF) section, and a small unplanted sub-surface flow (SSF) section just prior to the effluent outlet. The cells had a length to width ratio greater than 3 for highest hydraulic efficiency (Persson et al, 1999). Bank-full dimensions were 17.5 m long and 5.5 m wide. The cells had a trapezoidal cross section with a side slope angle of ~ 35° and an even depth (except for the inlet bay). The bottom of each cell was covered with a 20 mil (0.5 mm) PVC liner. The liner penetrations had been sealed with flanging and clay plugs. The planting substrate has been backfilled to a depth of 30 cm (Figure 4-1). Cattails (Typha Latifolia) Influent Spreader Pipe Influent Backfilled with Surrounding Soil Lateral Discharge Collector Effluent 0.5mmP.V.C Liner Inlet Bay 40 mm Washed Gravel Length: 17.5m Width: 5.5 m Figure 4-1 Wetland cell cross section The front bay was intended to provide a small settling basin to prevent any suspended solids entering the system from influent. The main treatment activities were assumed to occur in the large surface flow section. In this section, influent was flowing over the Arash Masbough 54 MASc Thesis (2002) surface of the soil substrate and through the root mats and stalk of the developing plants. The subsurface flow section was intended to act as a polishing unit. In this section, wastewater was brought in contact with a biofilm layer as it flowed through the gravel matrix. Any large suspended materials, such as algae or detritus, were screened out in this section. A lateral effluent collection pipe (perforated 100 mm PVC pipe) was buried in the bottom of the gravel section, which was connected to a swivelling discharge pipe (100 mm PVC pipe). The design depth was 40 cm. The level of the wastewater in the cells was controlled using the swivelling pipe. At the design depth, the volume of each cell was 20 m . HRT was controlled separately for each cell using the influent valves. More sensitive valves were installed downstream to the old valves in order to have a more controlled inflow (Figure 4-2). During the experiment, the effluent was discharged in another separate pipe installed in the cells' surrounding ditch and then collected in the sump (Figure 4-3). Figure 4-2 Influent inlet, the replaced multi-port inlet, and the influent control valve Arash Masbough 55 MASc Thesis (2002) Influent was distributed across the width of the cells through multi-port inlets. The spreader pipes together-with the appropriate length to width ratio of the cells provided the best hydraulic efficiency with minimum short circuits and dead spaces. Optimal hydraulic efficiency provides the most appropriate conditions for promoting necessary biological and chemical processes involved in wastewater treatment (Persson et al, 1999). The previous spread pipes were replaced by a set of new and more robust pipes (Figure 4-2). Figure 4-3 Pilot-scale system site diagram (Not on scale) Arash Masbough 56 MASc Thesis (2002) Four of the six cells had been randomly chosen and planted. The remaining two cells were identical in construction to the others with the exception of remaining unplanted (Figure 4-4). The unplanted cells were serving as experimental controls. The results from those cells provided an opportunity to define the effect of plants on the treatment performance. Due to their local availability and demonstrated capability to survive in the leachate, broad-leaved cattails (Typha latifolia) had been selected as the emergent plants. Each of the four cells was planted with 120 cattails with an approximate of three plants per m . The vegetation had been planted in lateral bands in order to ensure that the flow resistance was dispersed evenly across the width of the cells (Frankowski, 2000). Figure 4-4 General view of the pilot scale wetland cells (as seen from top of the woodwaste pile) The leachate was too strong for treatment in the wetlands without prior dilution. A dosing tank was used to provide sufficient dilution using nearby sources of water. The tank was Arash Masbough 57 MASc Thesis (2002) located in a higher elevation than cells in order to supply enough hydraulic head for the influent to flow into the cells. Leachate was transferred from the pool to the dosing tank via an electric pump installed next to the pool. A similar pump was installed beside a nearby slough to provide the dilution water. A third pump was installed at the sump in the surrounding ditch to transfer the effluent back to the pile. G&L® lhp centrifugal pumps (Model NPE, 230 V, single phase) were used. They were equipped with brass foot valves in order to supply the initial prime. The intake of the pumps was made completely of stainless steel, which prevented them from corrosion. This was necessary considering the low pH of the leachate. Pumps were protected from climatic effects using wooden shelters with concrete floors (Figure 4-5a). Arash Masbough 58 MASc Thesis (2002) The capacity of the dosing tank was -10,000 L. The dilution water and leachate were delivered to the tank via 30 mm PVC pipes. The influent was flowing continuously to the cells through 30 mm PVC pipe, and was evenly distributed between them. Dilution ratios were adjustable using timer-controlled pump switches (Figure 4-5b). In addition, the influent level in the tank was maintained using a floating switch. In order to provide the necessary mixing of the leachate and the dilution water, a small fish tank air pump was added to the system on May 2000. The air was pumped near the influent outlet of the tank. Figure (4-6) shows the details of the dilution tank. From Leachate Pool Dilution Water Source Fuses, Switches and v Timers X. Box Floating Switch o o o| 0>$ o o<Pe O Influent (to Cells) Figure 4-6 Dosing tank cross-section and details A nearby slough was used as the source of dilution water in the first season of sampling (2000). In the second season, due to lack of precipitation and some construction activities on the dyke road, there was not enough water available in the slough. On June 2001, a 12 Arash Masbough 59 MASc Thesis (2002) m-deep well was drilled as a substitute source of dilution water (Figure 4-7a). Casing was installed at the top 3 meters of the well. The rest of the depth was protected with perforated pipe (screening). The same pump was used to deliver the well water to the dosing tank. Figure 4-7b shows the details of the drilled well. Figure 4-7 a) Drilling a well as the dilution water source replacement (top)-b) Details of the well (right) (dimensions in m) Ground Level Casing __2 Water Table Screening Foot Valve River Bed .5 To the Pump 3.6 11 Previous microcosm study suggested that an HRT of 8 to 15 days results in a considerable amount of pollutant removal in the constructed wetlands (Frankowski, 2000). The HRT in the cells was controlled with the amount of inflow. Because of the transportation and lab work cycle convenient, an HRT of seven days was maintained throughout the research. Arash Masbough 60 MASc Thesis (2002) 4-1-2) Nutrient Addition and pH Adjustment As discussed in section 3-2, the level of nutrients and nutrient to carbon ratio were very low in the leachate. In an attempt to compensate for this lack of nutrients, phosphorous and urea were added to two of the planted cells. On the last week of June 2000, slow release fertilizer pellets were added to cells #2 and #4 (Figure 4-3). The pellets contained 17% total phosphorus weight ratio (Sterling, 1997). The fertilizers were put in meshed bags and were placed along the width of the cells. Each bag contained 0.5 kg of fertilizer and a total of 2.5 kg was used for each cell. In the first week of July 2001, 2 kg of a different type of fertilizer (Organico®) in meshed bags was added to each of the cells #2 and #4 in order to balance the nitrogen content of the cells. The weight composition of Organico® fertilizer was 20% total N (9% from polymer coated urea), 4% P2O5, and 10% K2O. The nutrient levels were measured inside and in the effluent of the cells in order to estimate the amounts utilized throughout the fertilized cells. To consider the possibility of neutralization of the pH, 5 kg Dolomite® soil conditioner was added to cell #4. It contained 53% calcium carbonate and 41% magnesium carbonate. The neutralization effect of the soil conditioner on the leachate was investigated in the lab before application. Arash Masbough 61 MASc Thesis (2002) 4-1-3) Sampling and Analytical Protocols Sampling was conducted for a total of 34 weeksT during two separate periods (May-September 2000 and June-October 2001) on a weekly basis. Effluent samples were collected from the outlet of each cell using the swivelling pipe. A single influent sample was collected from the outlet of the dosing tank. Leachate and dilution water source (i.e. slough in 2000 and well in 2001) were also sampled to measure any seasonal variations. Samples were collected following the same manner discussed in Section 3-1. Temperature and DO were measure at each sampling location using the meter described in Section 3-1. In addition to temperature and DO, all samples and lab and field blanks were analysed for pH, specific conductivity, BOD, COD, tannin and lignin, VFAs, and nutrients (i.e. ammonia, nitrate and nitrite, and ortho-phosphate). TSS was measured only in 2000. All the analytical protocols were identical to the ones discussed in Section 3-1. 4-2) Results and Discussion 4-2-1) Characterization of Dilution Water Sources An important step in this experiment was to determine the influence of the dilution water on the influent characteristics. In particular, it was necessary to ascertain that the dilution Arash Masbough 62 MASc Thesis (2002) water sources (i.e. slough in 2000 and.well in 2001) did not contribute to the pollutant character of the influent. Therefore, all appropriate analyses as mentioned in sections 3-2-1 and 3-2-2 for the leachate were carried out for these sources. The results of dilution water source characterization are summarized in Table 4-1. Table 4-1 Characterization of dilution water sources (slough in 2000 and well in 2001) Parameter Slough Average1 (Std. Dev.) n2 Well Average (Std. Dev.) n Temperature (°C) (ambient) 20.8 9 10 3 (2.0) (1.2) Dissolved Oxygen (ambient) 2.1 13 2.8 3 (0.4) (0.3) pH 6.18 13 6.35 10 (0.2) (0.17) Specific Conductivity (us.cm"1) 126 8 257 10 (7) (27) Biochemical Oxygen Demand (BOD) 12 19 2.0 13 (6) (2.0) Chemical Oxygen Demand (COD) 131 19 24 8 (31) (25) Tannin and Lignin (as tannic acid) 17 18 1.0 14 (7) (1.0) Total Volatile Fatty Acids (C2 - C6) 30.1 15 26.0 15 (22.5) (22.1) Ammonia (NH 3 -N) 0.2 15 0.2 14 (0.2) (0.1) Nitrate + nitrite (NO x" -N) 0.08 15 0.08 14 (0.06) (0.10) Ortho-phosphate (P043"-P) 0.11 15 0.14 14 (0.08) (0.36) Total Suspended Solids 49 17 _ (65) - -All concentrations are reported in mg.L", unless otherwise noted 2 n: number of samples Arash Masbough 63 MASc Thesis (2002) Concentrations of most chemical constituents measured were at least an order of magnitude less than that of the leachate. Both dilution water sources had a pH well above six. Consequently, these sources were appropriate to reduce the strength of the leachate. 4-2-2) Treatment Performance The pilot-scale constructed wetlands were capable of increasing the pH of the leachate. As mentioned before, the dilution water sources had a pH value greater than 6. However, due to their low buffering capacity, the influent (diluted leachate) still had a very low pH. The average pH of influent was 3.9 in 2000 and 4.3 in 2001 (Table 4-2a, 4-2b). Plants in surface flow wetlands have a major role in pH improvement. Photosynthetically active macrophytes generate oxygen and remove carbon dioxide from the water causing an increase in water pH (Wood, 1995). During this study, reactors were able to increase the pH up to 2 units. The planted cells performed better in increasing pH than the unplanted cells (Figure 4-8). Such a result was expected considering the effect of photosynthetic activity of the plants on the water pH. Adaptation of the wetlands also had a noticeable effect on pH improvement. As it can be seen in both sampling seasons (Figure 4-8), after a few weeks of initial habituation, the pH starts to increase more rapidly in planted cells. Arash Masbough 64 MASc Thesis (2002) Table 4-2a Field data, pH, and conductivity measurements for influent and effluent, 2000 Influent Effluent Control Planted Nutrient added Parameter Average2 Average Average Average (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Temperature (°C) 20.4 21.4 21.3 21.3 (1.7) (1.7) (1.9) (1.8) pH 3.91 4.60 4.78 5.51 (0.18) (0.26) (0.71) (0.65) Dissolve Oxygen (mg.L"1) 1.1 0.6 0.6 0.6 (0.2) (0.2) (0.2) ' (0.2) Specific Conductivity (us.cm"1) 582 415 466 425 (390) (113) (77) (110) These cells were planted 2 Temp: n = 9 for influent, and n = 18 for each reactor set pH and DO :n = 13 for influent, and n = 26 for each reactor set Conductivity: n = 8 for influent, and n = 16 for each reactor set Table 4-2b Field data, pH, and conductivity measurements for influent and effluent, 2001 Influent Effluent Control Planted Nutrient added Parameter Average Average Average Average (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Temperature (°C) 12.2 13.3 14.0 14.3 (2.0) (4.9) (3.2) (3.0) pH 4.33 4.77 4.89 5.10 (0.30) (0.28) (0.39) (0.54) Dissolve Oxygen (mg.L"1) 1.5 0.4 0.3 0.4 (0.9) (0.4) (0.1) (0.3) Specific Conductivity (us.cm"1) 692 593 605 597 (280) (173) (181) (179) These cells were planted 2 Temp: n = 14 for influent, and n = 28 for each reactor set pH and DO: n = 14 for influent, and n = 28 for each reactor set Conductivity: n = 15 for influent, and n = 28 for each reactor set Arash Masbough 65 MASc Thesis (2002) 6.50 % 5.00 - Cell Influent - Date ——A — Average implanted -—•— Average nutrient added and planted -—/K — Average planted Figure 4-8 Average pH improvement in pilot scale cells (top: 2000, bottom: 2001) (note: averages are between two identical cells over time) Because of the higher buffering capacity of the source of dilution water in 2001 (i.e. well), influent had a higher average pH than the previous year (Table 4-2a, 4-2 b). During the second period of treatment trials (2001), leachate neutralization capability of the soil conditioner (Dolomite®) was measured in the lab using pure leachate. The lab results Arash Masbough 66 MASc Thesis (2002) showed that pH in the leachate started to rise up as soon as it came to contact with the soil conditioner (i.e. in a few seconds). Then, as the soluble, outer layer was dissolved, the pH became stable. Meanwhile, a large amount of the soil conditioner (almost 80% of the weight) remained insoluble after 10 minutes (Figure 4-9). It was concluded that the conditioner is capable of increasing pH without dissolving rapidly, so it can stay in the cells for a long period. Measuring the remaining weight of the soil conditioner located in cell #4 showed that 25% of the 5 kg was used up after 2 weeks. During a stage from end of August to beginning of September 2001 (Figure 4-8), the pH increased noticeably because of this base addition. 0 5 10 Time (min) Figure 4-9 pH neutralization measurements during three different time steps using 10 g.L"1 limestone (Dolomite®) and pure leachate Arash Masbough 67 MASc Thesis (2002) Wetlands are generally excellent sediment traps (Kadlec, 1995). During the first season of this study (2000) total suspended solids were reduced from 32.1 mg.L"1 in influent to an average of 24 mg.L"1 in effluent (Table 4-3a). Specific conductivity measurements indicated that dissolved solids were partially removed in the cells (Table 4-2a, 4-2b). Considering the relatively high conductivity of the dilution water sources (specially in the well water, 2001, Table 4-1), it can be concluded that a portion (21 to 37%) of the dissolved solids in the influent was inorganic and thus very hard to remove through biological processes. Table 4-3a Summary of removal performances for targeted parameters in the pilot-scale constructed wetlands, 2000* Influent Effluent Control Planted Nutrients Added2 Parameter Average ' Average %-Removal Average %-Removal Average %-Removal (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Biochemical Oxygen Demand (BOD5) 1702 769 55% 832 51% 642 62% (532) (299) (17%) (273) (17%) (259) (12%) Chemical Oxygen Demand (COD) 3221 1609 50% 1928 40% 1591 51% (1112) (533) (24%) (436) (25%) (530) (21%) Tannin and Lignin (as tannic acid) 978 569 42% 675 31% 570 42% (444) (159) (22%) (197) (26%) (212) (18%) Total Volatile Fatty Acids (VFAs) 499 244 51% 323 41% 163 69% (142) (149) (25%) (172) (24%) (138) (24%) Total Suspended Solids (TSS) 32.1 24.3 22.6 _ 25.0 _ (32.1) (9.9) - (12.5) - (9.2) -n = 19 for influent, and n = 38 for each reactor set 2 These cells were planted * All values reported in mg.L"' Arash Masbough 68 MASc Thesis (2002) Table 4-3b Summary of removal performances for targeted parameters in the pilot-scale constructed wetlands, 2001* Influent Effluent Control Planted Nutrients Added2 Parameter Average' Average%-Removal Average%-Removal Average%-Removal (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Biochemical Oxygen Demand (BOD5) 3465 1414 59%. 1442 63% 1393 60% (1631) (760) (12%) (668) (11%) (772) (16%) Chemical Oxygen Demand (COD) 3980 2827 29% 2632 34% 2973 25% (1513) (1219) (15%) (1031) (16%) (1253) (23%) Tannins and Lignin (as tannic acid) 1160 771 44% 769 40% 797 40% (638) (313) (21%) (276) (21%) (303) (32%) Total Volatile Fatty Acids (VFAs) 707 399 44% 435 38% 439 37% (513) (235) (43%) (186) (55%) (241) (56%) n = 15 for influent, and n = 30 for each reactor set 2 These cells were planted * All values reported in mg.L"' Treatment wetlands are efficient users of external carbon sources, manifested by excellent reductions in BOD and COD (Kadlec, 1995). Removal of BOD was observed throughout the experiments. BOD removal had an average of 52-63%. The removal in "planted and nutrient added" cells was better than other cells in year 2000 (Table 4-3a). In general planted cells showed marginally better removal efficiencies than unplanted ones in 2001 (Table 4-3b). Percentage reductions for COD were lower than BOD. During the two stages of performance evaluations, COD was removed with an average of 25-51%. The removal efficiencies were lower in 2001. In the case of COD, there was no definable difference between the three groups of reactors (Table 4-3a, 4-3b). Arash Masbough 69 MASc Thesis (2002) In both sampling periods, a higher proportion of BOD was removed compared to COD. This can be explained by the fact that easily biodegradable materials (i.e. VFAs) are used up by microbial communities faster than recalcitrant materials (i.e. tannin and lignin). As the microbial communities utilize the readily biodegradable sources of carbon, the amount of BOD decreases faster. Dissolved oxygen levels in treatment wetlands are normally low (Knight et ah, 1993). In the pilot scale study, the dissolved oxygen level was consistently lower than 0.5 mg.L"1. Considering the very high levels of oxygen demand in the influent, low dissolved oxygen values were expected. In the absence of free oxygen gas, anaerobic respiration is an alternative catabolic process to aerobic respiration. A lower amount of carbon is degraded during anaerobic respiration (Kadlec and Knight, 1996). Total tannin and lignin removal rate was in the range of 31-44%. In the case of tannin and lignin, there were no significant removal differences amongst different wetland cells. This demonstrated that the microbial communities that developed in the substrate (water and sediment) of unplanted cells were also capable of contaminant degradation. VFAs were reduced throughout the treatment process. The reduction rate of VFAs was in the range of 37-69%. The relatively high removal rate of VFAs was supported with noticeable pH improvements through the cells (Figure 4-8). Tables 4-4a and 4-4b summarize the removal of the individual fatty acids. Arash Masbough 70 MASc Thesis (2002) Table 4-4a Summary of removal performance for volatile fatty acids (C2-C6) in the pilot-scale constructed wetlands, 2000* Influent Effluent Parameter Control Planted Nutrients Added' Average1 Average %-Removal Average %-Removal Average %-Removal (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Total VFAs: 499 244 51% 323 41% 163 69% (C2 - Ce) (142) (149) (33%) (172) (59%) 138 (61%) acetic acid 215 90 58% 107 50% 47 78% (69) (60) (42%) (71) (33%) (46) (75%) Propionic 85 39 54% 55 35% 21 75% acid (21) (23) (42%) (27) (29%) (23) (77%) butyric + iso 110 64 42% 89 19% 48 * 56% -butyric acid (31) (38) (36%) (45) (12%) (37) (48%) valeric acid 52 25 52% 42 19% 20 62% (25) (20) (45%) (26) (11%) (19) (59%) hexanoic 37 26 30% 30 19% 27 27% acid (28) (43) (42%) (33) (21%) (43) (38%) 'n = 19 for influent, and n = 38 for each reactor set 2 These cells were planted Table 4-4b Summary of removal performance for volatile fatty acids (G2-C6) in the pilot-scale constructed wetlands, 2001* Influent Effluent Parameter Control Planted Nutrients Added2 Average1 Average %-Removal Average %-Removal Average %-Removal (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Total VFAs: 707 399 44% 435 38% 439 38% (C2 - C6) (513) (235) (43%) (186) (55%) (241) (56%) acetic acid 216 114 47% 122 44% 117 46% (225) (74) (49%) (68) (51%) (18) (29%) propionic acid 97 57 41% 58 41% 64 34% (85) (45) (31%) (39) (33%) (49) (36%) butyric + iso 220 126 43% 131 40% 123 44% -butyric acid (149) (64) (24%) (55) (22%) (58) (34%) valeric acid 95 56 41% 69 28% 77 19% (87) (66) (46%) (51) (32%) (44) (26%) hexanoic 79 46 42% 55 30% 58 27% acid (67) (60) (51%) (56) (46%) (57) (41%) n=15 for influent, and n=30 for each reactor set 2 These cells were planted * All values reported in mg.L-1 Arash Masbough 71 MASc Thesis (2002) As it was expected, there was a slightly better removal of smaller VFAs (i.e. acetic and propionic) comparing to larger ones (i.e. valeric and hexanoic) in planted cells (Table 4-4a, 4-4b). There was likely production of VFAs in the anoxic conditions presented in the wetland cells. As larger molecules (tannin and lignin, hemicellulose) were broken down. Lower dilution was applied in the second period of the study. Consequently, a higher strength influent was applied to the cells in the second stage of trials (year 2001). The concentration of BOD in 2001 was twice as high as that in 2000 (Table 4-3a, 4-3b). Other parameters of the influent (i.e. COD, tannin and lignin, and BOD) were also considerably higher in the second year of experiments. The percentage of removals for BOD increased, proving the wetlands could handle higher levels of easily biodegradable material. On the other hand, the removal rate for COD declined. Up to a limit, wetlands provide more treatment if the detention time is increased (Kadlec, 1995). Lower removal rate for COD was because of the fact that microbial communities need longer retention times to break down the more recalcitrant material in the leachate. Despite the higher strength of the influent in 2001, the HRT remained equal to one week. To provide optimal removal, we would have to either reduce the hydraulic loading rate or increase the HRT. The low BOD to COD ratio may be due to the high cellulose and VFAs content of the treated water (Morris and Herbert, 1997). In this study, the overall BOD to COD ratio was 0.7 for influent and 0.47 for effluent (Table 4-5). These ratios also support the fact Arash Masbough 72 MASc Thesis (2002) that there was higher BOD removal within the wetlands and that greater recalcitrant portion of COD passed through the system. 4-2-2-1) ThOD Comparisons with Measured COD The ThODs were calculated for VFAs and tannin and lignin in both influent and effluent using balanced oxidation reactions (Appendix B). These values were then compared to the measured COD, which represents the total chemical oxygen demand. This comparison gave an estimation of the fraction of total COD that correspond to these two classes of compounds. It also provided a qualitative estimate of the utilized fraction of tannin and lignin and VFAs during the treatment process. Table 4-5 summarizes the ThOD to COD ratios over two sampling seasons for influent and effluent. Table 4-5 Oxygen demand ratio comparisons Influent Average n2 ThOD ofVFAstoCOD 0.25 60 ThOD ofT&L to COD 0.35 68 Total ThOD 1 to COD 0.60 60 BOD to COD 0.70 68 Effluent Average n ThOD of VFAs to COD 0.24 60 ThOD ofT&LtoCOD 0.40 68 Total ThOD ' to COD 0.64 60 BOD to COD 0.47 68 1 Total ThOD = VFAs ThOD + T&L ThOD 2 n: number of samples Chemically and biologically inactive substances are not easily altered or removed, and so they pass through the system in wetlands (Kadlec, 1995). As shown in Table 4-5, the ThOD to COD ratio for tannin and lignin was slightly higher in the effluent compared to the influent. As discussed before in section 3-2-2, tannin and lignin contain large, Arash Masbough 73 MASc Thesis (2002) recalcitrant molecules that are not easily biodegradable. This was the main reason that a larger fraction of COD remained in the effluent. The ThOD to COD ratio for VFAs almost stayed the same in influent and effluent. As previously mentioned, this could be due to the possible production of VFAs in the cells. Figure 4-10 shows that the seasonal changes of COD were consistently followed by changes in total ThOD. In other words, the difference between total ThOD and COD during the sampling periods for both influent and effluent remained constant. As ThODs were calculated using the VFAs and tannin and lignin results, the three sets of measurements are in good agreement. Tannin and lignin and VFAs accounted for over 60% of the COD in both influent and effluent. The remaining compounds contributing to COD were not identified or measured in this study. As discussed in section 3-2-2, those compounds could be hemicellulosic compounds, pectins and resin acids (Bertaud et al, 2002, Sun et al, 2001, Gabrielii et al, 2000, Teschke et al, 1999). Arash Masbough 74 MASc Thesis (2002) 3000 a) COD Comparison with ThOD for Cell Effeluent (2000) 000 E1000 2 u. 2 ^ <-i SJ > -C — cro 1 Date b) COD Comparison with ThOD for Cell Influent (2000) 5000 4000 _j 3000 E 2000 1000 0 2 OJ 2 N» Pi p OJ Date 1 CTQ 1 Hi -~ Measured Chemical Oxygen Demand •• - Total ThOD for VFAs -A— Total ThOD for T&L -•— Total ThOD for VFAs + T&L c) COD Comparison with ThOD for Cell Effluent (2001) 6000 d 4000 If 2000 Date d) COD Comparison with ThOD for Cell Influent (2001) 10000 ^ 8000 ^6000 E 4000 Figure 4-10 COD comparisons with ThOD for VFAs and tannin and lignin: effluent (a and c) and influent (b and d) during two evaluation periods (average values for all 6 cells) 4-2-2-2) Effects of Nutrients on Treatment Performance It is important to note that the quantity of nutrients, play a key role in the contaminant removal performance of a wetland. In general, in lack or absence of molecular oxygen (i.e. inside the wetland cells), other oxidized inorganic compounds (e.g. nitrate or nitrite) Arash Masbough 75 MASc Thesis (2002) should be present as electron acceptors to support microbial degradation (Metcalf and Eddy, 1991). The capability of wetlands to remove nutrients has been discussed in most studies of constructed wetlands (Gopal, 1999, Bavor et al, 1995, Kadlec, 1995, Wood, 1995). In particular, those have shown that: 1) phosphorus removal occurs via sorption and plant uptake; and 2) nitrogen removal is through plant uptake, nitrification, denitrification, and sorption processes. The rates of nutrient removal processes depend on the concentrations of the nutrients present and indicate that at low levels, removal does not occur. In fact, due to very low levels of nutrients in the cells in this research (Table 4-6a , 4-6b), nutrient supplement was considered rather than its removal. Reduction of food sources can result in the destruction of microbial communities (Gopal, 1999). Kadlec and Knight (1996) suggest that an N to P mass ratio of 7.2 is required for bacterial mass. As noted in Table 4-6, not only the level of the nutrients was low in the wetlands, but also the N to P ratio was much lower than 7.2. Table 4-6a Summary of performance for nutrients in pilot-scale constructed wetlands, 2000* Influent Effluent Control Planted Nutrients added1 Parameter Average2 Average Average Average (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Ammonia (NH 3 -N) 0.3 0.2 0.2 0.1 (0.3) (0.3) (0.2) (o.i) Nitrate + nitrite (NO x" -N) 0.21 0.25 0.24 0.21 (0.09) (0.10) (0.10) (0.10) Ortho-phosphate (PO 4 3"-P) 0.75 0.38 0.54 0.75 (0.20) (0.21) (0.32) (0.73) These cells were planted 2 n = 15 for influent, and n = 30 for each reactor set * All values reported in mg.L"1 Arash Masbough 76 MASc Thesis (2002) Table 4-6b Summary of performance for nutrients in pilot-scale constructed wetlands, 2001* Influent Effluent Control Planted Nutrients added1 Parameter Average2 Average Average Average (Std. Dev.) (Std. Dev.) (Std. Dev.) (Std. Dev.) Ammonia (NH 3 -N) 0.3 0.2 0.5 1.4 (0.3) (0.2) (1.3) (0.3) Nitrate + nitrite (NO x" -N) 0.07 0.06 0.09 0.06 (0.07) (0.04) (0.14) (0.06) Ortho-phosphate (PO 4 3"-P) 1.19 0.63 0.68 1.17 (0.96) (0.37) (0.29) (0.68) These cells were planted 2 n = 15 for influent, and n = 30 for each reactor set * All values reported in mg.L"1 A lack of phosphorus can limit biomass growth and subsequently the treatment efficiency. When the plants growth is accelerated (i.e. in spring), phosphorus should be added to wetlands in order to attain greater biomass (Bulc et al., 1997). As mentioned before, nutrient sources were added to two of the planted cells (# 2 and # 4) in June 2000 and July 2001. The level of nutrients inside the cells was measured. In the first year, one week after applying the fertilizer pellets, the level of ortho-phosphate increased to 2.2 mg.L"1 inside the cells. However, the effluent of those two cells had lower concentration (average of 1.6 mg.L"1 after fertilizer addition). The difference between these two concentrations (~ 0.7 mg.L"1) was the amount of phosphorus utilized over one HRT. The level of phosphorous stayed higher in the effluent of those two cells until the entire soluble fraction of the pellets were depleted (Figure 4-11). In year 2001, the pellets were added almost in the beginning of operation period. As a result, the concentration of phosphorous increased constantly throughout the operation period, (Figure 4-11). Arash Masbough 11 MASc Thesis (2002) P04 Concentrations in 2001 > > rj 03 00 00 C .C ^ ,g .g o o o o Date ••- Avg. Cells •Avg. Fert. •Avg non Fert. Figure 4-11 The effect of fertilizer addition on ortho-phosphate concentrations of the cells effluent Partly because of nutrient addition in 2000, the removal ratio for BOD and VFAs for both "nutrients added" cells increased considerably in comparison to the other cells (Table 4-3a and Figure 4-12). This showed that, although the desirable N to P ratio was not satisfied, the efficiency of biological degradation in the cells improved with the addition Arash Masbough 78 MASc Thesis (2002) of phosphorous alone. There was not an explicable difference in removal ratio of tannin and lignin between these cells (# 2 and # 4) and "planted only" cells. This was attributed to the low biodegradability of these compounds. BOD5 3500 -i • Influent B Unplanted Control • Planted Only • Nutrient Added & Planted Figure 4-12 Wetlands seasonal variations for BOD5 and VFAs removal in 2000 (Note the increased efficiency in nutrient added cells after fertilizer addition) In addition to phosphorous bearing pellets, a different type of fertilizer, which contained urea, was added to cells # 2 and # 4 in 2001 in order to achieve the desirable the N to P Arash Masbough 79 MASc Thesis (2002) ratio. As a result, the levels of nitrogen ammonia both inside the cells and in their effluent increased (Table 4-6b). In spite of this, no significant treatment improvement was noticed in those cells during the second evaluation period. The urea fertilizer had a very high solubility and disappeared from the meshed bags in less than two weeks. It should be mentioned that the removal efficiency of cell # 2 significantly dropped after a 2-week shock-loading incident in 2001. The shock loading resulted from a temporary malfunction of the dilution water (well) pump. Consequently, pure leachate was pumped to the cells for two weeks. It affected the general performance of the system and its negative effect persisted for a few weeks thereafter (Appendix D). Although including those data reduced the average removal ratios of the system, these problems may occur in the "real world", and they were not excluded from the calculation. 4-2-2-3) Seasonal Effects on Wetlands Performance Wetland hydrology is a primary driving force influencing wetland ecology, its development, and persistence (Souch et al, 1996). However, little attention has been paid to the seasonal variations in the concentration of the wastewater and the effects of climate changes on wetlands (Gopal, 1999). Surface flow wetlands respond to rain and evapotranspiration (Kadlec, 1995), and therefore, these should not be ignored in the performance evaluation process. The performance evaluation in this research includes nearly three seasons in two stages (from spring to fall). The climatic data (temperature and precipitation) were obtained during the two assessment episodes. Figures 4-12 and 4-Arash Masbough 80 MASc Thesis (2002) 13 graphically summarize detailed seasonal changes of wetlands' treatment performance for targeted pollutants are in year 2000. The graphical presentation of treatment performance in year 2001 is summarized in Appendix D. Likewise, the climatic changes for the same periods are summarized in 2000 are presented in Figure 4-14 for year 2000 and in Appendix C for 2001. Precipitation and evapotranspiration influence the water budget and cause unpredictable flow of wastewater through the wetland (Rash and Liehr, 1999). During hot summer days of July and August with minimal rainfall (Figure 4-14), there was almost no outflow from the outlet of the cells. Although the strength of the influent was reduced (i.e. more dilution applied), effluent quality of the system decreased considerably during that period. The main reason was the high amount of evaporation, since wetlands have a large surface area to depth ratio. The concentration of the wastewater in the cells increased to a level that the system was no longer capable to carry out the desirable treatment. Dry and hot weather affected the system during two periods in 2000 (mid-June to mid-July and end of July to mid-August, Figures 4-12,13,14) and second half of August 2001 (Appendix C, Figures Cl,2 and Appendix D, Figures D 1,2,3,4). Moreover, in two points during the treatment period (Second half of July 2000, Figure 4-14, and end of July 2001, Appendix D), the dilution water pump malfunctioned due to technical problems. This resulted in periods of pumping pure leachate into the cells. These shock loadings affected the performance of the system and the recovery lasted a few weeks. The relationship between climatic changes and wetlands performance can be noticed with a quick look at the related Figures (Appendix C, D). Arash Masbough 81 MASc Thesis (2002) COD 7000 -i T&L 2500 -i— I Influent • Unplanted Control • Planted Only • Nutrient Added & Planted Figure 4-13 Wetland seasonal variations for COD and tannin and lignin removal in 2000 (Error bars represent standard deviations between two identical cells) Arash Masbough 82 MASc Thesis (2002) Temperature (2000) 30.0 i—. i i—. oo on S 5* & &, f» p P OO 1 Ol ho C-3 un un un ON i— o K> U) ~-J J O, i J*- i E. era c oo > c 00 to OJ i i > > c c CTQ UO 00 T3 I 00 Date •Mean Temperature • • Maximum Temperature • Minimum Temperature 40.0 30.0 o ••s 20.0 Precipitation (2000) 10.0 1 oo M Oh •May •May •May oo KJ 1—. 0J i Ol OJ O -J -Aug <—i <—i 5; <—I -Aug 3 C c c c c_ -Aug 13 B B -Aug > c 00 > e 0Q J> > e oo > c 00 ^1 I 00 ft T3 00 ft 13 Date *— Precipitation (mm) Figure 4-14 Climatic data for year 2000, top: temperature and bottom precipitation Arash Masbough 83 MASc Thesis (2002) Wetlands require an adaptation period to reach a stationary state. This period includes vegetative aerial fill-in, root and rhizome development, litter development, and microbial community establishment. Therefore, a newly constructed treatment wetland would be expected to require many months, including at least one year to stabilize (Kadlec and Knight, 1996). Operation of the studied constructed wetlands had been started about six months before the beginning of this study. Due to limited time and other logistical constrains, it was not possible to run the wetlands on a year-round basis. As a result, wetlands were out of operation for a few months during the study period. Therefore, a new habituation phase was started in the beginning of each evaluation period (i.e. May 2000 and June 2001). Still the performance of the wetlands improved due to partial adaptation during the 4 to 5 months of operation. In the last few weeks of each assessment period, the treatment efficiency increased significantly (Figures 4-12, 4-13, and Appendix D). A much better performance of the wetlands would be expected during a continuous, year-round operation as compared to the intermittent situation in this study. A brief comparison between the results of this study and the previous study on the same system (Frankowski, 2000) shows that the treatment performance has increased in this research. In best cases, average BOD, COD, tannin and lignin, and VFAs removal were 49%, 32%, 46% and 43% respectively and pH never passed over 3.8. Several factors may have contributed to this. The monitoring of wetland performance was conducted during Arash Masbough 84 MASc Thesis (2002) the colder season (October to December 1999). Average temperatures were much lower in that period (6-8°C) relative to temperatures in this study (20-22°C). Temperature has a significant effect on the biological treatment processes (Metcalf and Eddy, 1991). As mentioned above, the habituation of wetlands increases the treatment efficiencies. As the microbial and macrophytes communities were developed, the system was expected to improve over time. The first result of the better-developed macrophytes was noticeable pH improvements. In the prior study, pH of the effluent rarely increased to a value above four. In this study, effluent pH had an average of ~ 5.0. Thus, the wetland conditions were favourable to a broader range of microbial communities and their activities. As the wetland conditions got closer to optimal, the cells promoted removal. This resulted in 5% to 20% higher removal efficiencies in this study. 4-3) Conclusions Treatment of woodwaste leachate under field conditions was established in this research. Constant increase of pH was observed. Reductions of BOD5, COD, tannin and lignin and VFAs were consistently achieved. Closer to neutral pH, along with higher mean temperatures during the warmer period of year, favoured microbial activities. This resulted in better removal efficiencies as compared to the previous study on the same system. An important reason for treatment improvements was the habituation of the wetlands. Still, the wetlands need even more time for full ecological maturation under continuous operational conditions. Arash Masbough 85 MASc Thesis (2002) The treatment performance of "planted cells" was better in the case of pH improvement. Addition of nutrients to planted cells favoured the treatment efficiency of the wetlands. Taking into account the lack of nutrients in the leachate, it is feasible to consider continuous nutrient addition in order to supply sufficient food source to microbial communities. However, the desirable N to P ratio should be satisfied in order to obtain the optimum results. Hydrological conditions of the field (i.e. temperature, evaporation, and precipitation) had a great impact on the treatment performance. In hot and dry summer days, the concentration of the contaminants clearly increased in the effluent and there was almost no wastewater flowing out from the outlets. This meant that all of the volume of inflow evaporated and contaminants were remaining inside the cells. Although the wetlands may have been functioning properly, as the wastewater was concentrated inside the cells, removal ratios decreased. Proper dilution along with shorter HRT (i.e. higher flow rate) may lessen this impact. Arash Masbough 86 MASc Thesis (2002) 5) GENERAL CONCLUSIONS AND RECOMMENDATIONS The woodwaste leachate studied in this research should be considered a strong industrial wastewater, which is harmful to the environment. It was acidic, and had a very high oxygen demand. At least half of this oxygen demand was due to readily biodegradable compounds that supported the biological treatment option for the leachate. A limited number of studies have evaluated the characteristics of different leachates from wood and woodwaste. However, none has demonstrated a feasible and continuing treatment method for wood leachate. Constructed wetlands were capable of woodwaste leachate treatment in an earlier study by Frankowski (2000). They were chosen because of their low cost, low monitoring requirements, and high flexibility. The pilot-scale constructed wetlands systems were established as an effective treatment system for woodwaste leachate. After initial hydraulic/mixing modifications in the site, persistent increase in pH, and decrease in BOD, COD, tannin and lignin, and volatile fatty acids concentrations were observed during the period of this study. The emergent plants proved effective for treatment improvements. The level of pH increased more in planted cells compared to unplanted ones. The positive effects of plants, such as photosynthesis (which was accelerating the rise in pH), oxygen transfer Arash Masbough 87 MASc Thesis (2002) through the root mass, and creation of larger surface area for microbial attachment, enhanced the treatment effectiveness. On the other hand, unplanted cells were still effective in pollutant reduction. This showed that the substrate soil and the water column above it could support the development of microbial communities responsible for biological degradation of the contaminants without the existent of the plants. Taking into consideration the low level of nutrients in the leachate, nutrient addition enhanced the treatment ability of the system. As expected from the very high levels of carbon in the leachate, nutrients were undoubtedly a limiting factor in the microbial degradation process. In general, very low levels of nutrients and oxygen in the wetland cells (i.e. the lack of electron acceptors) certainly had a negative effect on the treatment efficiency. Climatic changes and removal fluctuations were related. Higher temperatures improved the treatment ability and yet, high evaporation concentrated the wastewater in the cells and reduced the system efficiency. The treatment effectiveness of the cells increased in the last few weeks of each investigation period. This proved that a longer exposure time would increase acclimatization of the whole system and hence its treatment efficiency. Continuous, year-round operation of the system can help to attain robust results under different climatic conditions. The constant function of the wetlands also gives them the Arash Masbough 88 MASc Thesis (2002) opportunity to develop the required acclimatization without suffering from the impacts of the intermittent operation. Hydrological studies and a water balance calculation in the wetland cells would be beneficial in elucidating the performance fluctuations. Microbiological studies would also assist to understand the causes of treatment vacillation. An investigation of the limiting factors is needed to assess the treatment capabilities of constructed wetland systems for treatment of woodwaste leachate. Possible continual addition of nutrient sources (i.e. nitrogen and phosphorous) with the desirable ratio theoretically will increase the ability of microorganisms to biodegrade the targeted pollutants. Also, providing an adequate supply of electron acceptors, such as nitrate for heterotrophic bacteria needs to be investigated in this wetland system with very low levels of dissolved oxygen. 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Arash Masbough 97 MASc Thesis (2002) APPENDICES Arash Masbough 98 MASc Thesis (2002) APPENDIX A Raw Data Table Al Temperature, pH, DO, and Conductivity in Constructed Wetland Cells in 2000 Temperature (°C): Jul Jul Jul Aug Aug Aug Aug Aug Sep Sample ID 06/00 13/00 27/00 03/00 10/00 17/00 24/00 31/00 08/00 Cell 1 21.5 19.5 20.0 24.0 18.0 24.0 23.0 22.0 23.0 Cell 5 21.0 20.5 22.0 23.5 19.0 23.5 22.0 21.0 22.0 Cell 3 21.5 19.5 21.0 23.0 17.0 23.0 22.0 22.0 22.0 Cell 6 22.0 19.0 21.0 23.0 18.0 23.0 22.0 22.0 22.0 Cell 2 22.0 19.0 21.5 23.5 18.0 23.5 22.0 21.0 22.0 Cell 4 22.0 20.0 22.0 24.0 16.5 24.0 21.0 20.0 21.0 Cell Influent 21.0 19.0 20.0 23.0 18.0 23.0 20.0 20.0 20.0 Leachate Pool 27.0 26.0 27.0 30.0 25.0 30.0 31.0 29.0 31.0 pHj Sample Jun Jun Jun Jun Jul Jul Jul Aug Aug Aug Aug Aug Sep ID 09/00 15/00 22/00 29/00 06/00 13/00 27/00 03/00 10/00 17/00 24/00 31/00 08/00 Cell 1 Cell 5 Cell 3 Cell 6 Cell 2 Cell 4 4 3 4 5 4 61 98 48 73 55 4 4 4 4 4 4 13 54 88 34 08 93 4 5 4 4 4 4 83 00 27 53 54 66 4 4 4 4 5 4 47 60 10 38 29 68 4 4 4 4 5 5 33 22 08 35 34 00 4 4 4 4 5 5 51 49 23 51 22 06 4 5 4 5 5 6 82 01 44 26 59 06 4 4 4 5 6 5 52 72 35 66 05 83 4 4 4 5 6 5 66 93 46 83 23 89 4 4 4 6 6 6 46 86 49 15 38 38 4 4 4 6 5 6 81 99 42 03 97 12 4 4 4 6 5 6 35 21 54 12 87 12 4 4 4 5 5 5 45 50 42 98 66 98 Cell Influent 3 71 3 68 3 87 3 67 3 66 3 88 4 15 3 97 4 03 4 09 4 03 4 08 3 95 Leachate Pool 3 30 3 29 3 32 3 18 3 25 3 42 3 54 3 31 3 50 3 46 3 36 3 45 3 36 Slough 6 05 6 01 6 29 5 83 5 97 6 27 6 50 6 40 6 43 6 18 6 01 6 26 6 15 Arash Masbough 99 MASc Thesis (2002) Summary DO (mg.L"1) Sample ID Jun Jun Jun Jun Jul Jul Jul Aug 09/00 15/00 22/00 29/00 06/00 13/00 27/00 03/00 Aug 10/00 Aug 17/00 Aug 24/00 Aug 31/00 Sep 08/00 Cell 1 0.4 0.7 0.6 0.8 0.4 0.6 1.0 0.5 0.4 0.5 0.4 0.3 0.4 Cell 5 0.4 0.7 0.7 0.5 0.9 0.8 1.0 0.5 0.4 0.5 0.6 0.7 0.6 Cell 3 0.5 0.8 0.5 0.7 0.7 0.6 0.9 0.4 0.4 0.4 0.7 0.8 0.7 Cell 6 0.8 0.5 0.4 0.4 0.5 0.6 0.9 0.5 0.3 0.5 0.8 0.8 0.8 Cell 2 0.6 0.6 0.4 0.9 0.6 0.8 0.9 0.4 0.5 0.4 0.8 0.9 0.8 Cell 4 0.8 0.6 0.5 0.4 0.6 0.7 0.8 0.6 0.4 0.6 0.7 0.7 0.7 Cell Influent 1.5 1.4 1.3 1.5 1.0 1.1 1.1 1.0 0.8 1.0 0.9 0.9 0.9 Leachate Pool 0.3 0.3 0.2 0.3 0.3 0.3 0.4 0.2 0.1 0.2 0.2 0.2 0.2 Conductivity (uS.cm"1) Sample ID Jul Jul Aug 13/00 27/00 03/00 Aug 10/00 Aug 17/00 Aug 24/00 Aug 31/00 Sep 08/00 Cell 1 584 306 368 410 495 457 409 123 Cell 5 509 286 383 489 505 490 479 349 Cell 3 490 492 404 328 457 468 479 608 Cell 6 490 492 404 328 457 468 479 608 Cell 2 456 375 317 484 350 420 468 519 Cell 4 434 287 341 494 364 354 388 752 Cell Influent 515 262 404 463 446 483 560 1523 Leachate Pool 1721 1792 1943 1924 2090 2041 1940 1991 Slough 123 116 120 124 122 129 136 135 Arash Masbough 100 MASc Thesis (2002) Table A2 Solids Concentrations in Constructed Wetland Cells in 2000 (mg.L1) Sample Date: May 04/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 - - -Cell 2 22.5 1.0 21.5 Cell 3 30.5 2.5 28.0 Cell 4 74.7 16.7 58.0 Cell 5 45.0 10.0 35.0 Cell 6 20.5 1.5 19.0 Cell Influent -0.4 2.0 -2.4 Leachate 8.0 0.8 7.2 Pool Slough 58.4 12.4 46.0 Blank 1.2 1.2 0.0 Sample Date: May 11/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 - - -Cell 2 25.0 -34.0 59.0 Cell 3 20.0 2.0 18.0 Cell 4 18.0 4.0 14.0 Cell 5 26.0 3.0 23.0 Cell 6 35.0 12.0 23.0 Cell Influent -5.0 -14.0 9.0 Leachate Pool 17.0 6.0 11.0 Slough 9.0 4.0 5.0 Blank 2.0 0.0 2.0 Arash Masbough 101 MASc Thesis (2002) Sample Date: May 16/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 26.5 4.0 22.5 Cell 2 16.0 1.5 14.5 Cell 3 16.0 3.0 13.0 Cell 4 13.5 2.5 11.0 Cell 5 26.0 2.5 23.5 Cell 6 22.0 3.0 19.0 Cell Influent 29.0 9.5 19.5 Leachate Pool 10.5 1.0 9.5 Slough 7.0 2.0 5.0 Blank 0.0 -0.5 0.5 Sample Date: May 23/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 27.0 5.0 22.0 Cell 2 40.5 7.5 33.0 Cell 3 28.0 2.5 25.5 Cell 4 29.5 4.0 25.5 Cell 5 39.5 4.0 35.5 Cell 6 25.5 5.5 20.0 Cell Influent 42.5 9.5 33.0 Leachate Pool 28.5 5.0 23.5 Slough 51.5 18.5 33.0 Blank 0.5 0.5 0.0 Arash Masbough 102 MASc Thesis (2002) Sample Date: May 31/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 10.5 1.0 9.5 Cell 2 29.0 3.5 25.5 Cell 3 24.5 3.5 21.0 Cell 4 30.0 3.5 26.5 Cell 5 29.0 5.0 24.0 Cell 6 21.0 2.0 19.0 Cell Influent 18.0 2.5 15.5 Leachate Pool 15.0 2.0 13.0 Slough 22.0 3.5 18.5 Blank 0.0 0.5 -0.5 Sample Date: Jun 09/00 Sample ID TSS (mg/L) FSS (mg/L) VSS (mg/L) Cell 1 - - -Cell 2 36.0 1.5 34.5 Cell 3 21.0 1.0 20.0 Cell 4 19.5 0.5 19.0 Cell 5 32.0 2.0 30.0 Cell 6 26.5 2.5 24.0 Cell Influent 12.5 1.0 11.5 Leachate Pool 18.0 3.0 15.0 Slough 15.0 1.5 13.5 Blank -0.5 -2.0 1.5 Arash Masbough 103 MASc Thesis (2002) Sample Date: Jun 15/00 TSS FSS VSS Sample ID (mg/L) (mg/L) (mg/L) Cell 1 13.0 1.5 11.5 Cell 2 45.5 3.5 42.0 Cell 3 24.5 1.5 23.0 Cell 4 22.5 3.0 19.5 Cell 5 36.5 7.0 29.5 Cell 6 16.5 0.0 16.5 Cell Influent 36.0 3.0 33.0 Leachate Pool 15.0 0.0 15.0 Slough 21.0 3.0 18.0 Blank -1.0 -1.0 0.0 Sample Date: Jun 22/00 Sample ID TSS (mg/L)FSS (mg/L) VSS (mg/L) Cell 1 42.5 4.5 38.0 Cell 2 19.5 2.0 17.5 Cell 3 19.0 1.5 17.5 Cell 4 31.5 6.5 25.0 Cell 5 42.0 7.5 34.5 Cell 6 28.5 4.0 24.5 Cell Influent 87.5 6.5 81.0 Leachate Pool 23.0 4.0 19.0 Slough 46.5 7.0 39.5 Blank 2.0 1.5 0.5 Arash Masbough 104 MASc Thesis (2002) Sample Date: Jun 29/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 41.0 2.0 39.0 Cell 2 18.0 1.5 16.5 Cell 3 25.5 2.5 23.0 Cell 4 30.0 3.5 26.5 Cell 5 28.0 4.0 24.0 Cell 6 22.0 2.0 20.0 Cell Influent 14.5 1.5 13.0 Leachate Pool 15.5 3.0 12.5 Slough 10.5 3.5 7.0 Blank 1.0 0.5 0.5 Sample Date: Jul 06/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 27.5 1.5 26.0 Cell 2 19.5 2.0 17.5 Cell 3 22.5 2.0 20.5 Cell 4 - - -Cell 5 23.5 0.0 23.5 Cell 6 23.0 2.5 20.5 Cell Influent 25.5 2.5 23.0 Leachate Pool 112.0 4.5 107.5 Slough 16.0 2.0 14.0 Blank 1.0 0.5 0.5 Arash Masbough 105 MASc Thesis (2002) Sample Date: Jul 13/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 26.5 -1.5 28.0 Cell 2 21.0 4.0 17.0 Cell 3 15.0 0.0 15.0 Cell 4 15.0 1.5 13.5 Cell 5 24.5 2.5 22.0 Cell 6 12.5 0.5 12.0 Cell Influent 63.0 4.0 59.0 Leachate Pool 37.5 7.0 30.5 Slough 39.5 15.5 24.0 Blank 0.0 -0.5 0.5 Sample Date: Jul 27/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 19.5 3.0 16.5 Cell 2 22.5 3.0 19.5 Cell 3 44.0 4.5 39.5 Cell 4 21.5 6.5 15.0 Cell 5 41.5 10.0 31.5 Cell 6 18.0 4.0 14.0 Cell Influent 24.0 5.5 18.5 Leachate Pool 47.5 12.0 35.5 Slough 23.5 10.5 13.0 Blank 0.0 1.0 -1.0 Arash Masbough 106 MASc Thesis (2002) Sample Date: Aug 03/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 24.0 3.0 21.0 Cell 2 18.0 0.0 18.0 Cell 3 18.0 1.5 16.5 Cell 4 14.5 2.5 12.0 Cell 5 25.5 6.0 19.5 Cell 6 17.0 3.0 14.0 Cell Influent 16.0 2.5 13.5 Leachate Pool 67.0 12.5 54.5 Slough 33.0 8.0 25.0 Blank 2.5 2.0 0.5 Sample Date: Aug 10/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 26.5 2.0 24.5 Cell 2 19.5 3.5 16.0 Cell 3 4.0 -2.0 6.0 Cell 4 16.0 1.5 14.5 Cell 5 24.0 5.0 19.0 Cell 6 0.0 4.0 -4.0 Cell Influent 16.5 0.5 16.0 Leachate Pool 32.0 3.5 28.5 Slough 57.5 12.5 45.0 Blank 0.0 -0.5 0.5 Arash Masbough 107 MASc Thesis (2002) Sample Date: Aug 17/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 6.0 0.5 5.5 Cell 2 9.0 1.0 8.0 Cell 3 11.0 1.0 10.0 Cell 4 6.0 3.0 3.0 Cell 5 13.0 3.5 9.5 Cell 6 21.5 4.5 17.0 Cell Influent 25.0 7.5 17.5 Leachate Pool 60.5 14.5 46.0 Slough 140.5 106.0 34.5 Blank 1.0 1.0 0.0 Sample Date: Aug 24/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 37.5 11.5 26.0 Cell 2 27.5 5.5 22.0 Cell 3 15.0 1.0 14.0 Cell 4 14.0 3.5 10.5 Cell 5 17.0 6.5 10.5 Cell 6 22.0 3.0 19.0 Cell Influent 19.0 3.5 15.5 Leachate Pool 30.5 5.0 25.5 Slough 19.5 12.5 7.0 Blank -0.5 -0.5 0.0 Arash Masbough 108 MASc Thesis (2002) Sample Date: Aug 31/00 TSS VSS Sample ID (mg/L) FSS (mg/L) (mg/L) Cell 1 18.5 4.5 14.0 Cell 2 16.5 2.5 14.0 Cell 3 33.0 3.0 30.0 Cell 4 17.0 2.0 15.0 Cell 5 21.0 3.0 18.0 Cell 6 24.0 3.0 21.0 Cell Influent 122.7 20.0 102.7 Leachate Pool 34.0 5.5 28.5 Slough 270.5 150.5 120.0 Blank 2.0 0.5 1.5 Arash Masbough 109 MASc Thesis (2002) Table A3 BOD, COD, and Tannin and Lignin Raw Data In Constructed Wetland Cells in 2000 BOD5, (mg.L-1) Sample ID 04-Mav-00 11-May-00 16-Mav-00 23-Mav-00 31-May-00 09-Jun-00 15-Jun-00 22-Jun-00 29-Jun-00 06-Jul-00 Cell 1 1650 1680 420 539 540 1139 990 Cell 5 660 570 630 660 420 180 689 630 1139 1230 Cell 3 630 810 150 120 780 780 1289 1110 1499 1320 Cell 6 510 750 720 960 720 300 1019 870 1229 1080 Cell 2 330 630 540 1620 150 120 899 540 749 840 Cell 4 390 690 720 1020 660 180 509 780 1079 Cell Influent 1620 2160 1620 2100 1170 720 1859 1560 1799 1680 Leachate Pool 6450 6300 6150 7200 4950 5250 6749 7350 8399 8550 Slough 8 12 4 10 12 3 28 9 11 13 13- 27; 03- 10- 17- 24- 31- 08- 15-Jul- Jul- Aug- Aug- Aue- Aue- Aug- Sep- Sep- Average 00 00 00 00 00 00 00 00 00 1170 540 600 690 1080 960 930 899 - 922 1260 630 615 630 870 900 870 569 424 714 1410 1110 720 780 960 1110 990 1199 1224 947 1170 870 360 405 630 690 570 419 374 718 930 540 405 285 480 690 750 869 749 637 1020 780 435 465 630 600 600 509 399 637 1800 1560 840 1080 1800 1950 1620 2999 2399 1702 7650 7350 9000 7500 8550 9450 8700 7799 7349 7405 Arash Masbough 110 MASc Thesis (2002) COD, (mg.L-1) Sample ID May 04/00 May 11/00 May 16/00 May 23/00 May 31/00 Jun Jun Jun 09/00 15/00 22/00 Jun 29/00 Jul 06/00 Cell 1 2588 2450 1225 500 1213 2037.5 2075.0 Cell 5 1313 900 1075 2113 1250 1607 775 1250 1787.5 2525.0 Cell 3 1163 1275 1463 2100 1925 3472 1913 2338 2587.5 2412.5 Cell 6 1200 1238 1238 2300 2038 2183 1488 1825 2037.5 2075.0 Cell 2 850 1063 950 1813 2263 1131 1163 1450 1312.5 1537.5 Cell 4 638 1150 1263 2463 2250 1429 500 1825 1875.0 Cell Influent 3225 3525 2925 2775 3000 4484 2600 3075 3000.0 3025.0 Leachate Pool 12125 11125 11000 8000 6875 9921 9813 1537514187.516312.5 Slough 178 135 155 148 140 123 73 108 100.0 115.0 Jul 13/00 Jul 27/00 Aug 03/00 Aug 10/00 Aug 17/00 Aug 24/00 Aug 31/00 Sep 08/00 Sep 15/00 AVERAGE 2622.7 1124.0 1459.9 1975.0 2400 1975.0 2012.5 1675.0 - 1822 2661.5 1098.2 1498.7 1600.0 1562.5 2000.0 1912.5 1137.5 962.5 1528 2803.6 2325.6 2002.6 1837.5 2025 2112.5 2037.5 2775.0 2912.5 2183 2661.5 1343.7 1304.9 1362.5 1912.5 1775.0 1512.5 1300.0 987.5 1673 2054.3 1653.7 1343.7 1237.5 1425 1562.5 1725.0 1912.5 2050.0 1500 2080.1 1279.1 1408.3 1425.0 1337.5 1575.0 1487.5 3237.5 3212.5 1691 3410.9 1292.0 2403.1 1950.0 2525 2875.0 3675.0 5225.0 6200.0 3221 16731.3 14793.3 17506.5 14875.0 16187.5 17250.0 16000.0 18125.0 15500.0 13774 113.7 103.4 118.9 117.5 125 147.5 162.5 115.0 210.0 131 Arash Masbough 111 MASc Thesis (2002) Total Tannin and Lignin (mg.L"1) Sample ID Mav May 04/00 11/00 May 16/00 May 23/00 May 31/00 Jun Jun Jun Jun Jul 09/00 15/00 22/00 29/00 06/00 Cell 1 - 668 779 545 621 338 426 883 1016.1 Cell 5 316.76252.07 217 346 495 1177 431 274 808 732.7 Cell 3 292.61250.41 349 317 698 698 707 500 951 1023.0 Cell 6 225.85 349.92 102 450 647 1026 457 365 847 981.6 Cell 2 177.56 76.29 325 422 285 1019 479 219 658 732.7 Cell 4 176.14213.93 292 422 651 704 254 323 340 -Cell Influent 693.18407.96 651 570 922 1177 842 535 978 1168.2 Leachate Pool 2642 3325 4271 3720 3288 5482 2862 3651 5485 5806.5 Slough 6.53 4 23 18 27 18 4 13 12.8 Jul Jul Aug Aug Aug Aug Aug Sep Sep 13/00 27/00 03/00 10/00 17/00 24/00 31/00 08/00 15/00 AVERAGE 121.1 477 734 864 420 561 586 329 1610 646 363.2 365 640 743 399 336 934 535 383 513 370.5 938 945 916 710 838 982 1156 995 718 816.0 617 668 974 613 671.7 760 623 431 612 704.6 536 104 706 805 623.7 411 898 489 509 610.2 565 684 782 656 790.4 1078 1099 1317 609 595.6 737 1008 1451 905 919.2 1354 1326 2346 978 5447.9 5326 6527 6260 5190 6603.5 6517 6516 5847 4988 16.8 17 23 21 18 21.7 22 22 17 17 Arash Masbough 112 MASc Thesis (2002) Table A4 Total Volatile Fatty Acids Raw Data in Constructed Wetland Cells in 2000 Total Volatile Fatty Acids (mg.L1) Sample May May May May May Jun Jun Jun Jun Jul Jul Jul Aug Aug Aug ID 04/00 11/00 16/00 23/00 31/00 09/00 15/00 22/00 29/00 06/0013/0027/00 03/00 10/00 17/00 Cell 1 - .0 442 493 237 108 118 251 351 399 409 138 0 168 220 Cell 5 261 66 186 144 169 284 211 267 288 473 643 133 162 188 258 Cell 3 220 142 301 172 419 171 568 595 491 538 567 486 249 213 313 Cell 6 168 112 138 252 459 663 411 399 352 360 449 156 44 195 90 Cell 2 31 35 118 54 27 521 214 152 115 202 250 91 0 20 321 Cell 4 96 152 216 297 361 381 108 411 247 0 239 27 36 92 76 Cell Influent 526 409 474 576 591 590 593 619 588 545 726 197 294 355 400 Leachate Pool 2311 1876 1822 1867 2135 2175 1894 1879 1995 2413 2523 2829 2505 1641 1741 Slough 0 6 17 12 27 46 0 41 11 21 48 45 50 57 70 Acetic Acid (mg.L"1) Sample May Mav May Mav Mav Jun Jun Jun Jun Jul Jul Jul Aug Aug Aug ID 04/00 11/00 16/00 23/00 31/00 09/00 15/00 22/00 29/00 06/00 13/0027/00 03/00 10/00 17/00 Cell 1 - - 168 275 87 39 28 54 133 179 183 75 - 90 97 Cell 5 93 - 68 55 80 91 44 46 84 188 188 52 93 108 127 Cell 3 87 33 99 - 140 51 194 186 193 221 226 136 144 134 135 Cell 6 61 14 - 88 154 285 127 123 109 132 133 45 8 15 15 Cell 2 13 - 45 - 10 177 81 48 49 80 56 18 - 14 122 Cell 4 45 35 74 128 122 67 7 116 71 - 55 6 11 31 9 Cell Influent 261 128 196 285 241 254 226 259 287 269 305 87 162 131 141 Leachate Pool 1091 858 1018 1056 949 1061 945 1011 1141 1321 1151 1177 1167 - -Slough 0 6 10 8 13 19 - 15 11 18 19 22 26 28 34 Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Arash Masbough 113 MASc Thesis (2002) Propionic Acid (mg.L" ) Sample ID May 04/00 May 11/00 May 16/00 May 23/00 May Jun Jun Jun Jun Jul Jul Jul Aug 31/00 09/00 15/00 22/00 29/00 06/00 13/0027/00 03/00 Aug 10/00 Aug 17/00 Cell 1 - - 102 61 53 13 21 27 59 69 75 23 - 33 46 Cell 5 60 16 41 - 42 44 18 14 42 71 87 26 41 45 54 Cell 3 43 34 64 - 79 24 92 84 80 83 89 61 48 40 47 Cell 6 36 37 48 - 83 114 52 54 52 55 60 15 - 6 4 Cell 2 4 12 24 - 2 87 31 16 17 31 23 15 - - 63 Cell 4 24 43 55 - 65 29 2 46 32 - 21 1 3 7 5 Cell Influent 89 103 101 - 106 101 97 110 99 91 112 35 67 78 77 Leachate Pool 423 342 - - 369 317 275 252 288 378 375 460 405 406 436 Slough 0 - 0 0 3 3 - 2 0 2 4 5 5 5 7 Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 (Butyric + iso-butyric) Acids (mg.L' Sample ID May 04/00 May 11/00 May May May Jun Jun Jun Jun Jul Jul Jul Aug 16/00 23/00 31/00'09/00 15/00 22/00 29/00 06/0013/0027/00 03/00 Aug 10/00 Aug 17/00 Cell 1 - - 112 120 55 35 31 66 - 102 95 27 - 34 53 Cell 5 58 29 - 64 31 101 61 76 106 144 152 38 24 28 54 Cell 3 54 57 85 125 117 64 156 155 - 156 171 104 44 32 81 Cell 6 39 - - 119 133 122 121 124 128 115 122 40 24 141 33 Cell 2 - 19 32 39 12 149 63 46 31 59 65 23 - - 85 Cell 4 18 52 67 124 104 75 38 120 89 - 74 11 - 25 34 Cell Influent 105 106 - 166 110 107 105 124 122 - 146 40 - - 109 Leachate Pool 511 395 478 496 394 345 280 254 292 421 451 588 455 554 594 Slough 0 - 4 4 4 4 - 2 0 0 3 4 18 6 6 Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Arash Masbough 114 MASc Thesis (2002) Valeric Acid (mg.L"1) Sample ID May 04/00 May 11/00 May 16/00 May 23/00 May Jun Jun Jun Jun Jul Jul Jul Aug 31/00 09/00 15/00 22/00 29/00 06/00 13/0027/00 03/00 Aug 10/00 Aug 17/00 Cell 1 - - 28 38 27 16 14 42 66 49 29 12 - 5 15 Cell 5 25 10 20 25 2 48 30 38 57 69 66 16 2 1 9 Cell 3 22 19 32 46 56 33 77 76 75 78 73 46 2 1 27 Cell 6 18 9 23 45 60 90 52 59 63 58 59 19 11 17 20 Cell 2 3 4 16 14 3 72 29 24 18 31 39 24 - 1 33 Cell 4 4 21 1 45 47 35 19 60 55 - 45 9 7 14 15 Cell Influent 71 31 30 61 74 81 74 86 79 69 80 20 15 31 50 Leachate Pool 280 154 177 191 300 294 302 270 273 292 320 324 307 315 324 Slough 0 - 0 0 6 19 - 23 0 0 22 15 0 19 20 Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Hexanoic Acids (mg.L"1) Sample ID May 04/00 May 11/00 May 16/00 May Mav Jun Jun Jun Jun Jul Jul Jul Aug 23/00 31/00 09/00 15/00 22/00 29/00 06/0013/0027/00 03/00 Aug 10/00 Aug 17/00 Cell 1 - - 32' - 15 5 25 62 - - 24 - - 3 4 Cell 5 25 12 4 - 13 - 58 93 - - 140 - 3 1 7 Cell 3 14 21 - 27 0 50 94 - - 1 125 4 2 14 Cell 6 13 - - - 29 52 60 39 - - 64 26 1 10 11 Cell 2 5 - - - - 36 11 17 - - 54 - - - 14 Cell 4 4 - 19 - 23 176 43 69 - - 30 - 3 7 7 Cell Influent 1 42 49 64 60 46 91 40 - - 83 15 5 45 24 Leachate Pool - 127 148 124 123 157 92 92 - - 223 277 166 359 382 Slough 0 - 4 0 0 0 - 0 0 - 0 0 1 0 2 Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Arash Masbough 115 MASc Thesis (2002) Table A5 Nutrients Raw Data in Constructed Wetland Cells in 2000 NH3 (mg.L1) Sample May May May May May Jun Jun Jun Jun Jul Jul Jul Aug Aug Aug ID 04/00 11/00 16/00 23/00 31/00 09/00 15/00 22/00 29/00 06/0013/00 27/00 03/00 10/00 17/00 Cell 1 - - 0.2 0.3 0.1 - 0.0 0.0 0.9 0.81 0.47 0.16 0.11 0.12 0.23 Cell 5 0.0 0.0 - 0.0 - - 0.0 0.0 0.5 0.7 0.4 0.1 0.1 0.1 0.1 Cell 3 0.0 0.0 - - 0.0 - 0.0 0.0 0.7 0.7 0.4 0.4 0.2 0.2 0.2 Cell 6 0.0 0.0 0.0 0.0 0.0 0.3 0.0 0.1 0.7 0.71 0.39 0.14 0.13 0.11 0.10 Cell 2 0.0 0.0 - - - 0.0 0.0 0.0 0.3 0.4 0.3 0.2 0.1 0.3 0.3 Cell 4 0.0 0.0 - - - - 0.1 0.0 0.5 - 0.17 0.11 0.06 0.11 0.11 Cell Influent 0.1 0.1 0.5 0.7 0.2 - 0.0 0.2 0.7 0.7 0.4 0.0 0.1 0.1 0.1 Leachate Pool 2.3 1.7 2.0 1.9 1.6 2.7 2.2 2.8 5.1 5.6 3.2 3.2 3.7 2.7 3.3 Slough 0.1 0.6 0.2 0.0 0.4 0.2 0.2 0.1 0.2 0.1 0.5 0.1 0.3 0.3 0.2 Blank - - - - - 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 NO x (mg.L1) Sample ID May 04/00 May 11/00 May 16/00 May 23/00 May Jun Jun Jun Jun Jul Jul Jul Aug 31/00 09/00 15/00 22/00 29/00 06/0013/0027/00 03/00 Aug 10/00 Aug 17/00 Cell 1 - - 0.11 0.14 0.14 0.20 0.12 0.20 0.41 0.38 0.24 0.16 0.32 0.32 0.39 Cell 5 0.30 0..084 0.08 0.20 0.19 0.19 0.16 0.20 0.32 0.39 0.24 0.15 0.35 0.35 0.39 Cell 3 0.20 0.12 0.11 0.14 0.18 0.19 0.22 0.25 0.34 0.35 0.18 0.13 0.38 0.33 0.34 Cell 6 0.25 0.11 0.13 0.19 0.17 0.14 0.19 0.22 0.35 0.37 0.21 0.17 0.37 0.39 0.40 Cell 2 0.14 0.10 0.12 0.17 0.14 0.18 0.15 0.15 0.28 0.31 0.15 0.15 0.31 0.43 0.45 Cell 4 0.15 0.12 0.12 0.14 0.18 0.23 0.13 0.18 0.34 - 0.16 0.18 0.30 0.32 0.39 Cell Influent 0.32 0.10 0.11 0.18 0.13 0.14 0.18 0.20 0.26 0.27 0.16 0.11 0.30 0.35 0.31 Leachate Pool 0.42 0.11 0.15 0.16 0.14 0.08 0.21 0.18 0.24 0.31 0.14 0.00 0.00 0.00 0.00 Slough 0.05 0.08 0.17 0.17 0.08 0.06 0.10 0.09 0.14 0.13 0.08 0.00 0.00 0.00 0.00 Blank - - - - - 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Arash Masbough 116 MASc Thesis (2002) PQ4 (mg.L1) Sample May Mav Mav May May Jun Jun Jun Jun Jul Jul Jul Aug Aug Aug ID 04/00 11/00 16/00 23/00 31/00 09/00 15/00 22/00 29/00 06/0013/0027/00 03/00 10/00 17/00 Cell 1 - - 1.0 0.8 0.3 0.1 0.2 0.3 0.4 0.455 0.596 0.415 0.364 0.470 0.514 Cell 5 0.3 0.2 0.2 0.2 0.2 0.3 0.2 0.2 0.7 0.4 0.5 0.3 0.3 0.4 0.6 Cell 3 0.3 0.3 0.4 0.4 0.5 0.2 0.5 0.5 0.5 0.6 1.1 1.3 1.2 1.1 1.3 Cell 6 0.4 0.4 0.4 0.4 0.4 0.8 0.3 0.3 0.3 0.4 0.5 0.4 0.4 0.4 0.4 Cell 2 0.2 0.3 0.3 0.2 0.0 0.5 0.2 0.2 0.2 0.5 1.2 1.4 1.2 1.7 2.6 Cell 4 0.2 0.3 0.4 0.4 0.5 0.1 0.2 0.3 0.3 - 1.9 1.7 1.4 1.3 2.3 Cell Influent 0.9 1.0 0.9 1.2 0.8 0.8 0.6 0.7 0.6 0.7 0.9 0.4 0.5 0.7 0.7 ^eachate Pool 3.6 3.2 3.7 3.4 2.9 3.9 3.1 3.7 3.9 4.2 4.5 5.2 4.9 5.6 6.1 Slough 0.2 0.2 0.2 0.2 0.1 0.1 0.1 0.1 0.2 0.2 0.1 0.0 0.0 0.0 0.0 Blank _ _ _ _ 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Table A6 Temperature, pH, DO, and Conductivity Raw Data in Constructed Wetlands in 2001 Temperature (°C): Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep 14/01 Sep 25/01 Oct 05/01 Oct 12/01 Cell 1 0.0 0.0 15.5 15.0 15.0 16.0 16.0 15.5 16.5 15.0 17.0 15.0 9.0 7.5 Cell 5 8.0 17.0 15.0 15.5 16.5 16.0 16.0 16.0 17.0 16.5 16.0 15.0 7.5 7.0 Cell 3 - 11.0 16.0 14.5 15.2 16.0 16.0 16.0 15.0 17.0 14.5 17.0 15.0 9.5 7.0 Cell 6 7.5 16.5 15.0 15.0 14.5 16.2 16.2 15.5 17.0 13.5 15.5 14.3 8.5 7.0 Cell 2 9.0 18.0 15.0 15.6 16.0 16.5 16.5 15.5 16.5 15.0 16.5 14.5 9.0 8.5 Cell 4 - 9.0 16.0 15.0 15.5 15.5 16.0 16.0 16.0 17.0 14.5 15.5 15.0 9.0 8.0 Cell Influent 7.0 14.0 12.5 13.0 12.0 13.7 13.7 12.0 14.0 13.0 11.0 14.2 11.0 10.0 Leachate Pool - 11.5 14.0 20.0 20.0 22.0 23.0 23.0 22.5 24.0 23.0 27.0 20.8 16.5 15.5 Arash Masbough 117 MASc Thesis (2002) £H: Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/0125/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - - - 4.62 4.78 4.61 4.56 5.19 4.81 4.61 5.08 4.40 4.39 4.70 4.41 Cell 5 - 4.62 4.85 4.82 4.94 4.70 4.86 5.00 5.11 4.73 4.46 4.52 4.66 5.14 5.53 Cell 3 - 4.45 4.80 4.77 4.92 4.56 4.57 4.98 5.02 4.97 4.99 4.53 4.45 4.71 4.72 Cell 6 4.01 4.66 5.03 4.90 4.91 5.00 5.87 5.69 5.04 4.89 5.84 4.65 4.92 4.86 4.99 Cell 2 4.05 4.31 4.70 4.71 4.94 4.71 4.79 6.27 5.62 5.42 5.71 4.97 5.45 5.47 4.89 Cell 4 - 4.50 4.90 4.77 5.05 5.01 4.83 5.82 5.66 5.65 6.22 4.74 4.89 5.12 4.71 Cell Influent - 4.16 4.20 4.15 4.64 4.44 4.38 4.65 4.61 4.41 4.44 4.09 4.01 4.01 4.02 Leachat e Pool - 3.35 3.58 3.43 3.73 3.51 3.36 3.78 3.45 3.89 3.65 3.68 3.64 3.98 3.67 Well - 6.46 - - - 6.34 - 6.78 6.26 6.20 6.29 6.31 6.18 6.27 6.37 DO (mg.L1) Sample ID Jun Jul Jul Jul Jul Aue 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - 0.0 0.0 0.4 0.3 0.6 0.6 0.3 0.6 0.2 0.2 0.3 0.3 0.4 0.3 Cell 5 - 0.1 0.2 0.2 0.2 2.3 0.3 0.3 0.4 0.3 0.3 0.5 0.3 0.4 0.5 Cell 3 - 0.0 0.2 0.3 0.3 0.5 0.3 0.3 0.7 0.2 0.2 0.3 0.3 0.4 0.3 Cell 6 - 0.2 0.1 0.3 0.3 0.4 0.4 0.3 0.7 0.3 0.3 0.4 0.3 0.5 0.4 Cell 2 - 1.1 0.1 0.4 0.3 1.8 0.4 0.3 0.5 0.3 0.3 0.2 0.3 0.4 0.2 Cell 4 - 0.6 0.2 0.3 0.3 0.2 0.3 0.3 0.5 0.4 0.4 0.4 0.4 0.5 0.4 Cell Influent - 3.1 1.0 2.0 2.1 2.8 3.2 0.7 1.1 1.2 1.2 1.1 0.5 0.5 1.1 Leachate Pool - 0.5 0.2 0.6 0.6 0.4 0.4 0.4 0.2 0.3 0.3 0.5 0.4 0.5 0.5 Arash Masbough 118 MASc Thesis (2002) Conductivity (uJS.cm"') Sample ID Jun Jul 20/01 04/01 Jul Jul Jul Aug 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - - 435 590 537 490 497 420 464 493 834 797 622 657 Cell 5 - 687.0 644 561 591 553 462 530 205 561 552 927 756 444 378 Cell 3 - 600.0 632 572 610 553 563 489 441 433 482 711 686 651 623 Cell 6 1036.0 626.0 634 604 591 494 264 448 420 474 357 824 711 577 516 Cell 2 978.0 1087.0 783 748 788 732 76 639 530 527 522 906 778 707 666 Cell 4 - 671.0 657 588 588 537 504 464 352 380 391 927 755 602 600 Cell Influent 1390.0 581.0 582 549 669 551 508 449 410 540 594 1257 777 799 729 Leachate Pool 1345.01513.0 1380 1437 1473 1482 1632 1400 1397 1513 1489 1504 1553 1441 1433 Arash Masbough 119 MASc Thesis (2002) Table A7 BOD, COD, and Tannin and Lignin Raw Data In Constructed Wetland Cells in 2000 BOD5, (mg.L-1) Jun Jul Jul Jul Jul Aug Aug Aug Aug Aug Sep Sep Oct Oct Sample ID 20/01 04/01 11/01 18/01 25/01 01/01 09/01 16/01 23/01 30/01 07/01 14/01 05/01 12/01 Cell 1 - - - 1433 974 1337 1109 869 490 1247 963 2549 1298 1598 Cell 5 - 1979 3153 1535 1043 1289 1007 608 446 1208 1134 2789 782 779 Cell 3 - 1883 3255 1541 1103 1361 1055 899 497 833 984 1979 1433 1304 Cell 6 1219 1625 2961 1541 896 863 593 608 425 860 747 2033 1355 1238 Cell 2 1099 3239 3459 1703 1382 1637 1241 1088 493 1028 1023 1817 1283 533 Cell 4 - 1961 3201 1523 782 1139 1115 751 428 644 756 2153 1100 1325 Cell influent 5959 3779 4747 3749 2909 2759 3269 1574 1029 1949 1980 6734 3629 4439 Leachate Pool 10139 8984 9597 10859 6989 6719 7949 6449 6644 5339 7050 7679 7409 7199 Well - 3 0 0 0 2 0 3 3 2 3 3 8 2 COD, (mg.L') Sample ID Jun 20/01 Jul 04/01 Jul 11/01 Jul 18/01 Jul 25/01 Aug 01/01 Aug 09/01 Cell 1 0 - - 1825 2550 2200 2050 Cell 5 0 5100 3050 2350 2500 2125 1125 Cell 3 0 4600 3025 2425 2600 2200 2450 Cell 6 6395 4600 2975 2375 2475 1800 1825 Cell 2 5879 6850 3775 3325 3625 3325 3075 Cell 4 0 5250 3050 2450 2600 2150 2025 Cell Influent 10788 5375 3225 2725 4150 3100 2475 Leachate Pool 10659 18063 12000 11813 12438 12813 13563 Well - 25 - - - - -Arash Masbough 120 MASc Thesis (2002) Sample ID Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep 14/01 Sep 25/01 Oct 05/01 Oct 12/01 Cell 1 2100 1525 2100 2150 4850 4475 3050 3200 Cell 5 1875 1450 2375 2550 5925 3825 2800 1875 Cell 3 1800 1725 1650 1875 3950 4425 3025 2875 Cell 6 1575 1450 1800 1625 4325 4250 2700 1300 Cell 2 2925 1925 1850 1975 3550 3675 2975 2975 Cell 4 1925 1475 • 1238 1675 4325 3825 2700 2725 Cell Influent 2600 2725 2525 3350 6563 6563 4725 5625 Leachate Pool 12563 11125 10125 13125 14125 14438 12750 12500 Well 3 3 - 28 28 80 10 18 Tannin and Lignin (mg.L"1) Sample ID Jun 20/01 Jul 04/01 Jul 11/01 Jul 18/01 Jul 25/01 Aug 01/01 Aug 09/01 Cell 1 - - - 614 913 702 496 Cell 5 ' - 1322.65 856 776 934 690 453 Cell 3 - 1050.10 876 863 964 644 853 Cell 6 1380.31 1042.08 909 819 792 545 368 Cell 2 731.66 1935.87 1026 1056 1255 719 1056 Cell 4 - 1216.43 878 859 827 621 485 Cell Influent 2316.60 1138.28 927 776 1259 687 658 Leachate Pool 4305 4228 3117 3691 3515 3289 4135 Well 0.00 _ 0 0 0 1 0 Arash Masbough 121 MASc Thesis (2002) Sample ID Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep 14/01 Sep 25/01 Oct 05/01 Oct 12/01 Cell 1 452 415 669 542 1261 1036 1116 967 Cell 5 411 216 734 671 1665 559 486 450 Cell 3 504 427 575 528 1180 651 905 899 Cell 6 406 367 546 392 1137 816 632 620 Cell 2 724 321 573 488 1083 727 882 881 Cell 4 470 352 481 397 1117 702 706 620 Cell Influent 555 489 728 791 2511 1983 1320 1258 Leachate Pool 2912 2842 2897 3131 3167 3578 3151 3744 Well 2 3 2 1 3 3 3 2 • Table A8 Total Volatile Fatty Acids Raw Data in Constructed wetland Cells in 2001 Total Volatile Fatty Acids (mg.L') Sample ID Jun Jul Jul Jul Jul 20/01 04/01 11/01 18/01 25/01 Aug 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep 14/01 Sep 25/01 Oct 05/01 Oct 12/01 Cell 1 - 0 0 203 364 605 531 282 248 399 308 784 865 375 752 Cell 5 - 458 539 510 436 433 298 104 106 427 394 702 719 223 103 Cell 3 - 561 493 466 450 637 465 337 269 263 334 683 666 458 437 Cell 6 866 495 448 430 473 345 49 218 272 328 79 650 738 398 323 Cell 2 920 1195 432 583 585 704 557 497 197 225 172 395 430 294 450 Cell 4 - 573 325 295 556 361 363 260 157 132 97 702 544 292 446 Cell Influent 2039 517 744 449 361 473 564 295 109 476 577 1616 1106 716 558 Leachate Pool 1978 1963 2078 2194 2322 2224 2408 2017 1827 1987 2312 2111 1763 1942 2153 Well 0 3 71 23 0 56 0 23 32 51 42 13 19 24 6 Arash Masbough 122 MASc Thesis (2002) Acetic Acid (mg.L"1) Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - - - 4 15 32 29 20 19 29 18 57 48 35 47 Cell 5 0 35 19 20 36 31 18 5 8 26 22 53 34 17 -Cell 3 0 36 5 2 30 38 33 23 18 17 21 47 42 35 26 Cell 6 38 33 4 31 34 22 2 14 22 25 3 47 34 24 22 Cell 2 53 76 6 10 40 53 41 36 14 12 6 35 12 9 27 Cell 4 0 35 5 10 28 21 21 13 7 9 5 45 28 14 28 Cell Influent 153 36 44 24 10 20 28 16 4 34 40 125 102 55 7 Leachate Pool 145 909 173 195 193 190 222 157 161 141 203 193 140 139 168 Well 0 3 5 2 0 4 0 2 3 5 3 2 2 2 -Blank 0 0 0 2 1 2 1 0 0 0 0 1 0 1 0 Propionic Acid (mg.L"1) Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - - - 9 16 13 10 8 7 11 6 21 18 12 45 Cell 5 0 22 19 13 15 12 6 1 3 11 8 24 16 6 4 Cell 3 0 20 16 12 13 13 11 7 5 4 5 15 17 12 10 Cell 6 41 20 6 13 14 8 1 5 7 9 - 19 14 10 8 Cell 2 38 42 22 17 20 23 16 15 4 7 7 14 13 8 10 Cell 4 0 26 15 10 11 7 6 4 2 3 1 17 12 5 9 Cell Influent 72 19 19 18 15 16 11 8 4 12 15 47 13 18 19 Leachate Pool 72 7 66 67 71 65 75 57 53 54 67 57 40 47 55 Slough 0 0 0 0 0 0 0 - - 1 - - - 5 -Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Arash Masbough 123 MASc Thesis (Butyric + iso-butyric) Acids (mg.L"1) Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - - - 17 26 27 24 18 16 28 22 47 34 - -Cell 2 52 68 32 30 31 35 30 26 10 13 10 29 30 22 30 Cell 3 0 32 - 25 25 - 30 22 18 - 24 43 43 29 29 Cell 4 0 30 23 19 23 25 27 20 11 - 7 40 34 23 31 Cell 5 0 23 24 - 22 26 21 8 - 28 28 44 23 - -Cell 6 53 27 22 22 26 22 - 13 - 21 7 44 33 28 24 Cell Influent 108 28 _ 27 29 35 27 _ _ _ 36 95 34 _ 51 Leachate Pool 96 132 101 102 116 110 109 114 92 121 118 103 98 126 131 Slough 0 0 9 2 0 8 0 - - 4 5 - - - -Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Valeric Acid (mg.L"1) Sample ID Jun Jul Jul Jul Jul Aue 20/01 04/01 11/01 18/01 25/01 01/01 Aue 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - - - 8 10 12 9 7 8 12 10 22 74 6 15 Cell 5 0 7 11 11 9 11 9 5 4 13 14 12 70 4 4 Cell 3 0 15 15 14 13 13 13 10 9 9 11 22 22 11 16 Cell 6 23 12 11 12 12 11 4 7 8 10 6 9 68 13 11 Cell 2 22 33 17 17 16 19 16 15 7 8 7 1 21 14 16 Cell 4 0 15 14 12 12 12 12 10 7 6 6 38 35 12 15 Cell Influent 41 12 13 . 12 12 15 12 8 5 13 15 36 72 18 24 Leachate Pool 45 40 44 42 50 46 40 47 33 53 42 40 45 52 48 Slough 0 0 - 0 0 0 0 - - 1 - - - 5 -Blank 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 Arash Masbough 124 MASc Thesis (2002) Hexanoic Acids (mg.L"1) Sample Jun Jul Jul Jul Jul Aug Aug Aug Aug Aug Sep Sep Sep Oct Oct ID 20/01 04/01 11/01 18/01 25/01 01/01 09/01 16/01 23/01 30/01 07/01 14/01 25/01 05/01 12/01 Cell 1 - - - 3 5 37 34 3 - - 5 10 - 3 7 Cell 5 0 4 34 40 5 6 5 2 - 7 7 7 - 2 2 Cell 3 0 8 36 39 8 36 7 5 5 5 6 10 10 5 6 Cell 6 19 7 46 8 7 6 3 4 4 - - 11 - 5 -Cell 2 19 20 10 42 10 11 10 8 4 5 4 - 9 6 7 Cell 4 0 9 9 8 37 7 6 5 4 - - - - 5 6 Cell Influent 34 9 47 8 7 9 35 9 - 7 9 20 - 8 11 Leachate Pool 37 32 31 32 35 34 36 29 26 29 33 30 29 26 29 Slough 0 0 - 0 0 0 0 - - - - - - - -Blank 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Table A9 Nutrients in Constructed wetland Cells in 2001 NH3 (mg.L1) Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 0.0 0.0 0.0 0.2 0.2 0.2 0.2 0.2 0.1 0.2 0.0 0.3 0.7 0.3 0.4 Cell 5 0.0 0.5 0.4 0.3 0.2 0.2 0.2 0.2 0.0 0.0 0.1 0.6 0.6 0.1 0.1 Cell 3 0.0 0.4 0.5 0.3 0.5 0.3 0.3 0.2 0.1 0.1 0.0 0.2 6.8 0.5 0.4 Cell 6 0.0 0.4 0.5 0.3 0.3 0.1 0.0 0.1 0.0 0.1 0.0 0.3 0.5 0.3 0.1 Cell 2 0.0 1.0 0.7 0.5 0.9 0.6 0.8 0.6 0.1 0.1 0.0 5.8 4.2 1.6 0.7 Cell 4 0.0 0.4 0.9 0.6 0.3 0.2 0.2 0.1 0.0 0.0 0.0 12.8 4.7 0.5 0.3 Cell Influent 0.0 0.3 0.3 0.2 0.1 0.1 0.2 0.1 0.0 0.0 0.2 1.1 0.4 0.1 0.7 Leachate Pool 0.0 2.9 2.5 2.2 2.3 2.5 3.4 2.3 2.3 1.1 2.0 2.1 2.2 2.0 2.4 Well 0.0 0.2 0.0 0.2 0.0 0.2 0.0 0.2 0.2 0.2 0.3 0.3 0.3 0.2 0.2 Blank 0.0 0.0 0.0 0.0 0.0 0.0 0.4 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Arash Masbough 125 MASc Thesis (2002) NOx (mg.L1) Sample Jun Jul Jul Jul Jul Aug Aug Aug Aug Aug Sep Sep Sep Oct Oct ID 20/01 04/01 11/01 18/01 25/01 01/01 09/01 16/01 23/01 30/01 07/01 14/01 25/01 05/01 12/01 Cell 1 - 0.00 - 0.02 0.00 0.00 0.07 0.05 0.08 0.07 0.05 0.08 0.05 0.12 0.08 Cell 5 - 0.14 0.12 0.03 0.00 0.00 0.09 0.07 0.03 0.10 0.06 0.12 0.06 0.06 0.06 Cell 3 - 0.12 0.13 0.03 0.00 0.00 0.05 0.03 0.06 0.06 0.05 0.06 0.04 0.16 0.80 Cell 6 0.15 0.12 0.11 0.02 0.00 0.00 0.06 0.03 0.05 0.06 0.05 0.10 0.00 0.11 0.06 Cell 2 0.26 0.09 0.13 0.03 0.00 0.00 0.06 0.03 0.09 0.06 0.05 0.05 0.00 0.07 0.05 Cell 4 - 0.13 0.13 0.02 0.00 0.00 0.06 0.03 0.04 0.05 0.05 0.10 0.00 0.06 0.06 Cell Influent 0.22 0.12 0.09 0.02 0.00 0.00 0.03 0.03 0.03 0.10 0.08 0.07 0.00 0.19 0.09 Leachate Pool 0.32 0.09 0.08 0.00 0.00 0.00 0.00 0.11 0.22 0.22 0.09 0.00 0.00 0.28 0.08 Well 0.00 0.18 0.21 0.03 0.00 0.00 0.00 0.28 0.03 0.02 0.04 0.03 0.23 0.03 0.07 Blank 0.00 0.00 0.00 0.07 0.00 -0.03 -0.01 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 P04 (mg.L1) Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep Sep Oct 14/01 25/01 05/01 Oct 12/01 Cell 1 - 0.0 - 0.6 0.6 0.6 0.0 0.3 0.4 0.5 0.4 1.4 1.2 0.8 0.9 Cell 5 - 0.7 0.6 0.6 0.6 0.6 0.5 0.6 0.1 0.6 0.5 1.6 1.2 0.5 0.5 Cell 3 - 0.6 0.6 0.6 0.6 0.6 0.9 0.5 0.4 0.4 0.5 1.1 1.2 1.0 0.9 Cell 6 1.1 0.6 0.6 0.6 0.6 0.5 0.6 0.4 0.3 0.4 0.3 1.4 1.0 0.7 0.6 Cell 2 2.7 1.1 1.1 1.2 1.2 0.9 0.9 0.9 1.0 1.2 1.0 1.9 1.7 1.0 0.7 Cell 4 - 0.7 0.8 0.8 0.7 1.0 0.9 0.8 0.6 0.7 0.6 3.7 2.3 1.1 1.0 Cell Influent 3.2 0.6 0.8 0.8 0.6 0.9 0.5 0.4 0.2 0.7 1.0 3.2 1.0 2.4 1.5 Leachate Pool 3.0 2.9 3.1 3.3 3.3 3.7 3.7 3.2 3.2 2.9 3.4 3.5 3.5 3.5 3.5 Well 0.0 0.2 0.1 1.4 0.0 0.1 0.0 0.1 0.0 0.0 0.0 0.1 0.0 0.0 0.0 Blank 0.0 0.0 0.0 0.1 0.0 0.0 0.1 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 Arash Masbough 126 MASc Thesis (2002) APPENDIX B Theoretical Oxygen Demand Calculations APPENDIX B.l Theoretical Oxygen Demand Calculations Fatty Acids (general form): CnH2n+iCOOH Acetic Acid: CH3COOH + 202 -• 2 C02 + 2 H20 MW = 60.06 g/mol and MW of 02 = 32.0 g/mol Therefore ThOD = 1.07 mg 02 per 1 mg of acetic acid Propionic Acid: C2H5COOH + 3.502 -» 3 C02 + 3 H20 MW = 74.09 g/mol and MW of 02 = 32.0 g/mol Therefore ThOD = 1.51 mg 02per 1 mg of acetic acid Butyric Acid: C3H7COOH + 502 -> 4 C02 + 4 H20 MW = 88.12 g/mol and MW of 02 = 32.0 g/mol Therefore ThOD = 1.82 mg 02per 1 mg of acetic acid Valeric Acid: C4H9COOH + 6.502 -> 5 C02 + 5 Ff20 MW =102.15 g/mol and MW of 02 = 32.0 g/mol Therefore ThOD = 2.04 mg 02 per 1 mg of acetic acid Hexanoic Acid: C5H, ,COOH + 802 -> 6 C02 + 6 H20 MW = 116.18 g/mol and MW of 02 = 32.0 g/mol Therefore ThOD = 2.20 mg 02 per 1 mg of acetic acid Tannin and Lignin (uses tannic acid as surrogate) Tannic Acid: C76H52046 + 66 02 -» 76 C02 + 26 H20 MW = 1701.28 g/mol and MW of 02 = 32.0 g/mol Therefore ThOD = 1.24 mg 02 per 1 mg of acetic acid Arash Masbough 127 MASc Thesis (2002) Table Bl Total ThOD for VFAs, 2000 Sample ID Mav 04/00 Mav 11/00 Mav 16/00 Mav 23/00 Mav 31/00 Jun 09/00 Jun 15/00 Cell 1 0.00 0.00 664.13 0.00 360.99 168.21 200.80 Cell 5 134.91 121.50 279.08 225.98 238.69 443.80 372.68 Cell 3 48.30 226.86 467.44 322.16 654.35 273.33 894.60 Cell 6 400.46 183.92 240.35 401.54 717.74 995.10 670.03 Cell 2 0.00 60.47 176.63 100.54 42.64 816.64 329.41 Cell 4 331.08 240.52 328.30 452.89 563.11 708.94 211.29 Cell Influent 257.06 637.88 708.93 869.68 899.54 884.88 929.71 Leachate Pool 749.39 2740.91 2640.30 2687.57 3166.57 3182.58 2748.75 Sample ID Jun 22/00 Jun 29/00 Jul 06/00 Jul 13/00 Jul 27/00 Aug 03/00 Aug 10/00 Aug 17/00 Cell 1 440.50 534.67 579.89 591.67 188.05 0.00 223.17 308.43 Cell 5 490.57 460.49 710.73 1050.38 195.21 213.87 239.54 351.43 Cell 3 967.82 738.28 802.52 834.92 794.52 317.96 270.00 448.14 Cell 6 643.63 555.66 551.04 716.72 240.25 76.55 337.94 146.90 Cell 2 247.24 170.72 303.92 410.59 132.74 0.00 18.26 477.28 Cell 4 686.03 397.40 0.00 383.58 45.52 51.28 134.55 125.03 Cell Influent 930.53 839.57 775.79 1105.37 291.16 397.54 546.43 617.74 Leachate Pool 2671.96 2739.61 3339.04 3755.99 4286.78 3672.39 3051.86 3236.27 Table B2 Total ThOD for Tannin and Lignin, 2000 Sample ID May 04/00 May 11/00 Mav Mav Mav Jun Jun Jun Jun Jul Jul Jul Aug 16/00 23/00 31/00 09/00 15/00 22/00 29/00 06/0013/0027/00 03/00 Aug 10/00 Aug 17/00 Cell 1 - - 829 967 677 770 419 528 1097 1261 150 592 911 1072 522 Cell 5 393 313 269 430 614 1461 535 341 1003 910 451 453 794 922 495 Cell 3 363 311 433 394 866 866 878 621 1181 1270 460 1164 1173 1137 882 Cell 6 280 434 126 558 803 1273 567 453 1052 1219 1013 766 830 1209 761 Cell 2 220 95 404 524 354 1265 595 271 817 910 875 666 130 876 1000 Cell 4 219 266 362 524 808 874 315 401 422 - 757 702 849 971 814 Cell Influent 861 506 808 708 1144 1461 1046 664 1214 1450 739 915 1251 1802 1123 Leachate Pool 3280 4128 5302 4617 4081 6806 3553 4533 6810 7208 6763 6611 8103 7771 6443 Arash Masbough 128 MASc Thesis (2002) Table B3 Total ThOD for VFAs, 2001 Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep 14/01 Sep Oct 25/01 05/01 Oct 12/01 Cell 1 - - - - 599 1041 917 441 377 612 504 1220 1446 542 1150 Cell 2 1474 1895 767 1094 919 1089 871 779 313 371 296 565 756 514 730 Cell 3 • - 885 937 910 713 1076 731 537 433 426 544 1083 1067 705 710 Cell 4 - 900 582 510 976 592 595 441 269 208 163 1123 902 492 719 Cell 5 - 683 956 922 657 679 482 178 163 688 648 1065 1230 338 188 Cell 6 1430 768 890 674 735 554 89 351 415 500 140 1006 1268 643 505 Cell Influent 3131 805 1260 727 621 791 985 489 183 747 906 2472 1684 1100 1004 Leachate Pool 3057 2980 3129 3259 3507 3340 3539 3095 2720 3112 3444 3125 2719 3042 3304 Table B4 Total ThOD for Tannin and Lignin, 2001 Sample ID Jun Jul Jul Jul Jul Aug 20/01 04/01 11/01 18/01 25/01 01/01 Aug 09/01 Aug 16/01 Aug 23/01 Aug 30/01 Sep 07/01 Sep 14/01 Sep Oct 25/01 05/01 Oct 12/01 Cell 1 - - - 762 1133 871 616 561 516 831 672 1566 1286 1386 1200 Cell 5 - 1642 1062 963 1160 856 562 510 269 912 833 2067 694 603 558 Cell 3 - 1304 1087 1071 1196 800 1059 626 530 714 656 1464 808 1123 1116 Cell 6 1714 1294 1128 1017 984 677 457 504 455 678 487 1412 1013 785 769 Cell 2 908 2403 1273 1312 1558 893 1311 899 399 712 606 1345 903 1095 1094 Cell 4 - 1510 1089 1066 1027 772 602 583 437 597 493 1386 871 876 769 Cell Influent 2317 1413 1151 963 1563 853 817 689 607 904 982 3117 2462 1639 1562 Leachate Pool 4305 5249 3870 4582 4364 4083 5134 3615 3529 3597 3887 3931 4441 3912 4648 Arash Masbough 129 MASc Thesis (2002) APPENDIX C Climatic Data Figure Cl Temperature Data of Abbotsford, B.C. for 2001 (Source: Environment Canada, 2001) a o B 'S, 45.0 40.0 35.0 30.0 25.0 20.0 15.0 10.0 5.0 0.0 • • < • • • • * • • : • 'm\ * - •* ; • V <^ ,^ J° J°- J° J> c& . c& ^ 0* 0* Day Precipitation (mm) Figure C2 Precipitation Data of Abbotsford, B.C. for 2001 (Source: Environment Canada, 2001) Arash Masbough 130 MASc Thesis (2002) Table Cl Climate Normals, Abbotsford, BC, 1944-1990 (Environment Canada 1999) Jan Feb Mar Apr May Jun Jul Aug Sep Oct Nov Dec Year Temperature Daily Maximum (°C) 5.4 8.4 10.9 13.9 17.4 20.4 23.2 23.6 20.5 14.9 9 5.7 14.4 Daily Minimum (°C) -1 0.7 1.7 3.8 6.5 9.4 10.9 10.9 8.5 5.1 2.2 -0.5 4.9 Daily Mean (°C) 2.2 4.6 6.3 8.8 12 14.9 17.1 17.3 14.5 10 5.6 2.6 9.7 Extreme Maximum (°C) 17.7 20.6 22.8 29.7 36 34.7 37.8 36.3 37.5 29.3 20.6 18.2 Extreme Minimum (°C) -21.1 -18.9 -12.8 -4.4 -2.2 1.1 2.2 3.3 -1.7 -7.5 -16.7 -20 Deeree-Davs Above 18 °C 0 0 0 0.1 2.1 6.6 20.2 21.5 5 0.1 0 0 56 Below 18 "C 489.6 378.9 361.7 274.7 189.1 98.1 48.9 43.8 109.3 247.9 371.2 480 3093 Above 5 °C 16.8 30.6 57.2 116.4 215.9 298.5 374.3 380.7 285.7 156.7 51.1 20 2004 Below 0 "C 29.7 7.1 1.5 0 0 0 0 0 0 0.2 5.3 26.2 70 Precipitation Rainfall (mm) 174.2 151.1 139.1 113.3 89.2 66.7 50.7 53.1 85.4 156.2 215.7 191.5 1486.2 Snowfall (cm) 26.3 12.8 5.5 0.3 0 0 0 0 0 0 5.8 23.9 74.6 Precipitation (mm) 201.4 163.5 144.6 113.8 89.2 66.7 50.7 53.1 85.4 156.2 221.8 216.6 1562.9 Extreme Daily Rainfall (mm) 78.2 83.1 76.2 59.9 53.8 49.5 70.1 44.2 53.7 83.3 95 89.6 Extreme Daily Snowfall (cm) 49.8 26.4 33 3.8 0 0 0 0 0 1 31.8 43.8 Extreme Daily Precipitation (mm) 89.7 83.1 76.2 59.9 53.8 49.5 70.1 44.2 53.7 83.3 95 89.6 Month-end Snow Cover (cm) 2 1 0 0 0 0 0 0 0 0 1 5 Davs With Maximum Temperature >0°C 28 28 31 30 31 30 31 31 30 31 29 28 357 Measurable Rainfall 16 16 16 15 14 11 7 7 10 15 19 18 166 Measurable Snowfall 5 3 2 * 0 0 0 0 0 * 1 5 16 Measurable Precipitation 19 17 17 16 14 11 7 7 10 15 20 21 174 Freezing Precipitation 1 * * 0 0 0 0 0 0 0 * * 3 Fog 4 3 1 * * * 1 3 5 7 3 5 34 Sunshine (Mrs) N N N 166.4 203.9 216.9 287.6 254.5 182.3 N 67.9 N N Station Pressure (kPa) 101.02 100.96 100.84 100.96 100.99 100.95 101.01 100.91 100.94 101.04 100.85 100.97 100.95 Moisture Vapour Pressure (kPa) 0.6 0.67 0.71 0.82 1.02 1.24 1.4 1.43 1.26 1 0.77 0.65 0.96 Rel. Humidity - 0600L (%) 83 84 85 86 86 86 87 90 91 90 86 85 Rel. Humidity - 1500L (%) 74 67 61 58 58 58 56 56 59 67 73 76 Wind Speed (km/h) 12 12 11 11 10 9 8 8 8 9 11 12 10 Extreme Hourly Speed (km/h) 72 80 71 80 56 45 48 53 56 89 76 80 Direction S S SW S S S S E S S S SE Extreme Gust Speed (km/h) 121 137 103 121 84 68 64 63 80 145 113 121 Arash Masbough 131 MASc Thesis (2002) 5N 8 IS rn 'I <3 1^ Figure D6 Seasonal variability in Ammonia in Constructed Wetland Cells in 2001 - Avg Cells —•-—Avg Fertilized A Cell Influent Arash Masbough 136 MASc Thesis (2002) Figure D7 Seasonal variability in Nitrate+Nitrite in Constructed Wetland Cells in 2000 0.50 0.00 -I 1 , 1 1 1 , , 1 , 1 , , , , r1 '0~JJ>— 'J>.H-.OO. ' N> NO ON ' ' o\ N<o3jap3ja 333 ^- — 3- CTQ 0Q C *< >< >-< CTQ Date - •» - Avg. Cells —•—-Avg. Fert. —*—Cell Influent Figure D8 Seasonal variability in Nitrate+Nitrite in Constructed Wetland Cells in 2001 0.30 NO ON .V © -U — ' oo i— OO <Jt < • era era cro ~ 13 73 Date •- - Avg Cells —•—Aveg Fertilized —*—Cell Influent Arash Masbough 137 MASc Thesis (2002) Figure D9 Seasonal Variability in ortho-Phosphate in Constructed Wetland Cells in 2000 Figure D10 Seasonal Variability in ortho-Phosphate in Constructed Wetland Cells in 2001 - •• - Avg Cells —•—Aveg Fertilized A Cell Influent Arash Masbough 138 MASc Thesis (2002) 

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