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An assessment of constructed wetlands for the treatment of greenhouse wastewaters Prystay, Ward A. 1997

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AN ASSESSMENT OF CONSTRUCTED WETLANDS FOR THE TREATMENT OF GREENHOUSE WASTEWATERS by Ward A. Pry stay B.Sc, The University of British Columbia, 1989  A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE in THE FACULTY OF GRADUATE STUDIES Bio-Resource Engineering Program  We accept this thesis as conforming to tjje required s^dard^  THE UNIVERSITY OF BRITISH COLUMBIA December 1997  ©Ward A. Prystay, 1997  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  CjIrVgrnVCAL- \  EAQ~fc=50o'g.C€r  The University of British Columbia Vancouver, Canada  Date  DE-6 (2/88)  &oCsito6Ett-V>sl£,  ABSTRACT The greenhouse vegetable industry in British Columbia is an expanding agricultural sector producing peppers, English cucumbers, tomatoes, and butter lettuce. Current production methods generate up to 4.5 litres of high nutrient runoff per square metre production area per day. The disposal of this wastewater untreated poses a significant environmental concern due to the potential for the high concentrations of nitrate and phosphate to induce eutrophication and alter the structure and dynamics of aquatic ecosystems.  Technical problems surrounding the sterilization and recycling of greenhouse overdrain has lead the greenhouse industry to investigate the use of constructed wetlands as a wastewater treatment option. In the spring of 1995 a pilot scale research project was initiated to assess the use of constructed wetlands for treatment of this low organic carbon, high nutrient wastewater. Five wetland designs, based on conventional surface flow (SF) and subsurface flow (SSF) design approaches, were assessed. These designs were: 15 cm water depth planted SF wetlands; 30 cm water depth planted SF wetlands; 30 cm water depth unplanted SF wetlands; 60 cm depth gravel bed planted SSF wetlands; and, 60 cm depth gravel bed unplanted SSF wetlands. Samples were collected every second week between April and December 1996 from three sites within each wetland and analyzed for: ammonia, nitrate, total Kjeldahl nitrogen, total phosphorus, ortho-phosphate, total solids, total organic carbon and biochemical oxygen demand.  Results of this study indicate that none of the individual designs assessed is capable of providing the highest treatment effect for all parameters concerned; however, the surface flow design emerged as the most appropriate design for the remediation of greenhouse wastewaters. No treatment effect was observed for either total Kjeldahl nitrogen or total solids in any of the designs assessed. The highest mean reductions of phosphorus was 65 % observed in one of the two unplanted SF wetlands. Peak nitrate reductions of 54% were observed in the 15 cm deep SF wetlands and ammonia removal of 74% were achieved in the unplanted SF wetlands. An increase in biochemical oxygen demand and total organic carbon was seen in all wetland designs. Based on available literature and the results of this research project, a multi-stage design, consisting of an unplanted pre-treatment basin followed by a 25 to 35 cm deep surface flow marsh with open water components, is recommended.  ii  TABLE OF CONTENTS  ABSTRACT  ii  T A B L E OF CONTENTS  iii  LIST OF FIGURES  vi  ACKNOWLEDGEMENTS  vii  1.0 INTRODUCTION  1  2.0 OBJECTIVES  4  3.0 LITERATURE REVIEW  5  3.1 WETLAND DESIGN AND TREATMENT PERFORMANCE 3.1.1 SURFACE FLOW WETLANDS  5 6  3.1.2 SUBSURFACE FLOW WETLANDS  10  3.1.3 VERTICAL F L O W WETLANDS  15  3.2 NUTRIENT R E M O V A L PROCESSES  16  3.2.1 ORGANIC CARBON REDUCTION PROCESSES  17  3.2.2 NITROGEN R E M O V A L MECHANISMS  19  3.2.3 PHOSPHORUS R E M O V A L MECHANISMS  25  4.0 MATERIALS AND METHODS  30  4.1 MONITORING PROGRAM  34  4.2 STATISTICAL ANALYSES  38  iii  5.0 RESULTS AND DISCUSSION  38  5.1 PHOSPHORUS  40  5.2 NITRATE..!  48  5.3 AMMONIA  53  5.5 COST ANALYSIS  56  6.0 CONCLUSIONS  57  7.0 BIBLIOGRAPHY  61  APPENDIX 1. RAW DATA  65  APPENDIX 2. CHARTS AND GRAPHS  76  APPENDIX 3. STATISTICAL ANALYSES  92  iv  LIST OF TABLES  T A B L E 1. M I C R O B I A L L Y M E D I A T E D O R G A N I C C A R B O N O X I D A T I O N A N D R E D U C T I O N  18  T A B L E 2. C A L C I U M PHOSPHATES  26  T A B L E 3. A N A L Y T I C A L M E T H O D S  36  T A B L E 4. W A T E R Q U A L I T Y L A B O R A T O R Y A N A L Y S E S  37  T A B L E 5. T O T A L PHOSPHORUS R E S U L T S ( M G / L )  41  T A B L E 6. O R T H O - P H O S P H O R U S R E S U L T S ( M G / L )  41  T A B L E 7. N I T R A T E R E S U L T S ( M G / L )  50  T A B L E 8. A M M O N I A R E M O V A L ( M G / L )  54  T A B L E 9. W E T L A N D CONSTRUCTION COSTS  57  v  LIST OF FIGURES  FIGURE l. T Y P I C A L SF W E T L A N D DESIGN FIGURE 2. T Y P I C A L SSF W E T L A N D DESIGN FIGURE 3. T Y P I C A L V F W E T L A N D DESIGN FIGURE 4. L O C A T I O N M A P F I G U R E 5. P L A N VIEW OF T Y P I C A L W E T L A N D WITH S A M P L I N G SITE LOCATIONS F I G U R E 6. C H A N G E IN 0 - P 0 4 CONCENTRATIONS IN C E L L S 5 & 6 O V E R T I M E F I G U R E 7. W E T L A N D C E L L S #5 & #6.  C H A N G E S IN P H O V E R T I M E  F I G U R E 8. T O T A L PHOSPHORUS A N D ORTHO-PHOSPHATE vs. P H FIGURE 9 RELATIONSHIP B E T W E E N B O D A N D T O C S  FIGURE 10.  C H A N G E IN T O T A L O R G A N I C C A R B O N T H R O U G H E A C H W E T L A N D DESIGN  FIGURE 11.  C H A N G E IN A M M O N I U M A N D P H O V E R T I M E  vi  ACKNOWLEDGEMENTS Support and funding of this research project was generously provided by ECL Envirowest Consultants Limited, Houweling Nurseries Ltd., the Science Council of British Columbia (Technology BC program), the BC Ministry of Agriculture, Fisheries and Food (Partners in Action program), Environment Canada (Green Plan) and the BC Vegetable Greenhouse Research Council. The time and effort of a number of very generous individuals was pivotal in putting this research project together. In particular I would like to thank: Ian Whyte and Mark Adams (ECL Envirowest Consultants Limited), Casey Houweling (Houweling Nurseries Ltd.), Bev Locken (BC Ministry of Environment, Lands and Parks), Jim Portree (BC Ministry of Agriculture, Fisheries and Foods) and Victor Lo (Bio-Resource Engineering Program, UBC). Laboratory and field work would not have been successful without the help and friendship of Chang-Six Ra and the "tolerance" of Neil Jackson and Jurgen Pelke. To Alison Ivan, I would like to say a very special "thank-you" for your unlimited support and patience over these past three years.  vii  1.0  INTRODUCTION  The greenhouse vegetable industry in the Lower Mainland of British Columbia is a rapidly expanding agricultural sector generating more than fifty-five million Canadian dollars in annual revenues. Red, green and yellow peppers, English cucumbers, tomatoes, and butter lettuce are grown in an inert rockwool or yellow cedar medium with all nutrients provided via drip feed directly to the root zone. To ensure maximum nutrient and water uptake and to prevent salt accumulation in the root-zone, the plants are over watered by 25 to 45% generating up to 4.5 litres of high nutrient runoff per square metre production area per day at peak water use (BCMAFF 1993, Hardgrave and Hufton 1995). Most greenhouse operators are reluctant to recycle this effluent due to the potential of reduced crop production and disease and currently discharge the overdrain untreated to the environment.  The term overdrain is industry nomenclature for the feed solution which is not  consumed by plant uptake or evaporation and runs off from the production area. For the purposes of this document, the terms overdrain, effluent and wastewater all refer to this un-utilized high nutrient concentration solution and are used interchangeably.  Discharge of this untreated effluent to the environment may potentially result in degradation of ground- and surface water quality and fish and wildlife habitat. As a result, the regulatory agencies in British Columbia have been directing the greenhouse industry to control the quality of their wastewater discharge utilizing two pieces of legislation including the Federal Fisheries Act and the Code of Agricultural Practice for Waste Management under the Provincial Waste Management Act. Under section 36(3) of the Fisheries Act, it is an offence to deposit any deleterious substance into water frequented by fish, including water that may eventually enter water frequented by fish. Part 5, Section 11 and Section 13 of the Provincial Code of Agricultural Practice for Waste Management states that agricultural waste must not be directly or indirectly discharged into a watercourse or groundwater.  1  Greenhouse effluents are unique with respect to other well characterized and studied wastewaters due to their high nutrient and low organic carbon concentrations.  Due to the high nutrient content,  greenhouse effluent is considered as an agricultural waste and therefore cannot be discharged directly to the environment.  Of particular environmental concern are the high nitrate and phosphate  concentrations present in greenhouse overdrain and the potential for these nutrients to induce eutrophication of the receiving waters and alter the structure and dynamics of aquatic ecosystems. Algae blooms are one of the most common biological phenomena associated with eutrofication and can result in reduction of the dissolved oxygen (DO) in the water column and development of anaerobic sediments due to decay of the algal biomass. Reduction of the DO levels in receiving waters in the Greater Vancouver region is a concern as salmonids, most commonly coho salmon, rainbow trout and coastal cutthroat trout, often utilize agricultural ditches and/or the downstream creeks and rivers as year-round or over-wintering habitat (Ian Whyte, ECL Envirowest Consultants Limited, pers. comm.).  Research over the past 16 years has demonstrated constructed wetlands to be effective tools for nutrient management and suggests that they may be more cost-effective than other treatment alternatives (Haberl and Perfler 1990, Johnston 1991, Rogers et al. 1991, Reed and Brown 1992, 1995). The beneficial aspects of using wetlands for wastewater treatment include relatively low construction costs, low maintenance requirements, tolerance to variable hydrological and contaminant loading rates and reliable wastewater treatment. Further, periods of high wetland productivity roughly parallel the greenhouse vegetable production season with the winter dormancy period for wetlands coinciding with winter shutdown and periods of low wastewater production.  The alternative to treating the wastewater is to recycle it. By recirculating the effluent, the greenhouse operators would optimize fertilizer utilization and reduce the volume of water required for the operation  2  of the facility. The potential of spreading diseases by recycling the wastewater dictates sterilization of the overdrain water prior to reuse. Three methods are available for sterilization: ultraviolet radiation (UV), ozone (O3) and heat. UV sterilization works by damaging the DNA and RNA of the bacteria, fungi and viruses within the wastewater. As the ultraviolet radiation must penetrate the prospective disease vector to be effective, the water must be relatively free of suspended solids. In contrast, ozone sterilization is a chemical process. Ozone is generated by applying a high voltage across a stream of air or pure oxygen producing 0.5 to 3 percent ozone in the air stream or 1 to 6 percent ozone in the pure oxygen stream. The ozone is then bubbled through the wastewater where it reacts with water molecules forming HO and HO2 free radicals. The free radicals in turn react with the cellular membrane or cell wall of the vectors inducing lysis. Due to the nature of UV and ozone sterilization, both processes are inhibited by the presence of suspended solids. Vectors are encapsulated by suspended particles would be protected from both processes (Metcalf and Eddy, Inc. 1991).  Heat sterilization, which acts by denaturing cellular proteins and genetic material, is not affected by the presence of suspended particles and therefore is the most effective sterilization approach. For complete viral and fungal destruction by heat sterilization, the wastewater must be heated to 95°C for a minimum of 30 seconds. The energy for sterilization is typically generated by natural gas or by electricity with the heat being transferred to the wastewater by titanium diffusion plates. This process can be negatively affected by the presence of soluble organic compounds in the overdrain which can damage the diffusion plates.  Soluble organic materials, such as tannins and lignins, are present in overdrain due to the  utilization of yellowcedar as a planting medium (BCMAFF, 1994).  These technical problems surrounding the sterilization of greenhouse overdrain has lead the greenhouse industry to look at alternative treatment options. One option is the use of constructed wetlands. In the spring of 1995, a partnership of three groups in the Greater Vancouver area, namely the Department of  3  Chemical and Bio-Resource Engineering (Bio-Resource Engineering Program) at the University of British Columbia, ECL Envirowest Consultants Limited and Houweling Nurseries Limited, initiated a pilot scale research project to assess the potential use of constructed wetlands technology for the treatment of the low organic carbon, high nutrient wastewaters generated by the B.C. vegetable greenhouse industry. The duration of the research program was two years ending March 31,1997.  2.0  OBJECTIVES  The primary objective of this research project was to assess the capability of constructed wetland technology to reduce and remove the excess nutrients present in the overdrain generated by vegetable production in greenhouses.  The primary constituents of concern in the effluent are nitrogen and  phosphorus with secondary concern for biochemical oxygen demand (BOD), total solids, and organic carbon. The water quality criteria utilized to assess the efficacy of the wetland treatment are the provincial and federal water quality guidelines published in Canadian Water Quality Guidelines (CCME 1995) and Water Quality Criteria: Approved and Working Criteria for Water Quality (MELP 1994).  A secondary objective of this project was to identify water quality objectives specific to wetland treatment of greenhouse overdrain. This required the characterization of greenhouse wastewater with respect to nitrate, ammonia, total Kjeldahl nitrogen, ortho-phosphate, total phosphorus, total solids, total organic carbon, BOD and pH. The analysis of water samples from specific points within each wetland 5  design, to assess treatment efficacy relative to wetland size.  The final project objective was to  determine the most efficient and cost effective design and, if possible, publish a document which will offer greenhouse operators a design approach for a treatment wetland which will allow their operations to meet MELP discharge guidelines.  4  3.0 3.1  LITERATURE REVIEW WETLAND DESIGN AND TREATMENT PERFORMANCE  The use of wetlands for the treatment of polluted waters has been under investigation since the early 1950's with interest in this "low-tech" approach to water quality improvement dramatically increasing since 1980 (Kadlec and Knight 1996). During this period, three major design approaches (surface flow, subsurface flow and vertical flow) have evolved and been used to remediate municipal sewage, stormwater, landfill leachate, acid mine drainage, industrial wastewaters and agricultural runoff (Hammer 1989, Moshiri 1993). By constructing artificial wetlands it is possible to maximize the treatment processes of natural wetlands and protect the fish and wildlife habitat values of natural wetland systems.  The primary advantage of using constructed, or treatment, wetlands is their  potential to provide low cost, low maintenance water treatment with ancillary aesthetic and wildlife benefits.  The constructed wetland approach to water treatment takes advantage of intrinsic processes occurring within natural wetlands. Water borne pollutants entering the wetland system are eliminated through a combination of physical, chemical and biological processes which include settling, flocculation, precipitation, adsorption to soil and organic compounds, volatilization, assimilation into plant tissues, microbial decomposition and microbial transformations. With the exception of plant assimilation and the various adsorptive processes, the contaminant processing mechanisms in wetlands are very similar to the removal processes that occur in package treatment plants, lagoons and other conventional wastewater treatment facilities. As these processes are naturally occurring in the wetland environment, treatment objectives similar to those established for traditional biological wastewater treatment facilities can theoretically be met at a relatively low developmental and operational cost.  5  Compared to  conventional wastewater treatment technologies, wetlands have lower construction costs, lower maintenance costs, require less operational attention and rarely require the addition of chemical reagents. The chief drawback to the use of wetlands is related to the natural treatment processes which are inherently slower; as the biological removal mechanisms are operating under non-ideal conditions, enzymatic activity of the wetland micro-organisms is lower than that found in the microflora of traditional/conventional systems. Hence, longer residence times are required to meet treatment objectives and therefore constructed wetland facilities have large land requirements.  3.1.1  SURFACE FLOW WETLANDS  Of the three wetland designs that have developed, the surface flow (SF) wetlands are the simplest design and the most common in North America. SF wetlands have a number of "aliases" including free-water surface (FWS), artificial marshes and biofdtration marshes. These systems mimic natural marshes in that the water primarily flows above-ground in a sheet-like manner through emergent wetland plants. A simple SF wetland consists of an excavated basin with a 20 to 30 centimetre (cm) layer of a planting media overlying the bottom of the basin, 10 to 50 cm of water flowing over the soil and emergent vegetation covering greater than 50 percent of the surface area. Wastewater is directed into the system across the inlet end of the basin and is intended to move in a sheet-flow manner through the marsh to the outlet structure(s). Typically, the bottom of the wetland is level and, where infiltration of ground water into the system or seepage of the wastewater from the treatment wetland into the groundwater is a concern, the wetland is lined with an impermeable synthetic material or clay layer (USEPA 1988). Length to width ratios have traditionally been 3:1 or greater to prevent the water from short-circuiting; however, recent publications have suggested that ratios of 1:1 may be  6  sufficient. The use of berms and regions of open water, greater than one metre in depth, have also been suggested as tools to reduce the possibility of short circuiting (Knight et al. 1994).  SCALE V 1:25 H 1:50  NATIVE MATERIAL  Figure 1. Typical SF Wetland Design  Wetland plants provide mineral cycling and the surface area required by the attached microbial populations which mediate the majority of the treatment processes. Choice of plant species is primarily limited by the hydroperiod and therefore by the design. As most SF wetland systems are flooded yearround, the plant choice is limited to emergent macrophytes. Wildlife habitat values and the option of planting more than one species are also features that should be considered. By planting more than one variety of wetland vegetation there is an increased habitat value and there is a reduced potential for a large scale die-off due to disease negatively impacting the system. Additionally, non-native species should be avoided as they have the potential invade surrounding wild wetlands and out-compete native species. Suitable species of wetland plants that are common in British Columbia include broadleaf cattail (Typha latifolia), rush (Juncus spp.), bulrush (Scirpus spp.), sedge (Carex spp.), mannagrass  7  (Glyceria spp.), bentgrass (Agrostis spp.), reedgrass (Calamogrostis spp.) and bluegrass (Poapalostris spp.).  A large body of literature on treatment wetlands exists addressing topics ranging from the role of the plants in constructed wetlands to design approaches to results of various research projects. Most of the design information is based on traditional wastewater treatment design approaches in combination with the results of academic and industry based wetland research. Research on SF treatment wetlands over the past two decades has primarily occurred in the United States (US). This is attributable, in large part, to the availability of larger parcels of land in the US, lower construction costs of SF designs with respect to SSF designs, and various federal and state environmental policies which promote the creation of wetland habitat. A database of North American constructed wetlands, released by the USEPA Risk Reduction Engineering Laboratory in 1994, compiled the data from 203 treatment wetland systems at 178 sites, five of which were in Canada. Of these treatment wetland systems, 151 were constructed (as opposed to natural wetlands) and 89 were SF. The majority all wetlands in the database were constructed for municipal wastewater treatment. Although there are a number of published papers on SF treatment wetlands, the majority of the readily available nutrient and organic carbon removal data for this design comes from the USEPA wetland database. The information in this database has been used extensively for the development of design criteria by Kadlec and Knight (1996).  Between August 1991 and July 1994, van Oostrom et al. (1994, 1995) assessed the potential of using SF wetlands planted with giant sweet grass (Glyceria maxima) for treating nitrified meat processing effluents in New Zealand. Bench-scale laboratory experiments conducted at 20 °C demonstrated a mean denitrification rate of 3.8 grams per square metre treatment area per day (g/m /d) under anoxic 2  conditions. In these experiments 2.1 grams of plant biomass carbon was consumed per gram of  8  nitrate denitrified. In the two pilot-scale research projects, van Oostrom used 40 cm deep surface flow constructed wetland systems vegetated by a floating mat of giant sweet grass (Glyceria maxima). Mean nutrient characteristics of the wastewater being treated were reported as 197 mg/L total nitrogen (TN), 121 mg/L N0 +N0 , 405 mg/L COD and 38 mg/L BOD . The corresponding 2  3  5  loading rates were 11.2 g/m /d TN, 6.9 g/m /d N0 +N0 , 23.5 g/m /d COD and 2.2 g/m /d BOD . 2  2  2  2  2  3  5  Over the course of the first year (1992) the reported nitrogen removal rates varied between 0.5 g N/m /d during the winter months to 3.0 g N/m /d in the summer. Increased removal rates as high as 2  2  9.5 g N/m /d during summer operation, with a year-round average of 5.3 g N/m /d with an average 2  2  nitrogen loading rate of 11.2 g N/m /d, were reported (van Oostrom et al. 1995). Approximately 87 2  percent of the nitrogen removal realized was attributed to denitrification with 13 percent removal due to accumulation in the plant biomass and wetland sediments.  Martin and Johnson (1995) reported extremely high treatment efficiencies for a SF treatment wetland receiving landfill leachate in Escambia County, Florida. Leachate from a primary treatment pond was fed into a series of ten interconnected 11 m by 93 m wetlands comprising a system 1.1 hectares in area and close to one kilometre in length. Two hydraulic loading rates with resulting hydraulic retention times of 4.4 days and 7.2 days were assessed. Under both operating conditions, Martin and Johnson (1995) reported a 99% reduction in TN and the wetlands were able to attain 88% and 94% reductions in TP, during the 4.4 day HRT and 7.2 day HRT, respectively.  Unlike van Oostrom  (1994, 1995) who reported his data as loading rates, all data presented by Martin and Johnson (1995) was reported as influent and effluent concentrations in mg/L with ammonia the primary nitrogen component of the total nitrogen measurement. In the 4.4 day HRT assessment, the total phosphate concentrations in the lagoon effluent (wetland influent) averaged 3.4 mg/L and produced an average effluent concentration of 0.2 mg/L. Total nitrogen and ammonia nitrogen concentrations through this  9  phase of the data collection averaged 391 mg/L and 350 mg/L, respectively, while average wetland effluent concentrations were 2.2 mg/L and 0.1 mg/L, respectively.  Results from a two year pilot-scale SF constructed wetland treatment system installed at a pulp and paper mill in Florida were reported by Knight et al. (1994). The pilot wetlands were put into operation in July 1991 and monitored through to June 1993. In this study, the authors compared the effects of aspect (length to width) ratios, the effect of deeper open water areas and various hydraulic loading rates on the treatment efficiencies of SF systems. Mean influent concentrations were: 9.09 mg/L TN; 3.35 mg/L NH ; 0.89 mg/L N0 "; 0.97 mg/L TP; 21 mg/L BOD ; and, 73 mg/L TOC. Of 3  3  5  the design parameters assessed, HLR and the presence of unvegetated deep open water regions across the wetlands had the greatest impact on treatment efficiencies. The cell operating with the lowest HLR and containing the open water sections yielded the highest treatments with reductions of 67% BOD , 91% NH , 73% TN, 71% TP, and 88% N0 . An inverse relationship between TSS removals 5  4  3  and HLR was also reported.  3.1.2  SUBSURFACE FLOW WETLANDS  Subsurface flow (SSF) treatment wetlands are known by a number of pseudonyms depending on what part of the world you are in. Vegetated submerged beds (VSB), reed beds, root-zone systems and gravel-bed wetlands are all commonly used terms for SSF treatment wetlands. Of the three treatment wetland design options, SF, SSF or VF, SSF wetlands are the most common world-wide. Simple SSF systems consist of an excavated bed 20 cm to 100 cm in depth with a gentle bottom slope between 0 and 0.5% andfilledwith a porous media ranging between sand to mixed gravel to cobbles (USEPA 1988, Kadlec and Knight 1996). As with the SF systems, if protection of the groundwater  10  is an issue, the cells are isolated with an impermeable synthetic or clay liner. The wastewater to be treated is distributed across the inlet end of the wetland and flows horizontally through the root zone of the plants, below the surface of the gravel, to the outlet(s).  The choice of bed material/media and plant species are critical factors in SSF design. It is important to choose a substrate material with sufficient void space available such that the wastewater can pass around/through the material without overland flow occurrence yet provide a high surface area for microbial biofilm development and thus treatment. For SSF wetlands with aspect ratios of 6:1 or greater, overland flow conditions often result if a coarse bed material is not used. In selecting a material that will provide an adequate void space to allow subsurface flow of the wastewater, it is important to realize that a heavy material may restrict the development of the plant root system and thus reduce the efficiency of the system (i.e. a large diameter rock material will provide high hydraulic conductivity but the weight will impede full root development). Microbial attachment sites are located on the surface of the media as well as on the root themselves.  "Leakage" of oxygen and biochemically active  organic molecules such as growth factors and vitamins from the root system allows aerobic microbial populations to develop within an otherwise anaerobic environment resulting both anaerobic and aerobic treatment microcosms. As a result, it is important to match the bed depth with a plant which has a dense root network of equal depth. If short-circuiting or overland flow does occur, the system ends up performing as a SF wetland with a short residence time. Subsequently, the treatment efficiency decreases. Other factors to consider in selecting a substrate include adsorptive capacity of the material, potential adsorbed or inherent contaminants and cost. As with the SF wetlands, emergent macrophytes are the plants of choice due to the permanently saturated root-zone; however, as there is no standing water in a properly designed SSF system, a larger selection of plant species, including grasses such as mannagrass, bluegrass, bentgrass and reedgrass, are available to choose from.  11  SSF wetlands are the predominant treatment wetland systems found around the world with their application being, almost exclusively, for single household or municipal wastewater treatment. The majority of published work on SSF designs originates from, in descending order, Europe, Australia and the United States of America (Hammer 1989, Moshiri 1993, Haberl et al. 1995). Although these systems have higher construction costs than SF designs on a per hectare basis, primarily due to the cost of the bed media, they have smaller land requirements than SF systems for treating BOD and TSS. Other significant advantages of the SSF system include a greater tolerance to low temperatures (because the treatment is occurring below the ground surface and therefore is insulated) and the greater adsorptive capacity due to the high surface area available (Maehlum etal. 1994, Wood 1995).  il/f/^ \ / Phragmites  DIRECTION OF FLOW —  II  2  GREENHOUSE EFFLUENT  SCALE V 1:25  Figure 2. TypicaVs^F Wetland Design  NATIVE MATERIAL  A number of review articles have been written summarizing the design and performance of SSF wetlands. Cooper et al. (1990) provided a brief description of the principals underlying reed bed treatment systems and summarized the performance data from 26 operational municipal wastewater treatment systems in the United Kingdom (UK). The majority of the conclusions presented were related to choice of bed materials, design details and practical suggestions on bringing SSF systems into operation. Although the authors did not specifically address the removal efficiencies of the systems described, treatment reductions ranged from 68% to 89% for BOD , 70% to 93% SS, -9% to 68% 5  12  ammonia and 1% to 69% reductions for ortho-phosphate. Where data was available for more than one year, an improvement in treatment efficiency was observed over time for BOD, SS and NH -N 4  suggesting an evolution of the bacterial populations responsible for much of the wetland performance; however, in these systems O-PO4 reductions decreased suggesting that phosphate removal in subsurface systems is via an adsorptive mechanism and may have a limiting removal capacity.  Green and Upton (1994) reported the details of Severn Trent Water Ltd.'s constructed wetland program for effluent polishing at 16 sites in England. The standard tertiary treatment reed beds at the various Severn Trent operations comprise 0.6 m deep gravel beds planted with common reed (Phragmities australis). While the primary goals of these systems are to produce an effluent with TSS and BOD concentration less than 45 mg/L and 25 mg/L, respectively, nitrogen and phosphorus treatment was also monitored.  Wetland data was provided for five of the described systems and were in use in  communities with populations between 400 and 1,150.  The wetland areas ranged between 0.78  m /person to 1.17 m /person although a standard 5 m of wetland area per cubic metre wastewater to be 2  2  2  treated per day was used for the designs. As described by Cooper et al. (1990), treatment performance for organic carbon, solids and nitrogen improved as the systems matured. Reductions in organic carbon and nutrients ranged from 77% to 88% for BOD , 77% to 87% SS and -7% to 90% reductions in NLL-N 5  for their second year of operation. Only the first year data was available for ortho-phosphate with an average 12% reduction observed over the five systems. In all five cases the authors reported that SS and BOD5 objectives were exceeded; mean effluent concentrations for the combined data reported was 4.78 mg/L SS and 2.72 mg/L BOD . 5  Using the finding of a USEPA sponsored evaluation of American SSF systems, Reed and Brown (1995) attempted to identify the relationship between hydraulic residence time and removal performance for BOD5, TSS, ammonia-nitrogen and phosphorus. Fourteen full-scale SSF systems were used in the  13  5  study. Of the SSF treatment wetland systems, one was treating industrial wastewater, one was treating domestic wastewater, one hospital wastewater and the remainder were municipal wastewater treatment systems. With one exception (for TSS) all of the systems analyzed were able to produce a final effluent with BOD and TSS concentrations less than 20 mg/L. The authors also state that constructed wetland 5  are incapable of producing an effluent BOD below the 2-7 mg/L range, regardless of design, due to decomposing plant matter and other natural organic materials inherently present in wetlands. By plotting BOD removal (%) vs. HRT (d) the authors demonstrated a minimum of 60% BOD removal occurring within the first day of retention within the SSF wetlands with up to 90% plus reduction achievable within a 8 day HRT. The initial high rate of BOD and SS removal observed within the day 5  of treatment is due to filtration and settling of the wastewater while further reductions observed are due to microbial processes. Ammonia removal in the assessed wetlands ranged between a net export of nitrogen, due to decomposing organic matter in the system, to greater than 90% ammonia removal. Effective nitrogen reduction required an extended HRT and was limited by the low concentration of available oxygen in the systems. Reed attributes the high level of ammonia removal in two of the wetlands investigated in his study to the density and depth of root-zone development within the gravel bed. In the two systems showing very high ammonia removal, both wetlands had highly developed root systems extending to the bottom of the treatment beds.  As with the systems described above,  phosphorus removal in the wetlands studied was somewhat limited with removal ranges between 0% to 60%. No relationship between HRT and treatment efficiency for phosphorus was suggested.  Research conducted in the UK by Horticulture Research International for the Horticultural Development Council (Hardgrave and Hufton 1995) investigated the potential of using reed-beds for removing nutrients from run-off generated from hydroponic tomato and pepper crops. This report was the only research project assessing the application of wetland technology to the vegetable greenhouse industry identified in this literature review. The wetland used for this study consisted of  14  a 8 m by 3 m bed, 0.6 m in depth, filled with 10 mm pea gravel and planted with common reed {Phragmities australis) and Wood small reedgrass (Calamagrostis epigeious). An average 8.5 m per week of run-off from 450 m of production area was fed to the system in 50 L doses over the 2  course of the study. Overdrain nutrient concentrations of 234 ppm nitrate, 0.8 ppm ammonia and 30 ppm phosphate reported are similar to target concentrations for BC growers (BCMAFF 1993). This study demonstrated nitrogen and phosphorus mass reductions of 28% for NO3-N, 56.26% for NH -N 4  and 40%o for P. The reduction rates were lower than originally anticipated by the authors and have been attributed to the limited carbon source available to the microbial populations for denitrification and the limited absorptive capacity of the chosen wetland substrate for phosphorus removal, respectively.  In their report the authors recommend composting of the plant biomass from the  greenhouse operation and utilizing the product as a carbon supply for denitrification of the overdrain.  3.1.3  VERTICAL FLOW WETLANDS  Most recently investigations into vertical flow (VF) wetlands have been reported in the literature. These systems are very similar in design to SSF wetlands with the exception that the wastewater flows vertically rather than horizontally through the gravel bed, much like a trickling filter. Typically the wastewater is applied evenly over the surface of the wetland and is allowed to seep through the gravel bed and rhizosphere of the wetland to a collection grid installed at the bottom of the bed. If two beds are used there is the potential to alternate their use and allow one bed to drain and re-establish aerobic conditions to the system. The majority of the research to date assessing the application of VF wetlands has been conducted on a bench-scale level; however, there is some field testing being conducted in Europe (Perfler and Haberl 1993).  15  3  Figure 3. Typical VF Wetland Design  3.2  NUTRIENT REMOVAL PROCESSES  For any single element or natural compound, the combined natural mechanisms by which it is modified and eliminated from the wastewater stream comprise the biogeochemical cycle. These mechanisms include settling, flocculation, precipitation, adsorption to soil and organic compounds, volatilization, assimilation into plant tissues, microbial decomposition and microbial transformations.  The  biogeochemical cycles of most macro-nutrients have been extensively studied in wetlands and the natural environment as a whole. While these processes are common to all wetland systems, variability within the functional components of each system (i.e. water depth, substrates, plants, wastewater characteristics, temperature effects, etceteras) alter the biogeochemical cycling of the various wastewater constituents making it difficult to predict the response of any individual wetland system to different wastewater applications or to transfer results from one geographical area to another. As a  16  result, the effective design of a treatment wetland requires a strong understanding of the biogeochemical cycles of the individual wastewater constituents of concern and their impacts on the environment.  3.2.1  ORGANIC CARBON REDUCTION PROCESSES  Organic carbon in wetlands is derived from external inputs such a wastewater stream and from internal inputs due to photosynthetic activity of algae and higher plants within the wetland. In solution, organic matter can be expressed as dissolved organic carbon (DOC), particulate organic carbon (POC) and total organic carbon (TOC), or in terms of chemical or biological oxygen demand (COD and BOD). The compounds which are measured by these collective parameters include a wide range of biochemically synthesised compounds such as carbohydrates, amino acids, sugars, fatty acids, alcohols, and proteins as well as humic and fluvic acids, a loose group of poorly defined high molecular weight compounds characterized by their aromatic character and phenolic and carboxylic acid functional groups. These latter compounds, collectively known as gelbstqff, are the by-products of fungal and bacterial degradation of plant tissues and are far more recalcitrant than the former organic compounds due to their aromatic nature.  They are separated into the two groups by  solubility due to molecular weight with the humic acid fraction being larger and less soluble than the fulvic acid fraction (Zehnder 1982).  Removal or reduction of organic carbon and suspended solids in a wetland environment occurs via physical settling, fdtration and by microbially mediated processes. Physical settling and flocculation of suspended solids primarily occurs in the initial third of a constructed wetland system as flows entering the wetland slow down and spread out across the wetland (Wood 1995). Further resistance to water movement and removal of finer particles comes from the aboveground parts of the plants and organic litter which act like a fdter to the wastewater.  17  Once in the wetland environment a number of different bacteria and fungi utilize DOC and POC as a substrate for building cellular compounds and energy production. The microbial process which result in the oxidation of organic matter to inorganic carbon dioxide is dependant on the oxidationreduction state of the wetland environment and is often a sequential process involving more than one microbe species and/or purely chemical reactions. Table 1 summarizes the redox sequence of the biologically mediated oxidation of organic matter. The redox sequence changes from aerobic to anoxic to anaerobic from the top of the table to the bottom of the table. The denitrification and nitrate ammonification components of the redox sequence are important wetland processes and are discussed in the following section.  Table 1. Microbially Mediated Organic Carbon Oxidation and Reduction  ;Reaction Aerobic respiration [CH 0] + 0 2  Redox potential  exchanged (k.l/mol)  E"„ (mV)  117.5  810  112.0  750  94.5  500  74.0  360  24.3  -100  23.4  -180  18.0  -220  16.3  -250  C0 + H 0  2  2  2  Denitrification [CH 0] + / NCV + % H 4  2  -AG" per mol of c"  C0 + 7 N + / H 0  +  7  5  2  5  2  5  2  Manganese reduction [CH 0] + 2 Mn0 + 2 H - > MnC0 + Mn + 2 H 0 +  2  2+  2  3  2  Nitrate ammonification [CH 0] + V N0 " + H -> C 0 + 7 N H +  2  2  3  2  2  + 4  +7 H 0 2  2  Iron reduction [CH 0] + 4 FeOOH 2  (s)  +6H  FeC0 + 3 Fe + 6 H 0  +  2+  3  2  Fermentation [CH 0] -> 7 C 0 + 7 [C H O] 2  3  2  3  2  fi  Sulphate reduction [CH 0] + 2  7 S0 2  2 4  "+  7 H -»co + 7 HS" + H 0 +  2  2  2  2  Methane formation [CH 0] + 7 C 0 -> C 0 + 7 C H 2  2  2  2  2  4  (Grant 1985)  18  3.2.2  NITROGEN REMOVAL MECHANISMS  Constructed wetlands have been utilized for the removal of nitrogen from wastewater streams with highly variable degrees of success. Understanding the behaviour of nitrogen in this climate is an important component in the design of functional treatment wetlands. In the wetland environment, nitrogen has a complex biogeochemical cycle comprising multiple transformations occurring under extremely different environmental conditions.  Four of the seven possible oxidation states and  corresponding inorganic forms of nitrogen are observed in aquatic solutions: ammonia (-III); molecular nitrogen (0); nitrite (III); and, nitrate (V). The conversion of nitrogen between these states occurs via the microbially mediated processes of fixation, amnionification (mineralization), nitrification and denitrification. A fifth process, ammonia volatilization, is an important component of the biogeochemical cycle of nitrogen in wetlands and is the only chemical/physical process is involved in the removal of nitrogen from the aquatic environment (Bowden 1987).  Metabolically, all living organisms require nitrogen in the form of ammonia for its role in metabolic function (Boyd 1984, Vymazal 1995). Conversion of atmospheric nitrogen gas into ammonia is known as nitrogen fixation. This process is primarily mediated by a multitude of bacteria either as free organisms or in a symbiotic relationship with higher plants. Cyanobacteria, or blue-green algae, have species which are found in a free-living state and others living in a symbiotic relationship with fungi in lichens.  The mechanism involved is a enzymatic catalysis of molecular nitrogen by  nitrogenase which is only found in prokaryotes. The reduction of the triple bonds in N is a high 2  energy reaction requiring six electrons (equation 3.1) (Boyd 1984). Electrons required for nitrogen fixation are derived from photosynthetic reactions, such as in the cyanobacteria, or from the oxidation of organic carbon. The energy required for the reaction is supplied by ATP and the quantity of ATP necessary varies between one genus of bacteria to another. Once the nitrogen is in  19  the form of ammonia it is metabolized into glutamate and glutamine before its transamination to amino acids and eventual incorporation to protein (Boyd 1984).  6 H + 6 e• + N^N — (nitrogenase) -> 2 NH +  3  (3.1)  Although nitrogenase activity is inhibited by oxygen, the environment conditions under which nitrogen fixation occurs range from aerobic to anaerobic. As a result, the overall rate of nitrogen fixation is determined by a number of environmental factors depending on the dominant nitrogen fixing micro-organism present The most significant inhibiting factors are the availability of carbon substrate, low light intensities, high concentrations of oxygen and a high redox potential. In addition, nitrogen fixation is inhibited by high ambient concentrations of inorganic nitrogen and pH values greater than 8 and less than 5. Microoorganisms which fix nitrogen under aerobic conditions have evolved systems that will maintain nitrogenase activity. For example, when Azotobacter have a readily available source of carbon its respiratory rate is high enough that oxygen is reduced to water before it can interact with the nitrogenase.  When carbon becomes limited the respiration rate  decreases and the oxygen is not reduce as rapidly thus potentially inhibiting the nitrogenase. Under these conditions the cell produces a protein which reversibly complexes with the enzyme providing protection during periods when oxygen is present (Boyd 1984).  Mineralization is the microbial conversion of an element from its organic state to its inorganic form. Although plants readily uptake nitrate to fulfil their nitrogen requirements it must be reduced to ammonia before it can be utilized metabolically. As ammonia is the required nitrogen form for incorporation into biomass, it is the preferred form for uptake by algae and higher plants. Thus the minerialization of nitrogen from an non-bioavailable organic form to ammonia or ammonium (NH ) +  4  20  is an important process mediated by bacteria and fungi in nitrogen limited environments. The process occurs directly by enzymatic cleavage of nitrogen from various organic compounds or indirectly by carbon mineralization. Micro-organisms use a number of enzymes such as peptidases, proteases and deaminases to produce N H / - N from organic nitrogen compounds.  During the  mineralization of organic matter, bacteria and fungi obtain their energy from the oxidation of organic carbon to CO2.  As the C O 2 is released by respiration, the organism accumulates an excess of  nitrogen and eventually excretes the surplus to the surrounding environment where it is available to re-enter the nitrogen cycle. In wetlands treating municipal wastewater, which has a relatively high concentration of organic matter, nitrogen mineralization processes can drastically reduce the ammonia treatment efficiency of the system.  The sequential oxidation of ammonia to nitrite, and nitrite to nitrate, by bacteria is collectively known as nitrification. The group of bacteria which carry out these reactions are generally called nitrifying bacteria or nitrifiers. Nitrifying bacteria are strict aerobes yet can survive in conditions where oxygen is available in extremely low concentrations. In wetlands, nitrifiers can be found in the water column, at the sediment water interface and in sediments adjacent to the rhizosphere of the wetland plants. In this latter environment, the microorganisms are utilizing the microaerobic zone created by the radial oxygen loss from the root hairs of the emergent macrophytes.  Nitrification is a two step process. The first reaction, the oxidation of ammonia to nitrite (equation 3.2), occurs within obligate chemolithotrophic bacteria which are dependant on the oxidation of ammonia for their entire energy supply (USEPA 1993). While the overall reaction is relatively simple, it has been postulated that the reaction has a total of five steps: ammonia (NH /NH ) - » +  3  4  hydroxylamine (NH OH) -> nitroxyl (NOH) -> nitrohydrolylamine (N0 NH OH) -> nitrite (N0 ). 2  2  21  2  2  Various species within a number of prokaryotic genera have been identified as nitrifiers in soils but only one species, Nitrosomonas europaea, is capable of ammonia oxidation in freshwater habitats (Watsons al. 1981).  The second step in nitrification is the oxidation of nitrite to nitrate (equation 3.3).  Unlike the  oxidation of ammonia to nitrate which is catalyzed by a single bacterial species in fresh water aquatic environments and numerous species in soils, nitrite oxidation in both soils and fresh water is only carried out by a single species of bacteria (Watson et al. 1981, Grant and Long 1985). This microorganism, Nitrobacter winogradski, is a chemoheterotroph obtaining its carbon for growth and replication from organic sources and its energy form nitrite.  NH  + 4  + / 0 + 6 e N O V + H 0 + 2 rT 3  2  2  2  N0 • + 0.5 Q -> NOV 2  NH  (3.3)  2  + 4  + 2 0 -> NOV + H 0 + 2 fT 2  (3.2)  (3.4)  2  The rate of denitrification in wetlands is dependant on pH, temperature, alkalinity, inorganic carbon availability, organic carbon availability and ammonia concentration (Boyd 1984).  In laboratory  cultures, optimal growth of nitrifiers is between 25 and 35 °C (Watson et al. 1981).  Denitrification is loosely defined as the reduction of nitrate to a gaseous product, resulting in a loss of fixed nitrogen from the affected environment. More specifically, denitrification is the anaerobic bacterial process in which ionic and gaseous nitrogen oxides serve as terminal electron acceptors for respiratory electron transport.  The oxidation of organic carbon substrates under anaerobic or  22  microaerobic conditions generates free electrons which pass through a cascade of electron carriers before reducing some form of oxidized nitrogen. In theory, denitrifying bacteria have five electron cascades resulting from organic carbon oxidation. This first cascade utilizes nitrate as the terminal electron acceptor reducing the nitrate to nitrite. The second cascade utilizes nitrite as the terminal electron acceptor reducing it to nitric oxide and so on with the sequential reduction occurring as shown in equation 3.5 (Jeter and Ingraham 1981, Vymazal 1995).  nitrate -> nitrite —» nitric oxide — > nitrous oxide -> dinitrogen (N0 ")  (NOV)  3  (NO)  (N 0)  (3.5)  (N )  2  2  Energy generated by each cascade of the organic carbon oxidation is stored as ATP for use by the denitrifiers for other biochemical processes. The production of nitrogen gas by denitrification is depicted by equation 3.6 (Soderlund and Rosswall 1982, Boyd 1984).  6 (CH 0) + 4 N0 " -> 6 C 0 + 2 N + 6 H 0 2  3  2  2  2  (3.6)  On a global scale, denitrification is an extremely important ecological and geochemical process responsible for the formation of nearly all atmospheric nitrogen gas and it is the pathway of loss for most agricultural fertilizers. On a more regional scale, denitrification offers the most cost effective method for reducing fixed nitrogen concentrations in effluents, thereby reducing the impacts on the quality of receiving waters. In wetland soils denitrification occurs in anaerobic regions of the litter and below the aerobic sediments. The rate of denitrification is dependant on the supply of N0 ", 3  temperature, pH, redox potential and available biodegradable organic carbon. While in natural systems nitrate is typically found in very low concentrations, many wastewaters have high nitrate  23  concentrations. In these instances temperature and available organic carbon are the limiting factors for denitrification. van Oostrom et al. (1994) reported sufficient carbon production in a G. maxima SF wetland to sustain a denitrification rate of 2.4 - 4.8 g N/m /d. Further, it has been theorized that a 2  Typha wetland could denitrify 1.1 metric tonnes of nitrate per hectare per year if favourable temperatures existed (Reed et al. 1995).  The combined nitrogen reduction of treatment wetlands is often assessed based on the combined nitrification and denitrification of the system.  As these two processes are capable of occurring  simultaneously in wetlands due to the presence of aerobic and anaerobic zones, it is possible to provide a combined equation for the removal of ammonia from their environment (Vymazal 1995).  24 N H  + 4  (3.7)  + 48 0 -> 24 N0 " + 24 H 0 + 48 FT 2  3  2  (3.8)  24 N0 ~ + 5 C H 0 + 24 FT -> 12 N + 30 C 0 + 42 H 0 3  24 N H  6  + 4  12  6  2  2  2  + 5 C H , 0 + 48 0 -> 12 N + 30 C 0 + 66 H 0 + 24 H 6  2  6  2  2  2  2  +  (3.9)  The final mechanism for the removal of nitrogen from the wetland environment is the incorporation of nitrogen into plant tissues and eventually the sediments. As discussed above, ammonia is the required form of nitrogen for cellular metabolism. This does not limit cells to the uptake of ammonia or ammonium to meet cellular nitrogen requirements as all plants, fungi, yeast and many prokaryotes are able to reduce nitrate to ammonia for biosynthetic purposes.  Biomass analysis of natural and  constructed wetlands have shown wetlands to produce approximately one tonne of above-ground plant biomass annually (Vymazal 1995). Of this, up to 30% does not decompose over one year and slowly contributes to the development of the sediments (Godshalk and Barko 1985). Over long periods this accretion will result in the permanent loss of nitrogenfromthe biological cycle; however, on an annual  24  basis,  the  amount removed by this  route  in extremely  small when  compared to the  nitrification/denitrification cycle.  3.2.3  PHOSPHORUS REMOVAL MECHANISMS  The inorganic and biological cycling of phosphorus in the environment has been extensively investigated due to the importance of phosphorus in cellular function and that phosphorus is the primary limiting nutrient in unpolluted freshwater lakes, streams and rivers. Unlike nitrogen, which has more than one stable oxidation state and is present in the environment in a number of chemical forms, phosphorus has only a single environmentally stable form, phosphate  (PO4 ). 3  To remove  phosphate from the aquatic environment, it must be converted to a non-bioavailable form or permanently deposited into the sediments of the wetland.  A number of factors including pH, redox potential and concentration of Fe, Al and calcium Ca in the effluent and wetland soil contribute to the removal of phosphorous. Retention of phosphate in natural wetland systems has been demonstrated to be directly related to the content of iron (Fe) and aluminium (Al) in the sediments (Richardson, 1985 & 1986) Under acidic conditions PO4 can be precipitated as insoluble Fe and Al-phosphates, while Ca-phosphate precipitate formation is the dominant removal transformation under neutral to alkaline conditions (Faulkner and Richardson 1989). Adsorption to oxides and hydroxides of Al and Fe are also potential removal mechanisms under acidic conditions (Huang 1980). By understanding these processes it is possible to design wastewater treatment approaches which incorporate these processes and therefore maximize phosphorus reductions.  25  In a geological context, phosphate-bearing minerals exist in sedimentary, metamorphic and igneous deposits with 85% of all phosphate rock mined from sedimentary sources (Emsley 1980). Phosphate rocks have been classified into three categories based on their mineral composition: Fe-AI phosphates, Ca-Fe-Al phosphates and Ca phosphates. Of these categories, calcium phosphates are the dominant phosphate mineral deposits in the Earth's crust with 95% of the solid phosphate worldwide present as fluoroapatite (Emsley 1980). Table 2 below presents a list of six common calcium phosphate minerals in order of decreasing solubility. With the exception of calcium dihydrogen phosphate hydrate, calcium phosphates are insoluble a neutral pH.  Table 2. Calcium Phosphates Mineral  Formula  Calcium dihydrogen phosphate hydrate  Ca(H P0 ) H 0  Calcium hydrogen phosphate dihydrate  CaHP0 -2H 0  Octacalcium phosphate pentahydrate  Ca H (P0 ) -5H 0  Calcium phosphate  Ca (P0 )  Hydroxyapatite  Ca (P0 ) 0H  Fluoroapatite  Ca (P0 ) F  2  4  2  4  8  3  5  5  2  2  4  4  4  4  2  6  2  2  3  3  (Emsley 1980)  Dissolution of phosphate rock/mineral in soils and sediments is dependant upon the mineral composition (i.e. solubility constant), pH of the surrounding water and the concentrations of calcium and dihydrogen phosphate in the immediate aqueous environment.  The relationship between  solubility and these four characteristics is fairly predictable when considering solubility products and acid-base chemistry and is illustrated by the equation below. The solubility of phosphate minerals increase with decreasing pH, calcium and/or dihydrogen phosphate concentration. Using calcium phosphate as an example, decreasing pH is equivalent to increasing hydrogen ion concentration  26  which drives the reaction to a dissociated state (equation 3.10). Conversely, high concentration of calcium or dihydrogen phosphate will drive the reaction to an associated state. In solution, the ionic form of phosphate is acid dependant with H2PO4" the dominant ion at pH values less than neutral and HPO4 " 2  is dominant at pH values greater than 7.5 (Kadlec and Knight 1996).  Ca (P0 ) + 2 FT <-> 3 Ca + 2 H P0 "  (3.10)  2+  3  The  4  2  2  4  solubility product of calcium phosphate, Ca (P0 )2, is 2x10" and decreases to 10" for 29  51  4  3  hydroxyapatite and is even lower for fluoroapatite; however, the large difference in solubility does not directly influence the form of the precipitate. Environmental factors such as pH and the relative concentrations of the various metals or minerals present in solution have a greater influence the chemical composition of the precipitate. The mineralogical form of the precipitate is not relevant over long periods as it slowly converts to the more stable crystal structure of hydroxyapatite or fluoroapatite as isomorphous substitution of fluoride occurs (Khasawneh and Doll 1978, Emsley 1980).  One method of promoting phosphate precipitation in the presence of calcium, without the addition of a strong base to increase the pH, is to create an environment which will promote a dense algal population and subsequently a high rate of C 0 uptake. Natural waters are buffered by dissolved 2  inorganic carbon. The status of the C0 -HC0 "-C0 " equilibrium, with respect to which species is 2  2  dominant, is pH dependant.  3  3  The equilibrium state of the buffering system depends on the  concentration of hydrogen ion, amount of excess base, the partial pressure of carbon dioxide in the atmosphere and temperature. When algal biomass growth in a pond is rapid, the uptake of C 0  2  from  solution by the biomass outstrips the rate it can be replaced by atmospheric C 0 diffusion, 2  27  respiration, fermentation or readjustment of the solid carbonate equilibrium. When this occurs, HCO3" is converted to C O 2 by reaction 3.11 and the pH of the water increases (Zehnder 1982, Kadlec and Knight 1996).  (3.11)  HCO3" + H 0 -> H 0 + C 0 + OH" 2  2  2  Similarly, when the source of HCO3" becomes limiting, CO3 " is converted to C 0 by equation 3.12, 2  2  further increasing the pH of the water above pH 10.  (3.12)  CO3 " + H 0 -> C 0 + 2 OH" 2  2  2  To promote optimal calcium phosphate precipitation, a pH between 7.5 and 9 is ideal as the solution will be sufficiently basic to ensure all phosphate is present as dihydrogen phosphate and able to combine with the calcium in solution but not basic enough to promote calcium carbonate precipitation (above pH 9) which may interfere with the availability of Ca  2+  for further phosphate  removal.  While calcium phosphate precipitation can play a significant role in the role of phosphate from solution under neutral or basic conditions, dissolved iron and aluminium and components of wetland sediments have a dominant role in the physical and chemical removal of phosphate under acidic conditions. Phosphate precipitation using aluminum or iron is commonly practised by traditional wastewater treatment plants (Metcalf and Eddy, Inc. 1991). At pH values of 5 and 6, respectively, phosphate precipitated by aluminium and iron is predominately in the form of pure metal phosphates (AIPO4 and FeP0 ), with the proportion of hydroxyl precipitates increasing as the pH increases 4  28  (Metcalf and Eddy, Inc. 1991). Most natural surface waters contain less than 1 mg/L aluminum and 0.5 mg/L iron, although these concentrations can increase in acidic waters (CCME 1995). Above a pH of 6.5, the dominant ionic form of aluminum is Al(OH) " which no longer reacts with the 4  phosphate anion. The permanent removal of phosphate from solution as ferric phosphate precipitates is doubtful as the precipitates will likely end up in the sediments. Under the reducing conditions found in the sediment layer, iron is reduced from its ferric form to its ferrous form and a soluble Fe (P0 ) results. 3  4  2  The phosphorus retention capacity of natural wetlands can be predicted by the extractable aluminum and iron content of the soil (Richardson 1985). Sesquioxides are clays made up of oxides and hydroxides of aluminum and iron [Fe(III)] such as boehmite (AlOOH), gibbsite (A1 0 ), goethite 2  3  (FeOOH) and hematite (Fe 0 ) and have the potential to remove phosphate from solution by 2  3  adsorption. The adsorption mechanism at the surfaces of iron and aluminum oxides and hydrous oxides have been extensively studied in soil science. The mechanism of phosphate adsorption on iron sesquioxides is by a the formation of a bi-nuclear bridge between the phosphate anion and two iron molecules (Parfitt 1978). This reaction is far more stable than the attachment of phosphate to aluminum sesquioxides where the phosphate is integrated into mineral crystals such as taranakite (K H A1 (P0 ) 18H 0). 3  6  5  4  8  2  A study of fen, bog and swamp wetland soils by Richardson (1985)  demonstrated that the phosphorus retention capacity of a wetland can be predicted by the extractable aluminum content of the soil.  The final route of phosphorus removal from wetlands is by plant and animal uptake. Phosphate is a universal constituent of living cells and is an integral component of numerous biochemical compounds such as: nucleotides, the principal "building blocks" of DNA and RNA molecules and  29  energy storage/transport molecules in cells; phospholipids, which form the lipid bi-layer holding the cell together; inositol phosphates; NADP /NADPH, a oxidation-reduction molecule; phosphorylated +  sugar molecules; various vitamins; and, co-factors. The phosphorus fraction of higher plant biomass ranges between 0.08% to 0.64% by mass (Boyd 1978). Comparatively, the phosphorus content of freshwater algae ranges between 0.04% to 7.98%) (Vymazal 1995). Approximately 30% of emergent macrophyte biomass does not fully decompose in the course of one year (Godshalk and Barko 1985) resulting in an annual accumulation of nutrients in the sediment layer of the wetland. The permanent removal of phosphorus in Typha marshes which produce an average 1000 kg dry biomass per hectare per year is up to 6.4 kg of phosphorus per hectare annually. While this may not constitute a large component of the phosphorus loaded to a wetland system by a greenhouse operation, it does comprise 20% to 30% of the removal efficiencies observed in wetland systems utilized for treating municipal wastewaters.  4.0  M A T E R I A L S AND M E T H O D S  The intent of this research project was to assess the capability of treatment wetlands to remediate greenhouse overdrain at a pilot-scale level. Five wetland designs were assessed based on conventional surface flow and subsurface flow design approaches. Allfivedesigns were constructed in duplicate to ensure repeatability of the data. The wetland basins were constructed on the property of Houweling Nurseries Ltd., located at 2776 - 64 Street in Delta, BC, adjacent to the propagation greenhouse in th  March 1995. See Figure 4 for a location map of the site. The project was designed to utilize a total of 57,500 litres per day of the greenhouse wastewater flows originating from the propagation and pepper production areas. This is approximately 10% of total overdrain generated by the greenhouse operation. Overdrain flow from this production area was chosen due to the ebb and flood irrigation system in place which allowed collection of the overdrain from the entire production area at a single point.  30  The five wetland designs assessed were:  fifteen centimetre water depth surface flow wetland - planted; thirty centimetre water depth surface flow wetland - planted; thirty centimetre water depth surface flow wetland - unplanted; sixty centimetre depth gravel bed subsurface flow wetland - planted; and, sixty centimetre depth gravel bed subsurface flow wetland - unplanted.  All of the wetlands were designed with the same physical constraints: 7 metres wide by 35 metres long at mid water depth (5:1 aspect ratio); ten day hydraulic retention time (HRT); 20-25 mm nominal diameter gravel as the planting medium/treatment substrate; and, a 20 mil. thick PVC liner to prevent any infiltration of groundwater or exfiltration of wastewater.  Broadleaf cattail (Typha  latifolia), planted at a 0.5 metre spacing (four plants per square metre), was chosen for the wetland designs requiring plants. Wild stock from local donor sites was used. A 20 cm bed of gravel was placed in each of the SF wetland cells, including the unplanted systems, to anchor the wetland plants. Water depth was measured from the top of the substrate surface.  Overdrain flows from the greenhouse were initially pumped over an inclined fixed screen to remove any large pieces of plant debris, plastic clips and planting medium before being directed to a 45 cubic metre water silo. From the holding tank, flows were continuously pumped, 24 hours per day, through approximately 350 metres of 1.5 inch diameter black poly pipe to the wetlands. Two 1.25 inch ball valves were placed in-line between the pump and the wetlands to reduce the pressure and increase the flow rate in the main supply line immediately prior to the wetlands.  31  The flow into each wetland was controlled by a one-quarter inch brass needle valve. Based on the design HRT of ten days and water depth of each wetland the flow rates into each wetland was 2.55 L/min. for the 15 cm SF wetlands, 5.10 L/min. for the 30 cm SF wetlands and 3.57 L/min. for the SSF wetlands. During 1995, flows were supplied to the wetlands from the end of April through to October when the pipes froze. In March 1996 approximately 185 kg of wheat straw was added to each of the planted SF basins to enhance the litter layer and simulate a more mature wetland environment. Wheat straw was chosen for a number of reasons including expense, a C:N ratio near 120 (Haug 1993) and published studies indicating that straw has a capacity for adsorption of phosphate (Avnimelech 1993). Flows to the wetlands were re-established at the beginning of April 1996 and continued through to December 1996.  32  Figure 4. Location Map  33  4.1  MONITORING PROGRAM  Water samples were collected from the holding tank plus three sites within each wetland: 7 of the 3  length of the wetland; / of the length of the wetland; and, at the outlet of the wetland (see Figure 5). 2  3  These site locations allow the characterization of the wetland's remediation process and rates of treatment. Sample were collected every second week from each site of each wetland and analyzed for: ammonia-N (NH -N), nitrate-N (NO3-N), total Kjeldahl nitrogen (TKN), total phosphorus (TP), 3  orthophosphate (O-PO4), pH, total solids (TS), total organic carbon (TOC) and biochemical oxygen demand (BOD ). BOD was only determined for samples collected between May and mid-September 5  5  1996. Dissolved metals (Al, Ag, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, P, Pb, Si, Ti, Tl, V and Zn) were determined by ICP four times though the 1996 season. Metals and BOD were 5  not anticipated to be of concern and were not addressed in the study. Samples were only collected from the outlets of the unplanted SF wetlands (30 cm deep ponds) as these systems were well mixed by wind action and the collection of samples from within the basins could not give any indication of the rate of the treatment processes. All samples were collected in two litre opaque PET wide-mouthed screw-top containers and stored unpreserved at 4 °C. Ortho-phosphate and ammonia analyses were conducted within 36 hours of sampling and the remaining tests were conducted within 7 days. Samples for ICP analysis were stored at -20 °C in PET bottles prior to analysis. Methods and equipment utilized are presented in Table 3.  In the 1995 field season, some water samples were collected between July and October 1995; however, the absence of any decaying plant biomass or soluble BOD in the wastewater did not allow development of significant bacterial populations within the wetland basins and therefore little treatment was realized in this period. Water quality monitoring continued through to late October  34  1995 when temperatures at the research site dropped below freezing and the pipes conveying effluent to the experimental wetland froze. As it was not financially practical to bury the pipes to prevent periodic freezing, the pipes were drained for the winter. The intent of the 1995 season was not to obtain data on the treatment capacity of the wetlands but to.allow the vegetation and bacterial population to become established. All analysis of the water samples was conducted in the Bio-Resource Engineering laboratory at UBC.  UJ  DIRECTION OF FLOW  3  Figure 5. Plan view of typical wetland with sampling site locations  Biomass harvesting from all six planted wetland cells was conducted between November 6 and 9, 1995 with the assistance from Envirowest. Ten one square metre areas were completely harvested. The harvested biomass was dried and weighed at the UBC Department of Plant Science plant drying facilities.  The information from this analysis is used to estimate the available carbon for  denitrification. Table 4 shows sampling dates and analyses conducted. The raw data collected over the entire research project is presented in Appendix 1.  35  Table 3. Analytical Methods Parameter  Method  Equipment  Detection Limit  Chemisl r>  NO3-N  I.M. 33-96W  Technicon AutoAnalyzer II  0.1 ug/L  Diazo method  NH  I.M. 98-70W  Technicon AutoAnalyzer II  0.2 ug/L  Berthelot Reaction  I.M. 30-69W  Technicon AutoAnalyzer II  0.2 ug/L  Sulphuric acid digestion followed by Berthelot  3  TKN  1  Reaction TP  I.M. 327-74W  Technicon AutoAnalyzer II  0.008 mg/L  Sulphuric acid digestion followed by ammonium molybdate reduction using ascorbic acid  O-PO4  I.M. 94-70W  TOC  Std Mtds 531 OB  TS BOD5  Technicon AutoAnalyzer II  0.2 mg/L  Ammonium molybdate reduction using ascorbic acid  0.001 mg/L  Combustion-infrared  Std Mtds 2540B  0.0001 mg/L  Dried at 103-105 °C  Std Mtds 520IB  5 mg/L  2  pH  Shimadzu TOC-5050  Hanna Instruments  ±0.01 pH unit  Model HI 9214  1. Technicon Industrial Method. 2. Standard Methods for the Analysis of Water and Wastewater (AAWA 1995)  36  Table 4. Water Quality Laboratory Analyses Sampling  Ana Uses Conducted  l):iti-  NIL  TKN  TP  o-po  4  IOC  TS  HOD*  Metals  1995  V  Aug. 8 Aug. 21  V V '  V V V  Sept. 28 Oct. 10 Oct. 23  V  V  V  V  V  V V V V V V  V V V  1996 \piil 12  V  V '  April 25 May 2 May 16  V V V  V  X  V V  V V  June 27  V V  V V V  V V V  July 11  X  X  X  X  X  X  V  V V V  V V  V V  V  V V V V V V V  May 30 June 13  July 25 Aug. 8 Aug. 22  V  Sept. 5 Sept. 19 Oct. 3 Oct. 17  V V  Oct. 31 Nov. 14 Nov. 28 Dec. 12  V V  V  V X  V  . V V  X x  V V V  V  V  V V V V V  V V V V  V  X X  X  X  V  V V  V V V  V  V V  x = sample collection was scheduled but not collected. Valves to the 15 cm SF basins were plugged on June 13. Due low water levels no samples were collected from these wetlands.  37  4.2  STATISTICAL ANALYSES  Statistical analyses conducted with the data consisted of: •  developing correlation matrices for each of 0-P04, TP, NH , N0 -N, TKN, TOC and TS to 4  3  establish independence of the sampling; •  developing a randomized block design for the entire data-set and conducting a simple factorial analysis of variance (ANOVA) to identify the relative influence of design, replicate and sampling date on treatment effect;  •  conducting paired t-tests using the influent and effluent data from each of the ten wetland basins for each of the water quality parameters listed above to determine if a real treatment effect was observed; and,  •  conducting Scheffe tests for each of the parameters identified above, using the mean square error from the ANOVA, to determine if the treatment effects observed between the five wetland designs were different.  SPSS 6.0 for Windows was used to conduct the correlation matrices, randomized block ANOVA and the paired t-tests. The Scheffe tests were calculated manually using a Quattro Pro spreadsheet. The results of all statistical analyses are presented in Appendix 3.  5.0  R E S U L T S A N D DISCUSSION  Published literature show a highly variable ability of constructed wetland to remove nutrients from wastewaters. Similarly, the results of water quality analyses conducted on samples collected during the 1996 field season show a wide range of treatment effects. For TP, 0-P0 , N0 -N, NH , and 4  3  4  TOC, a statistically supportable treatment effect was observed in the majority of the wetlands but not  38  all. TKN and TS data show no reductions in concentration for any of the five wetland designs assessed.  Three aspect of the design of this research project have somewhat challenged the analysis of the results. These aspects are: the greenhouse production area supplying the overdrain to the wetlands was not consistently utilized for production of a single crop; the design HRT was 10 days yet the sampling period was 14 days; and, the root system of broadleaf cattails did not penetrate to the bottom of the SSF wetlands. The impact of these factors are further elaborated below.  Overdrain flows used for this research project were collected from a production area used for a number of crops.  Approximately half of the area was permanently utilized for green pepper  production while the other half was used for propagation of tomato and pepper starter plants, bedding plants and poinsettias. Each of these crops require different fertilizer regimes resulting in significant variations in the concentration of individual nutrients in the overdrain being fed to the experimental wetlands. It was not possible to directly monitor these fluctuations as the nutrients pass through the wetland due to the un synchronized sampling period and HRT.  The incomplete root penetration in the planted SSF wetlands resulted in the development of two distinct 'layers', and therefore two distinct flow paths, within the substrate bed. The maximum penetration of the Typha roots system is approximately 35 cm. As the root system developed in the upper portion of the wetland bed, it filled void spaces between the gravel leading to a higher resistance to water flow with respect to the regions of substrate with no roots present. In contrast, void spaces within the bottom portion of the substrate bed remained unaltered and two different flow paths, based on resistance, developed within the planted SSF basins. This difference in resistance to flow can be seen in the charts of nutrient concentration versus distance though the wetland for the  39  planted SSF basins (Appendix 2). For most of the parameters monitored in the SSF wetlands, water samples from 11.67 m and 23.33 m along the basin were collected from the middle of the bed via vertical sampling ports and show a trend of decreasing nutrient concentration; however, the outlet sample was taken from the outlet structure which collected flows from at the bottom of the gravel bed.  Nutrient concentrations in samples collected from this point show a marked increase to  concentrations near that of the raw greenhouse effluent/wetland influent.  An additional problem was encountered due to equipment failure. Between May 21 and July 13, 1996 the sump pump providing overdrain to the wetlands was rebuilt. During this period a smaller sump was used to pump the overdrain flows to the wetlands; however, this pump was unable to handle the plastic and organic debris in the raw overdrain and became plugged on a regular basis. As a result flows to the wetlands were intermittent over this seven week period.  5.1  PHOSPHORUS  The maximum allowable total phosphorus concentration for drinking water in British Columbia, established in Water Quality Criteria: Approved and Working Criteria for Water Quality (MELP 1994), is 10 ug/L. Acceptable total phosphorus levels for the protection of freshwater aquatic life in provincial lakes with salmonids as the predominant fish species are between 5-15 ug/L, site specific, with no standards established for lakes where salmonids are not the dominant fish species or for watercourses. As most waterbodies in British Columbia are oligotrophic or at the low end of the mesotropic range, these standards ensure that the natural phosphorus-limited status of provincial lakes is not degraded and algae populations are held constant.  To achieve a phosphorus  concentration of 15 ug/L or less in vegetable greenhouse overdrain, a removal efficiency greater than  40  99.98% is required. The Canadian Water Quality Guidelines (CCME 1995) does not provide any phosphorus guidelines for drinking water or aquatic life protection. Tables 5 and 6 below shows the average ortho-phosphate and total phosphorus outlet concentrations and treatment efficiencies for the ten wetlands between April and December 1996.  The total phosphorus results presented below are not considered highly accurate due to the analysis method utilized. Samples were acid digested and analyzed according to Technicon's Industrial Method 327-74W.  Although all standards were subjected to the same digestion process and R  2  values for the standard curves were 98.5% or greater, it is suspected that the acid concentrations in the analyzed samples suppressed the intensity or formation of the molybdem blue complex in samples with lower phosphorus concentrations. As a result, the calculated reductions presented in Table 5 are thought to be higher than the true removal efficiency with ortho-phosphorus results reflecting the accurate treatment effect.  Table 5. Total Phosphorus Results (mg/L) Design-  Average  StdDev  Greenhouse Effluent  99.31  81.92  305.79  8.14  N/A  1  15 cmSF#l  45.75  38.37  141.58  7.80  53.93%  2  15 cm SF #2  46.21  34.52  113.20  6.40  53.47%  3  30cmSF#l  71.78  59.99  193.22  11.52  27.72%  4  30 cm SF #2  73.98  64.18  206.71  10.38  25.50%  5  Unplanted SF#1  57.94  55.57  152.09  0.75  41.66%  6  Unplanted SF #2  39.31  43.31  108.20  1.26  60.42%  7  Unplanted SSF#1  46.20  27.98  89.36  10.77  53.48%  8  Unplanted SSF #2  38.86  25.92  89.40  9.76  60.87%  9  SSF#1  44.74  26.74  90.86  11.89  54.95%  10  SSF #2  53.22  31.60  95.54  16.02  46.41%  Cell #  41  . Max  IWin  *> % Reduction  Table 6. Ortho-Phosphorus Results (mg/L) Wetland Design  Average  StdIM  Max  Min  % Reduction  Greenhouse Effluent  98.87  39.67  155.26  19.69  N/A  1  15 cm SF #1  64.69  32.14  125.82  22.88  34.57%  2  15 cm SF #2  56.27  26.79  100.82  0.93  43.09%  3  30 cm SF#1  79.14  32.24  148.94  29.82  19.96%  4  30 cm SF #2  79.04  36.15  151.33  28.86  20.06%  5  Unplanted SF#1  76.32  43.14  148.02  17.42  22.81%  6  Unplanted SF #2  36.11  40.85  118.52  1.90  63.48%  7  Unplanted SSF#1  67.17  28.81  111.89  18.94  32.07%  8  Unplanted SSF #2  53.69  24.44  106.73  3.08  45.70%  9  SSF#1  65.19  27.71  120.76  21.42  34.07%  10  SSF #2  68.95  35.06  134.54  5.24  30.26%  Cell #  Paired t-tests comparing the mean of influent concentrations and outlet concentrations of TP and OP0 (Appendix 3) show a TP treatment effect for all of the wetlands except Cell #4 (the second 4  planted 30 cm SF basin) and a O-PO4 treatment effect for all wetlands except cells #3 (the first planted 30 cm SF basin) and #5 (the first unplanted 30 cm SF basin). Taking both total phosphorus and ortho-phosphate into account, the largest reduction of phosphorus was observed in Cell #6, the second unplanted SF wetland. The mean reduction in 0-P0 for this wetland over the entire field 4  season was 66.21%. It is important to note that most of this treatment effect was observed in the latter half of the year (Figure 6) and coincided with a significant increase in pH within the unplanted SF basins (Figure 7).  42  Change in 0-P04 Over Time  Figure 6. Change in 0-P04 Concentrations in Cells 5 & 6 Over Time  As discussed in Section 3.2.3, the three predominant modes of phosphate removal in wetlands are plant uptake, adsorptive processes and chemical precipitation. The high treatment effect documented in the unplanted SF wetland is attributed to chemical precipitation reactions under alkaline conditions. In their review article of design and performance of SSF treatment wetlands, Cooper et al. (1990) suggested that phosphate reduction observed in SSF wetlands occurs primarily via an absorptive mechanism and therefore may wetlands have an ultimate phosphorus retention capacity. Plant uptake is also limited by the storage capacity of phosphorous within the plant tissues. Given that the peak permanent removal of phosphorus in Typha marshes producing an average 1,000 kg dry biomass per year is 6.4 kg per hectare annually, a maximum of 0.157 kg of phosphorus removal observed in the planted wetland can be attributed to plant uptake. Figure 7 shows the change of pH in Cells 5 and 6 (in which the most significant reduction of P0 " was observed) over the course of the 4  1996 field season. The pH increase observed in the wetland cells is thought to be due to C 0 uptake 2  by algae as observed in natural marl lakes and described in Section 3.2.3. As the algal population in  43  the unplanted wetland basins increase they begin to uptake C 0 from solution faster than it can 2  diffuse from the atmosphere into solution resulting in an imbalance of the  CO2-HCO3-CO3 " 2  equilibrium. As these species attempt to return to an equilibrium status, OH" is generated, as shown in equations 3.11 and 3.12, and the pH in the basin increases. With the resulting increase in pH the proportion of phosphate in solution in the form of  HPO4 " 2  increases creating suitable conditions for  the formation of calcium phosphate which then precipitates from solution. Figure 8 clearly shows the strong relationship between pH and phosphorus (TP and O-PO4) concentrations for the combined data from both unplanted SF wetlands.  Figure 7. Wetland Cells #5 & #6. Changes in pH Over Time  44  275.00 j 250.00 225.00  PH Figure 8. Total Phosphorus and Ortho-Phosphate vs. pH  Figure 9. Relationship Between BOD and TOC Using Combined Data From All Wetlands 5  45  Over the course of the field season, when comparing the two unplanted surface flow wetlands, a higher concentration of algae was visually observed in Cell #6 with respect to Cell #5.  The pH  values measured in Cell #6 in the latter portion of the sampling season were also higher than in Cell #5. In an attempt to identity the cause of the chemical variations between these two basins, water samples from both cells were analyzed under a microscope to see if there was any difference in the algal populations between the two wetlands which may explain the observed differences. Scenedesmus sp. was the dominant species of algae identified in both basins although Cell #5 had a distinctly lower concentration of algae present with a significant protist component to the algal community. In contrast, Cell #6 had almost no protists present. The relationship between pH, algae population levels and the presence or absence of protists was not investigated; however, one hypothesis to explain the observation is that the high pH present in Cell #6 was outside the protists' environmental range of tolerance thereby inhibiting the establishment of a protist community. If this hypothesis is correct, the lack of any significant predator population would allow an algal population to develop to a density that would result in a depletion of free C O 2 in solution. It then follows that the grazing pressure exerted on the algal community of Cell #5 by the protists is the cause of the lower algal concentrations observed thereby inhibiting the development of a high pH environment.  Based on the data presented in tables 6 and 7, the treatment order of the wetland designs for phosphorus removal can be arranged, from most efficient to least efficient, as:  unplanted 30 cm SF > unplanted SSF > 15 cm SF > planted SSF > planted 30 cm SF.  This design progression suggests that, for the high phosphorus concentrations studied in this research project, the non-biological factors of phosphorus removal are not only more influential on the treatment efficiency but that phosphorus removal capacity is decreased by interactions of the  46  biological components. Unlike the unplanted 30 cm deep SF wetland, the unplanted SSF basins did not have a high pH and phosphorus reductions observed in these basins are likely due to adsorption processes to limestone, aluminum or iron mineral components of the rock used as substrate material. If this is the case then it is possible that SSF designs may have a limited capacity for phosphorus removal as suggested by Cooper et al. (1990).  More moderate removal efficiencies, between 19.96% and 43.09% for ortho-phosphate, were observed for the planted wetlands. This lower treatment capacity is in part attributed to the ability of the plants (Typha) to release phosphorus back into solution in the fall. A higher removal capacity was observed in the spring and early summer for all three planted wetland designs followed by no net phosphorus removal or a net export observed in the fall (see charts in Appendix 2). This follows the life cycle of the wetland vegetation of nutrient uptake during the high growth stage in the spring, the more static stage during summer development of flowers into seeds and the release of nutrients from the above-ground biomass during the late fall senescence. The long-term biological removal of ortho-phosphate from wastewaters by wetlands occurs by the incorporation of recalcitrant portions of the biomass becoming buried in the sediments.  This process is limited due to the relatively low  composition of phosphorus in plant tissues (0.02 - 1.15%) (Boyd 1978; Vymazal 1995).  The calculated loading rates for total phosphorus were 1.49 g TP/m /d for the 15 cm deep SF 2  wetlands, 2.98 g TP/m /d for the 30 cm deep SF wetlands and 2.08 g TP/m /d for the SSF wetlands. 2  2  By comparing the mass loading rates of phosphate to each planted wetland it is possible to demonstrate that the mass loading order (the 30 cm SF wetlands received a higher mass loading than the SSF wetlands which in turn received a higher mass loading than the 15 cm SF wetlands) is the inverse of the treatment efficiency sequence (53.70% average reduction for the 15 cm SF wetlands, 50.68% average reduction for the planted SSF wetlands and 26.61% average reduction for the  47  planted 30 cm SF wetlands). This suggests that for the removal of phosphorus, design is not as important as the mass loading rate for vegetated wetland systems. As SSF wetlands are significantly more expensive to construct than SF wetlands due to the cost of the bed material, it would be preferable to utilize a SF design and reduce the mass loading via a high pH pre-treatment pond where possible.  As the provincial water quality guidelines provide a total phosphorus criteria of 10 ug/L it is unlikely that a constructed wetland system could meet this target concentration; however, conventional wastewater treatment plants are unable to meet a 10 (ig/L criteria without the addition of tertiary biological nutrient removal technology. The ability of wetland systems to produce an effluent with phosphate concentrations less than 0.5 mg/L has been effectively demonstrated by Martin and Johnson (1995). To provide treatment of greenhouse effluents that would yield a effluent phosphate concentration in the 0.1 mg/L total phosphorus range a two stage wetland system would be required. Using an unvegetated wetland basin to promote optimal precipitation reactions followed by a vegetated wetland incorporating a mass loading design strategy, a TP concentration of 0.1 mg/L is achievable.  5.2  N I T R A T E  The maximum allowable concentration of nitrate in drinking water has been set at 10 mg/L as NO3N, or 45 mg/L, as NO3 in both Water Quality Criteria: Approved and Working Criteria for Water Quality (MELP, 1994) and in Canadian Water Quality Guidelines (CCME, 1995). In cases where nitrite is also present, the combined concentration of nitrate plus nitrite cannot exceed the 10 mg/L guideline. Where concentrations of nitrate in drinking water is greater than 10 mg/L as nitrate as  48  nitrogen, there is an unacceptable risk of methemaglobin formation in infants'. For the protection of freshwater aquatic life, an average concentration of 40 mg/L nitrate (as nitrogen) with a maximum of 200 mg/L is allowable (MELP 1994).  In wetland systems, the removal of nitrate from wastewaters can occur via two mechanisms, uptake by the algae and emergent macrophytes present in the wetland or by denitrification. Of these two process it is the latter which is the most important. Plant uptake of nitrogen is limited by the annual biomass production the wetland is capable of generating. Biomass analysis of Typha latafolia has shown the plants to contain between 0.51% and 2.94% nitrogen by mass (Vymazal 1995). Using an annual average dry weight biomass production of 1,000 kg per hectare, a maximum of 294 kg of nitrogen per hectare could be accounted for by plant uptake. As Houweling Nurseries Ltd. has reported an average overdrain production of 3 L/m /day with an average nitrate concentration of 250 2  mg/L, the maximum vegetation nitrogen storage of 294 kg would be exceeded by a one hectare vegetable production greenhouse in 40 days.  Based on the rate of nitrate discharge from the  greenhouse and that nitrogen uptake by macrophytes occurs primarily in high plant growth periods (i.e. the spring), denitrification is the more significant mechanism for nitrate removal for the majority of the greenhouse production season. Table 7 below shows the results of nitrate analyses for the 1996 field season.  ' Methemoglobin or "blue baby disease" occurs when nitrate, absorbed by the infant through drinking water, is reduced to nitrite in the blood-stream. The nitrite binds with haemoglobin in the red blood cells and forms methemoglobin which is unable to bind 0 . As it is the 0 -haemoglobin complex that gives blood its red colour, the lower concentration of haemoglobin, and therefore reduced oxygen carrying capacity by the blood, results in the infant's skin gaining a bluish colour. Brain damage and/or death of infants are both a risk in areas with high nitrate concentrations in the drinking water. 2  2  49  Table 7. Nitrate Results (mg/L) Design  Average  Std Dev  Max  Min  % Reduction  Greenhouse Effluent  223.22  92.60  362.25  28.96  N/A  1  15cmSF#l  105.20  93.31  328.29  6.55  52.87%  2  15 cm SF #2  81.94  54.74  224.15  17.36  63.29%  3  30 cm SF #1  111.57  67.50  235.68  12.23  50.02%  4  30 cm SF #2  115.80  70.76  246.88  21.63  48.12%  5  Unplanted SF#1  204.47  113.36  445.42  42.51  8.40%  6  Unplanted SF #2  171.55  87.50  295.05  37.38  23.15%  7  Unplanted SSF#1  175.67  74.37  297.70  44.70  21.30%  8  Unplanted SSF #2  162.22  76.86  239.61  22.52  27.33%  9  SSF#1  167.05  85.46  307.57  23.39  25.17%  10  SSF #2  193.37  124.75  428.80  16.21  13.37%  Cell #  As seen in the results presented, a relatively low reduction in nitrate concentrations was observed in all of the SSF design wetlands and in the unplanted SF wetlands. Results of paired t-tests for these basins indicates that there is insufficient evidence to conclude that any real treatment effect was observed in either the unplanted SF wetlands or the planted SSF wetlands.  These results are  consistent with nitrate removal reported by Hardgrave and Hufton (1995) and is not unexpected as the rate of denitrification is primarily dependant on temperature, pH, redox potential and available biodegradable organic carbon. Of these, low levels of available biodegradable organic carbon and high dissolved oxygen levels, respectively, were the limiting factors for denitrification of the greenhouse wastewaters by the SSF and unplanted SF designs. While no dissolved oxygen data was collected from the unplanted SF basins, the low organic content of the greenhouse effluent, high photosynthetic activity of the algae, the shallow unprotected nature of the basins and the constants winds originating from the Strait of Georgia and Boundary Bay all imply an oxygen saturated or supersaturated state in the unplanted basins. The TOC concentration of the greenhouse overdrain was consistently in the 20 mg/L range compared to the year mean nitrate concentration of 217.75  50  mg/L.  Additionally, there was minimal input of organic carbon to the water column from the  broadleaf cattail or algae biomass in any of the SSF or unplanted SF systems. Narkis et al. (1979) have reported that 2.3 mg BOD is required to completely denitrify 1 mg NO3 in bench-scale 5  activated sludge systems.  Using this 2.3:1 ratio and the relationship between TOC and BOD , 5  derived from the scatter plot of TOC concentration versus BOD concentration (Figure 9) obtained 5  from 1996 field data, 621.5 mg of TOC is required to completely denitrify each litre of overdrain (assuming 300 mg/L nitrate). Figure 10 shows the change in TOC in as flow passed through each of the five wetland designs assessed in this study. No increase in TOC was observed in either of the unplanted basins and a minimal increase was observed in the planted SSF wetland design. Additionally, there was a high level of wind mixing of the unplanted 30 cm deep SF basins. The shallow nature of these basins in conjunction with the regular wind blowing off Boundary Bay ensured that these wetlands were well aerated. This in itself is sufficient to suppress any potential denitrification.  Figure 10. Change in Total Organic Carbon Through Each Wetland Design  51  In contrast, the planted 15 cm and 30 cm SF wetlands showed fairly good levels of nitrate removal and had supplemental sources of carbon available to the denitrifying bacteria. Carbon sources in each of these basins consisted of decaying cattail, algae and duckweed biomass as well as the 225 kg of wheat straw added in the spring of 1996 to supplement the existing carbon sources and simulate a more mature marsh litter layer.  Combined, these carbon sources effectively doubled the TOC  concentration in the wetland effluent for both the 15 cm and 30 cm deep designs, with respect to the greenhouse overdrain, yielding average TOC outlet concentrations of 42.19 mg/L and 37.40 mg/L for each design, respectively (Figure 9).  This observed increase is statistically supported by paired-  sample t-tests. As the 30 cm deep wetlands have twice the volume of the 15 cm deep basins, there was twice the TOC available for denitrification.  Based on the 10 day HRT, no real difference in between the outlet nitrate concentrations of two planted SF designs was observed. However, if the data is analyzed from a mass loading perspective, the 15 cm SF wetlands had an average 3.26 grams of NO3-N applied per square metre surface area per day (g/m /d) with removal rates of 1.55 g/m /d and 1.94 g/m /d for each of the two replicates. In 2  2  2  contrast, the 30 cm deep SF wetlands had nitrate application rates of 6.53 g/m /d with mean removal 2  rates of 3.02 g/m /d and 2.89 g/m /d for each of the replicates. This higher rate of denitrification may 2  2  be attributed to the combination of a number of factors such as: higher levels of available organic carbon for denitrification; deeper waters resulting in more anaerobic environments for denitrification to occur; and, the submergence of more plant biomass in a deeper marsh results in a higher surface area available for biofilm development.  These nitrate removal rates are significantly less than the mean removal rate of 5.3 g N/m /d reported 2  by van Oostrom et al. (1995). Two significant design differences existed between the wetlands  52  studied by van Oostrom and the wetlands studied here. In van Oostrom's study Glyceria maxima was the wetland vegetation chosen and the water depth was 40 cm. Additionally, the concentration of organic matter was significantly higher in the meat processing effluent than in the greenhouse effluent.  Given the deeper water depth there is greater opportunity for development of anaerobic  zones which are required for denitrification. The additional organic carbon provided by the Glyceria biomass and the BOD present in the effluent would also promote a higher rate of denitrification.  Nitrate application rates used in this study did not allow either drinking water standards or protection of aquatic life criteria to be met. However, using the results presented above and the implication from van Oostrom's study that a higher rate of denitrification is possible with a deeper water depth, it is postulated that a nitrate application rate of 3.0 g N/m /day and a design wetland depth between 30 2  cm and 40 cm in depth would produce an effluent that meets provincial water quality criteria.  5.3  AMMONIA  The toxicity of ammonia to freshwater aquatic life is dependant on concentration, pH and temperature with the latter two parameters affecting the concentration of the toxic un-ionized ammonia. Acceptable 30 day average ammonia levels range between 2.08 mg/L at pH 6.5 and 0 °C to 0.102 mg/L at pH 9.0 and 20 °C. In any given sampling period, not more than one in five of the collected samples can be more than 1.5 times the criteria for that temperature and pH (MELP 1994). No guidelines, either federal or provincial, are proposed to limit the concentration of ammonia in drinking water. Tables 8 and 9 below shows the average ammonia and nitrate outlet concentrations and treatment efficiencies for the ten wetlands between April and December 1996.  53  Table 8. Ammonia Results (mg/L) Design  A\ cragc  Std Dev  Max  Min  % Reduction  Greenhouse Effluent  17.88  17.44  46.38  0.90  N/A  1  15 cm SF #1  5.43  5.89  22.10  0.00  69.66%  2  15 cm SF #2  5.13  5.34  17.45  0.00  71.32%  3  30 cm SF#1  8.16  7.40  24.40  0.65  54.34%  4  30 cm SF #2  8.35  7.76  24.40  0.72  53.28%  5  Unplanted SF#1  5.78  6.96  20.73  0.00  67.68%  6  Unplanted SF #2  4.38  6.86  20.98  0.00  75.50%  7  Unplanted SSF#1  11.00  8.66  25.85  0.00  38.46%  8  Unplanted SSF #2  9.33  9.09  27.49  0.00  47.83%  9  SSF#1  9.16  8.72  31.37  0.72  48.79%  10  SSF #2  9.05  8.66  27.15  0.85  49.41%  Cell #  With the exception of Cell #7, the first unplanted SSF wetland, the reductions in ammonia observed in all of the wetland basins can be statistically defended with the paired-sample t-test. Based on the data presented in Table 8, the treatment order of the wetland designs for ammonia removal can be arranged, from most efficient to least efficient, as:  unplanted 30 cm SF > 15 cm SF > planted 30 cm SF > planted SSF = unplanted SSF.  This order closely follows the relative potential for diffusion of oxygen from the atmosphere into solution.  The 67.68% and 75.50% average reductions in ammonia observed in the two unplanted 30 cm SF wetlands represent the highest ammonia treatment effects observed over the course of the 1996 field season.  These reductions are attributed to a combination of nitrification, uptake by algae and  volatilisation. As the water in both basins was well aerated by wind mixing and had significant algal  54  growth present, the conditions for the conversion of ammonia to nitrate and volatilisation of the ammonia were ideal. Of the two wetlands, a higher reduction was observed in Cell #6. This higher level of treatment can be explained by the higher pH and algae population observed in this wetland. As discussed in Section 3.2.2, most plants, including algae, preferentially uptake ammonia over other forms of inorganic nitrogen form for metabolic purposes.  Additionally, ammonia stripping is  enhanced at pH values greater than 10, which was observed in the late summer and fall in Cell #6.  • Influent m Cell 5 14 A Cell 6 - 13 xCell 5 pH 12 x Cell 6 pH  Amminium and pH Over Time 50 45 40  11  35 30  •  25  X  • X  A  20 15 10 5  X  A  ft  X  •  X  X  X  • •  04-Jul  - 10 9  ~o X  -8 -7 -6  • :  • A  -A—A—A—A-  15-May  X X  Q  •  0 26- Mar  X  23-Aug  •  -5  • *  A—A—fl—A—A— A-fA12-Oct  01-Dec  4 20-Jan  Date, 1997  Figure 11. Change in Ammonium and pH Over Time.  The difference in ammonia treatment observed between the two planted surface flow wetland designs cannot be totally explained by the difference in loading rates. While the 30 cm SF wetlands did receive twice the ammonia loading as the 15 cm deep designs, the treatment effect observed through the 30 cm deep wetland is primarily observed in the first third of the wetland. A continuing decrease in ammonia concentration was observed through both of the shallower systems. This difference may  55  be explained by a higher concentration of available oxygen in the shallower system. As there is less water to oxygenate, diffusion of oxygen from the atmosphere and from the roots of the cattails provide a greater opportunity for nitrification in the shallow water environment.  The poor treatment of the SSF wetlands is likely due to the short circuiting of the greenhouse effluent under the root zone of the cattails. Traditionally, SSF wetlands with well developed root systems are very efficient in reducing the concentration of ammonia in the wastewater.  One significant  advantage these systems have is that they contribute less ammonia to the wastewater while it is passing through the wetland as the majority of the decaying biomass is located above the water level.  5.5  COST ANALYSIS  The construction cost analysis is based on the cost of materials as determined in the construction phase of this project. To provide a base for the comparison of system expenses, the analysis has been standardized for a 1,000 square metre wetland.  Construction costs and infrastructure costs are  presented separately as the latter would not change between designs.  The value of in-kind and  volunteer contributions to this project (i.e. design, construction supervision and manual labour) has been estimated based on estimates from suppliers and professional consulting fees.  Infrastructure costs are constant for both designs and assume that there are no complications with the location of the wetland and that there are no significant barriers to laying the pipe conveying the wastewater from the greenhouse to the wetland. Basic requirements for a treatment wetland include: one pump (horsepower and voltage requirements are site specific) ($ 1,000), one 20,000 L surge/storage tank ($ 2,250); 250 metres of 3 inch 0 poly pipe ($ 600); 60 metres of 150 mm 0 PVC  56  pipe ($ 700); and, miscellaneous poly and PVC elbows, couplings and t-joints ($ 250). The total infrastructure cost is $ 4,800. It should be noted that this is a fixed cost, regardless of wetland size, and would only increase if the wetland was located more than 200 metres away from the greenhouse. General labour associated with installing the infrastructure is represented in the construction costs.  Table 9. Wetland Construction Costs Item  Surface Flow Wetland  Subsurface Flow Wetland  Design and construction supervision @  $ 3,900  S 3,900  $ 1,150  $ 1,350  $935  $ 1,100  Labourers @ $ 16/hour  $705  $ 705  20-25 mm nominal diameter gravel  $ 5,300*  $ 16,000  $ 3,400  $ 3,400  $ 5,000  $ 5,000  Infrastructure  $ 4,800  $ 4,800  TOTAL  $24,995  $ 36,060  $75/hour Excavator @ $90/hour including $175 haul-in fee Bulldozer @ $75/hour including $125.00 haul-in fee  20 mil. PVC liner Wetland plants @ $1.25 each (4 per m  2  with 80% survival guarantee)  Note that gravel was used as the planting medium for this research project to reduce the number of variables potentially influencing the comparison of results; however, native top soil from the wetland site can be used thereby reducing the total construction costs for a 1,000 m SF wetland to $ 19,695. 2  6.0  CONCLUSIONS  The results presented in Section 5 indicate that no one specific design is "the most efficient" for all parameters concerned. Of the five designs tested, the surface flow design emerged as the most  57  appropriate design for the remediation of greenhouse wastewaters. The treatment capacity of all wetland designs tested were significantly exceeded for all nutrients analyzed. This does provide information on the maximum treatment capacity of the various designs. Reductions of 74% ammonia and 65% phosphate were achieved in the second unplanted SF wetland. Reductions of 54% and 45% nitrate-nitrogen were realized in the 15 cm planted SF and 30 cm planted SF wetlands, respectively. Based on the results of the research and data obtained from the literature, a multi-stage design, consisting of an unplanted pre-treatment basin followed by a 30 cm surface flow marsh with open water, is recommended for the combined removal of phosphate, nitrate and ammonium from greenhouse overdrain.  For the removal of phosphorus as either total phosphorus or phosphate, pre-treatment of the greenhouse overdrain will be required to reduce the concentration of phosphorus entering the treatment wetland to a level than can be realistically treated.  Due to the high concentration of  calcium in the greenhouse effluents, this can be accomplished by raising the pH in a settling basin and precipitating the phosphorus from solution as hydroxyapatite. If a pH of 8.5 to 9.0 is maintained within the basin, more than 90% of the phosphate can realistically be removed from solution before the overdrain enters the marsh component of the treatment wetland. The pH can be raised to this level naturally by promoting algal growth or artificially by raising the pH using caustic soda (NaOH) or another inexpensive base. Artificially raising the pH of the pre-treatment basin would create an environment that permits the establishment of the desired algal communities. As high pH conditions are commonly found in municipal wastewater treatment lagoons, it is not unlikely that an algal community which promotes a high pH environment will develop.  Nitrate removal is accomplished in the marsh component of the wetland utilizing the decaying plant and algal biomass as the carbon source for denitrification. Based on the results from the 15 cm SF  58  and 30 cm SF experimental wetlands from this study, nitrate concentration in the greenhouse overdrain can be reduced to acceptable levels for the protection of freshwater aquatic life (less then 40 ppm) using a loading rate of 1.65 g N03-N/m /day and a design water depth of 30 cm or greater. 2  As the pH of raw greenhouse wastewaters is at the low end of the pH range for denitrifying bacteria, an ancillary benefit to having a pre-treatment basin for lowering the phosphate concentration is the alkaline wastewaters entering the marsh portion of a treatment wetland provides a more favourable pH for denitrification.  The primary objective of this research project was assess the capability of constructed wetlands to reduce and remove the excess nutrients present in the overdrain generated by vegetable production greenhouses.  It was also an objective to use the results of this assessment to identify the most  efficient constructed wetland design for the treatment of vegetable greenhouse wastewaters. Based on the findings of this research, a treatment wetland could effectively remediate the wastewaters generated from vegetable production greenhouses.  However, given the extremely high  concentrations of nitrate and very low concentrations of organic carbon in the overdrain, a very large area of land, in the order of 0.5 hectare of wetland per hectare of greenhouse, would be required for the wetland itself to generate sufficient carbon to denitrify all of the nitrate. If producers can achieve greater control over water and nutrient wastes, appropriately designed natural treatment options, such as constructed wetlands, can provide the necessary level of remediation.  Recommendations for further research in this field include conducting an assessment of a multi-stage design and more detailed assessments of denitrification rates in the wetland. Collection of dissolved oxygen and oxidation-reduction potential data would allow for a more accurate estimate of denitrification rates and the development of more specific design criteria. The identification of a higher supply of organic carbon for denitrification is also a necessity. One potential source of carbon  59  for use as a supplement to improve denitrification is the plant biomass which is removed from the production areas at the end of each growing season. Composting this plant matter and using the end product may provide the necessary mass of carbon for complete denitrification without the area requirements suggested by the results of this research project.  60  7.0  BIBLIOGRAPHY  1. American Waste Water Association. Standard Methods for the Analysis of Water and Wastewater. 1995. 2. 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Adsorption Processes in Soil. In. The Handbook of Environmental Chemistry. Berlin: Springer-Verlag; 1980; pp. 47-61. 23. Jeter, R. M. and J. L. Ingraham. The Denitritrifying Prokaryotes. In. The Prokaryotes: A Handbook of Habits, Isolation and Identification of Bacteria. Volume I. Berlin: Springer-Verlag; 1981. 24. Johnston, Carol A. Sediment and Nutrient Retention by Freshwater Wetlands: Effects on Surface Water Quality. Critical Reviews in Environmental Control. 1991; 21(5,6):491565. 25. Kadlec, R. H. and R. L. Knight. Treatment Wetlands. Boca Raton, FL: Lewis Publishers; 1996; ISBN: 0-87371-930-1. 26. Khasawneh, F. E. and E. C. Doll. The Use of Phosphate Rock for Direct Application to Soils. Advances in Agronomy. 1978; 30:159-206. 27. Knight, R., J. Hilleke and S. Grayson. Design and performance of the Champion pilot-constructed wetland treatment system. Tappi. 1994 May; 77(5):240-245. 28 Maehlum, T. Treatment of landfill leachate in on-site lagoons and consructed wetlands. Water Science and Technology. 1994; 32(3): 129-136. 29. Martin, C. D. and K. D. Johnson. The use of extended aeration and in-series surfaceflow wetlands for treatment of landfill leachate. Water Science and Technology. 1995; 32(3): 119128. 30. Metcalf and Eddy, Inc. Wastewater Engineering: Treatment, Disposal and Reuse. 3rd Edition. Revised by G. Tchobanoglous and F.L. Burton. New York: McGraw-Hill, Inc.; 1991; ISBN: 0-07-041690-7.  62  31. Mosheri, G. A. ed. Constructed Wetlands for Water Quality Improvement. Boca Raton, Florida: Lewis Publishers; 1993; ISBN: 0-87371-550-0. 32. Narkis, N., Rebhun, M. and Sheindorf, C.H. Denitrification at Various Carbon to Nitrogen Ratios. Water Research 1979, 13(l):93-98. 33. Parfitt, R. L. Anion Adsorption by Soils and Soil Materials. Advances in Agronomy. 1978;30:1-49. 34. Perfler, R. and R. Haberl. Actual experiences with the use of reed bed systems for wastewater treatment in single households. 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Research Journal of the Water Pollution Control Federation. 1991; 63(7):934-941. 41. Soderlund, R. and T. Rosswall. The Nitrogen Cycles. In. The Handbook of Environmental Chemistry, Vol. 1, Part B. Berlin: Springer-Verlag; 1982; pp. 61-81. 42. USEPA. Design Manual: Constructed Wetlands and Aquatic Plant Systems for Municipal Wastewater Treatment. Cincinnati, OH: USEPA; 1988. 43.  USEPA. Manual: Nitrogen Control. Cincinnati, OH: USEPA; 1993.  44. van Oostrom, A. J. Nitrogen removal in constructed wetlands treating nitrified meat processing effluent. Water Science and Technology. 1995; 32(3): 137-148. 45. van Oostrom, A. J. and J. M. Russel. Denitrification in constructed wastewater wetlands receiving high concentrations of nitrite. Water Science and Technology. 1994; 29(4):7-14. 46. Vymazal, J. Algae and Element Cycling in Wetlands. Boca Raton, FL: Lewis Publishers; 1995; ISBN: 0-87371-899-2.  63  47. Watson, W. W., F. W. Valois and J. B. Waterbury. The Family Nitrobacteracae. In. The Prokaryotes: A Handbook of Habits, Isolation and Identification of Bacteria. Volume I. New York: Springer-Verlag; 1981; pp. 925-1022. 48. Wood, A. Constructed wetlands in water pollution control: Fundamentals to their understanding. Water Science and Technology. 1995; 32(3):21 -30. 49. Zehnder, A. J. B. The Carbon Cycle. In. The Handbook of Environmental Chemistry, Vol. 1, Part B. Berlin: Springer-Verlag; 1982; pp. 83-110.  64  APPENDIX 1. RAW DATA  65  T o t a l p h o s p h o r u s  ( m g / L ) 2 2 - A u g  0 5 - S e p  3 1 - O c t  6 1 . 6 8 6 3 . 4 0  6 7 . 3 7  1 7 . 7 6  2 8 . 2 4  7 1 . 6 2  8 . 1 4  X  X  5 4 . 8 9  3 1 . 7 6  1 4 . 2 3  3 9 . 2 1  1 4 . 0 6  1 0 . 7 0  1 0 . 3 2  1 1 6 . 7 1 8 8 . 6 6  7 1 . 0 1  5 1 . 8 9  2 0 . 5 6  1 5 . 2 6  3 0 . 8 7  1 1 . 8 0  6 . 3 2  9 . 3 5  6 1 . 9 0  3 6 . 9 2  1 9 . 4 0  1 2 . 8 9  3 1 . 3 5  1 3 . 1 3  8 . 8 5  X  7 . 8 0  1 3 1 . 1 1  7 3 . 8 4  4 0 . 8 5  1 5 . 3 4  1 1 . 4 5  2 8 . 8 6  8 . 8 9  5 . 2 7  X  5 . 2 4  X  1 1 5 . 3 3  7 8 . 7 5  4 9 . 2 3  1 7 . 1 4  1 2 . 4 6  2 9 . 4 2  1 0 . 3 2  5 . 7 5  X  5 . 4 8  X  1 1 3 . 2 0  6 2 . 1 8  4 0 . 3 2  1 0 . 9 6  2 1 . 8 1  3 1 . 1 8  1 4 . 1 9  1 0 . 6 2  6 . 4 0 8 . 0 0  2 7 - J u n  1 5 3 . 4 9  1 5 3 . 9 3  3 0 5 . 7 9  9 9 . 0 0  7 6 . 9 1  1 2 9 . 0 5  X  X  1 1 2 . 0 5  5 8 . 9 8  6 7 . 2 9  1 4 1 . 0 6  X  X  5 6 . 1 4  5 3 . 2 1  1 4 1 . 5 8  X  X  8 8 . 0 8  8 4 . 3 5  1 4 0 . 1 2  7 2 . 7 8  X  2 b  8 8 . 7 2  8 6 . 8 1  1 1 5 . 8 8  7 2 . 7 3  2 c  7 2 . 4 7  7 7 . 8 4  8 9 . 5 1  5 0 . 0 1  1 6 - M a y  g e  1 4 1 . 5 7  8 3 . 1 6  1 a  8 0 . 0 1  7 9 . 5 4  1 b  6 9 . 6 6  1 c  6 2 . 9 2  2 a  2 8 - N o v  1 7 - O c t  1 3 - J u n  0 2 - M a y  1 4 - N o v  1 9 - S e p  3 0 - M a y  2 5 - A p r  0 8 - A u g  X  1 2 - D e c  3 a  8 1 . 0 0  9 6 . 2 8  1 2 2 . 2 0  2 4 1 . 7 2  2 6 3 . 8 9  9 9 . 9 8  1 0 9 . 1 3  4 8 . 5 4  3 9 . 0 8  2 9 . 9 8  1 3 . 7 1  3 3 . 5 4  1 1 . 8 1  6 . 2 0  3 b  6 5 . 3 7  8 7 . 0 3  1 1 5 . 3 4  2 3 7 . 3 0  2 4 9 . 3 0  1 0 1 . 9 2  6 5 . 9 4  6 2 . 3 4  4 4 . 2 5  3 0 . 5 2  1 5 . 6 4  2 8 . 4 2  1 3 . 7 9  6 . 6 7  9 . 9 4  3 c  7 4 . 9 5  8 8 . 2 2  1 2 5 . 3 6  1 9 3 . 2 2  1 9 0 . 6 0  9 8 . 5 7  5 9 . 1 2  8 2 . 0 7  4 5 . 5 4  2 6 . 0 6  1 7 . 8 3  3 7 . 0 8  1 4 . 9 2  1 1 . 6 4  1 1 . 5 2  4 a  7 8 . 6 9  1 0 2 . 8 6  1 2 6 . 6 1  2 4 1 . 0 4  2 3 7 . 1 3  9 1 . 0 1  1 1 6 . 2 3  6 0 . 8 5  3 8 . 1 0  1 5 . 6 0  1 3 . 6 8  1 9 . 0 5  1 1 . 4 3  8 . 8 1  7 . 5 8  4 b  4 5 . 1 7  8 0 . 6 0  1 2 4 . 4 0  2 2 0 . 0 8  2 3 4 . 4 5  1 0 0 . 3 1  1 0 4 . 1 7  6 2 . 0 1  3 9 . 3 2  1 5 . 0 6  1 4 . 7 9  3 4 . 8 7  1 2 . 0 2  9 . 0 8  8 . 6 9  4 c  8 7 . 9 9  8 9 . 3 4  1 2 5 . 1 7  2 0 2 . 4 0  2 0 6 . 7 1  8 8 . 5 7  7 4 . 2 8  8 4 . 7 1  4 0 . 3 9  1 8 . 0 4  1 6 . 7 3  3 7 . 5 6  1 6 . 4 7  1 0 . 3 8  1 1 . 0 3 6 . 6 0  5 c  6 0 . 3 4  8 5 . 0 4  1 3 8 . 8 2  1 2 1 . 9 1  1 3 9 . 9 6  1 5 2 . 0 9  0 . 7 5  6 0 . 1 0  3 2 . 8 1  2 0 . 1 1  1 2 . 0 3  2 0 . 0 2  1 0 . 7 9  7 . 6 9  6 c  6 2 . 1 7  8 3 . 6 1  1 0 2 . 7 2  1 0 5 . 2 1  1 0 8 . 2 0  3 7 . 3 8  6 1 . 0 0  6 . 5 7  6 . 0 6  4 . 3 5  2 . 8 3  1 . 2 6  5 . 0 0  1 . 8 5  1 . 3 8  7 a  5 3 . 9 7  8 2 . 5 9  1 1 1 . 1 3  1 2 3 . 3 3  7 6 . 1 1  7 7 . 3 6  1 0 3 . 9 8  6 0 . 2 5  2 6 . 9 7  3 3 . 4 8  1 4 . 9 4  3 0 . 9 1  1 2 . 1 4  1 2 . 0 5  9 . 3 7  7 b  5 4 . 5 3  7 2 . 6 7  8 1 . 2 0  9 1 . 1 6  5 1 . 0 3  4 9 . 2 7  2 8 . 4 7  4 6 . 7 8  4 0 . 1 2  2 6 . 7 7  2 5 . 5 5  3 2 . 8 4  1 4 . 6 9  9 . 2 9  8 . 5 5  7 c  5 3 . 2 1  6 5 . 5 8  7 6 . 1 1  8 9 . 3 6  8 5 . 7 4  6 6 . 2 8  3 6 . 4 1  6 6 . 8 2  2 6 . 7 7  1 7 . 8 2  2 0 . 6 1  5 0 . 8 2  1 5 . 5 7  1 0 . 7 7  1 1 . 0 3  8 a  6 0 . 2 9  8 4 . 1 2  1 1 4 . 6 7  7 7 . 2 5  5 2 . 7 2  6 6 . 2 1  2 0 . 0 3  4 5 . 6 6  2 5 . 9 2  2 4 . 3 4  1 5 . 6 7  1 9 . 2 2  1 3 . 2 1  5 . 9 2  6 . 1 0  8 b  3 5 . 4 5  5 8 . 7 6  1 1 1 . 5 1  6 8 . 8 4  3 6 . 1 4  3 7 . 1 7  1 7 . 4 5  1 8 . 4 7  2 6 . 2 7  1 3 . 3 5  1 5 . 9 3  2 3 . 1 1  1 1 . 1 5  1 0 . 2 0  7 . 2 0  8 c  6 7 . 4 8  7 2 . 8 8  8 9 . 4 0  6 9 . 6 1  4 5 . 9 5  5 0 . 0 5  3 8 . 4 0  2 6 . 8 8  2 8 . 4 4  1 0 . 2 0  1 8 . 6 7  2 8 . 3 1  1 6 . 3 1  9 . 7 6  1 0 . 4 9  9 a  4 2 . 8 4  7 2 . 7 3  6 4 . 6 3  1 5 . 9 4  2 1 . 9 5  2 6 . 2 2  8 7 . 5 7  4 9 . 3 7  3 0 . 7 0  3 0 . 0 6  1 4 . 7 3  3 0 . 4 2  1 1 . 7 2  1 1 . 0 7  9 . 3 7  9 b  1 6 . 3 3  5 1 . 6 9  4 3 . 8 6  2 3 . 1 6  1 . 9 6  2 1 . 7 9  1 5 . 2 7  3 3 . 0 4  3 1 . 6 6  1 7 . 7 6  1 8 . 3 4  3 5 . 4 1  1 1 . 6 0  1 1 . 7 6  9 . 2 8  9 c  8 3 . 7 7  9 0 . 8 6  7 8 . 0 1  5 2 . 4 0  4 9 . 3 7  5 5 . 0 3  3 4 . 9 2  6 7 . 2 2  4 4 . 5 4  1 7 . 3 9  1 9 . 3 6  3 9 . 4 9  1 4 . 3 0  1 2 . 5 5  1 1 . 8 9  1 0 a  4 7 . 1 4  7 6 . 8 9  7 3 . 3 5  7 4 . 0 4  X  1 0 1 . 9 9  1 0 3 . 3 0  5 9 . 3 4  3 2 . 0 1  1 7 . 8 0  1 6 . 2 3  3 5 . 6 8  1 5 . 1 2  1 4 . 3 3  1 0 . 3 2  1 0 b  8 . 3 3  3 7 . 7 3  4 0 . 7 3  3 5 . 3 0  2 4 . 6 4  5 4 . 5 8  1 9 . 8 6  4 9 . 6 5  3 4 . 8 2  2 1 . 4 1  1 6 . 9 4  3 2 . 1 0  1 2 . 4 1  9 . 9 3  6 . 8 9  1 0 c  8 0 . 3 7  8 7 . 3 4  9 5 . 5 4  9 4 . 0 3  7 3 . 2 8  7 9 . 5 3  3 0 . 4 9  6 3 . 4 6  6 8 . 3 5  1 6 . 8 6  1 6 . 8 6  4 0 . 1 1  1 7 . 4 7  1 8 . 6 3  1 6 . 0 2  66  A m m o n i a  ( m g / L ) 1 2 - A p r  2 5 - A p r  0 2 - M a y  1 6 - M a y  3 0 - M a y  1 3 - J u n  2 7 - J u n  2 5 - J u l  0 8 - A u g  2 2 - A u g  0 5 - S e p  1 9 - S e p  g e  4 1 . 3 3  4 6 . 1 5  2 7 . 8 7  2 8 . 2 6  4 6 . 3 8  1 2 . 2 8  1 5 . 7 9  3 . 2 7  4 . 3 8  4 . 4 5  4 . 5 1  1 a  2 3 . 7 8  1 5 . 4 2  1 4 . 2 1  3 . 4 3  2 1 . 4 6  X  X  3 . 5 1  2 . 5 2  1 . 8 8  2 . 7 5  1 b  1 6 . 5 3  1 6 . 0 0  6 . 9 2  2 . 7 6  2 6 . 8 1  X  X  2 . 5 2  1 . 9 5  0 . 7 8  1 4 - N o v  2 8 - N o v  1 2 - D e c  0 3 - O c t  1 7 - O c t  3 1 - O c t  4 0 . 0 4  2 . 5 9  3 . 1 4  4 . 7 4  0.90  1 7 . 2 2  2 0 . 2 0  5 . 0 7  4 . 6 7  3 . 9 4  5 . 1 2  3 . 8 6  1 . 4 4  1 1 . 4 5  1 0 . 3 8  4 . 3 6  3 . 1 4  2 . 0 8  2 . 9 3  4 . 3 1  X  x  1 c  8 . 9 2  1 4 . 0 9  6 . 8 3  0 . 7 4  2 2 . 1 0  X  X  1 . 6 6  0 . 5 2  0 . 0 0  0 . 7 6  8 . 0 0  6 . 8 6  5 . 3 1  1 . 2 4  3 . 1 1  3 . 9 5  2 . 7 1  2 a  1 4 . 3 9  1 8 . 3 5  1 5 . 7 0  2 0 . 3 1  1 . 8 2  X  X  3 . 0 1  2 . 7 4  2 . 1 1  1 . 6 1  7 . 1 1  1 5 . 2 3  1 . 4 4  2 . 6 1  1 . 0 7  2 . 4 8  2 . 6 4  2 b  1 7 . 2 5  2 1 . 1 4  1 7 . 5 5  1 6 . 3 4  2 . 1 7  X  X  2 . 4 9  1 . 0 9  0 . 4 5  1 . 2 5  4 . 5 1  3 . 4 3  3 . 9 9  2 . 5 9  2 . 1 3  2 . 7 1  2 . 4 3  2 c  1 0 . 7 7  1 7 . 4 5  1 5 . 1 8  9 . 5 3  0 . 8 7  X  X  1 . 9 5  1 . 5 4  0 . 0 0  0 . 7 5  3 . 5 2  1 . 2 1  6 . 0 4  1 . 9 1  3 . 7 1  5 . 0 3  2 . 6 0  3 a  1 0 . 9 5  1 9 . 6 7  2 0 . 6 1  2 4 . 4 0  1 6 . 1 0  1 4 . 8 3  2 . 8 6  1 . 8 6  2 . 6 7  2 . 9 6  4 . 0 5  1 7 . 0 9  2 1 . 1 6  7 . 3 0  4 . 4 3  3 . 6 3  3 . 2 5  2 . 3 6  3 b  1 3 . 2 3  1 6 . 3 7  1 9 . 0 9  2 4 . 4 0  1 3 . 7 3  1 4 . 6 9  2 . 4 4  0 . 8 4  2 . 4 4  2 . 0 0  2 . 9 1  9 . 9 6  6 . 2 3  1 . 7 3  1 . 7 8  3 . 3 0  2 . 9 4  2 . 0 0  3 c  1 2 . 7 5  1 9 . 8 2  2 2 . 0 9  2 4 . 4 0  1 2 . 0 3  1 . 8 3  1 . 5 5  0 . 6 5  2 . 0 9  2 . 1 2  2 . 5 2  9 . 2 1  9 . 9 3  6 . 1 2  2 . 9 5  6 . 0 5  6 . 3 2  4 . 5 5  4 a  1 1 . 7 8  1 8 . 8 1  2 0 . 5 2  2 2 . 0 4  9 . 9 2  1 1 . 8 7  1 . 9 3  1 . 8 0  1 . 8 0  1 . 9 0  1 . 0 5  1 0 . 1 5  6 . 0 9  3 . 2 6  4 . 9 6  2 . 8 9  4 . 9 4  2 . 5 7  4 b  1 6 . 5 3  1 0 . 4 2  1 6 . 5 4  2 4 . 4 0  8 . 4 9  7 . 6 7  1 . 8 6  1 . 3 3  2 . 1 5  1 . 5 6  0 . 8 7  4 . 8 5  4 . 3 3  4 . 2 9  2 . 4 9  4 . 6 3  4 . 6 0  2 . 9 3  4 c  1 2 . 9 3  1 9 . 8 2  2 4 . 0 8  2 4 . 4 0  1 2 . 3 1  3 . 6 2  0 . 7 2  0 . 7 3  1 . 6 2  0 . 7 2  2 . 2 5  1 1 . 2 7  2 . 8 2  9 . 7 7  4 . 5 8  7 . 5 1  6 . 2 0  5 . 0 1  5 c  1 7 . 9 8  1 1 . 5 3  1 5 . 4 9  2 0 . 7 3  1 1 . 0 3  8 . 6 6  0 . 1 2  0 . 0 0  0 . 0 0  1 . 6 9  2 . 2 2  6 . 9 1  6 . 7 4  0 . 0 0  0 . 2 3  0 . 4 9  0 . 1 9  0 . 0 0  6 c  1 7 . 5 7  8 . 6 9  1 1 . 6 0  2 0 . 9 8  1 3 . 2 3  2 . 0 1  0 . 0 6  0 . 0 0  0 . 0 0  0 . 0 3  0 . 4 8  2 . 3 4  0 . 9 5  0 . 0 4  0 . 4 2  0 . 0 0  0 . 3 9  0 . 0 6  7 a  1 4 . 4 2  9 . 2 4  1 3 . 9 3  2 4 . 4 0  2 7 . 0 9  2 4 . 3 7  2 7 . 3 2  2 . 0 9  0 . 0 0  2 . 6 6  2 . 5 2  1 6 . 8 9  1 2 . 9 5  8 . 8 1  1 . 1 1  3 . 1 9  4 . 3 7  0 . 0 3  7 b  1 4 . 2 7  7 . 4 7  1 1 . 8 4  2 2 . 9 3  2 0 . 9 5  1 2 . 5 3  1 1 . 1 4  1 . 6 6  0 . 0 0  1 . 1 8  2 . 2 0  1 1 . 1 9  1 4 . 5 0  1 7 . 0 8  2 . 5 0  1 . 5 3  3 . 3 7  0 . 5 7  7 c  2 5 . 8 5  9 . 0 1  1 0 . 7 6  2 0 . 9 5  1 9 . 7 2  2 1 . 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7  2 1 . 4 2  2 1 . 0 6  1 5 . 5 2  4 . 8 3  8 . 4 6  1 0 . 2 6  2 . 0 3  0 . 7 2  2 . 2 7  2 . 1 2  1 2 . 8 1  1 4 . 3 3  8 . 0 9  3 . 4 5  2 . 1 0  2 . 3 4  1 . 6 2  1 0 a  1 3 . 9 9  7 . 3 3  1 0 . 3 1  7 . 7 0  8 . 7 8  1 0 . 6 6  1 5 . 5 1  2 . 1 0  1 . 1 9  3 . 0 4  3 . 1 4  1 4 . 3 3  1 1 . 8 4  3 . 9 8  2 . 5 6  1 . 6 0  3 . 7 5  1 . 9 1  1 0 b  8 . 7 2  0 . 2 9  6 . 4 8  1 . 2 9  2 . 0 1  2 . 2 5  1 1 . 9 2  3 . 1 4  1 . 4 6  2 . 0 1  1 . 1 3  1 1 . 1 0  6 . 1 2  5 . 7 5  2 . 5 4  0 . 8 3  3 . 0 6  1 . 3 1  1 0 c  2 7 . 1 5  2 0 . 5 4  1 9 . 8 1  1 6 . 4 6  1 8 . 1 4  1 2 . 1 2  1 8 . 6 6  0 . 8 5  1 . 2 3  2 . 2 4  3 . 0 1  2 . 1 6  2 . 9 0  5 . 7 3  4 . 0 7  3 . 1 6  3 . 2 9  1 . 3 0  67  N i t r a t e - n i t r o g e n (mg/L) 0 3 - O c t  1 7 - O c t  3 1 - O c t  1 4 - N o v  2 5 1 . 3 3  6 6 . 4 5  2 0 9 . 7 4  1 6 8 . 0 7  2 8 . 9 6  X  1 8 8 . 1 5  1 7 9 . 0 6  7 6 . 3 1  6 5 . 7 8  6 6 . 8 7  3 0 . 6 1  2 1 9 . 7 9  1 2 2 . 0 2  1 7 2 . 3 2  8 6 . 1 6  2 6 . 6 7  2 0 . 4 9  9 . 1 4  0 . 3 2  1 9 7 . 7 4  1 8 8 . 5 5  1 0 5 . 6 6  1 1 9 . 7 4  8 6 . 9 1  3 5 . 9 1  4 8 . 7 7  2 5 . 6 0  6 . 5 5  2 3 9 . 9 9  2 2 9 . 5 5  3 2 7 . 8 8  9 4 . 0 0  1 8 6 . 4 7  5 5 . 2 3  4 6 . 8 7  1 0 . 1 1  5 . 4 5  1 6 . 5 4  2 4 8 . 1 5  1 6 5 . 3 7  1 8 5 . 6 3  5 9 . 6 5  8 0 . 3 4  6 0 . 1 8  4 0 . 3 3  2 4 . 6 2  6 . 8 4  9 . 2 0  2 2 4 . 1 5  1 4 5 . 8 9  1 3 4 . 8 4  5 0 . 1 9  3 5 . 4 3  8 1 . 2 0  4 9 . 8 5  5 6 . 7 2  4 5 . 3 5  1 7 . 3 6  1 9 8 . 0 9  2 2 0 . 9 7  1 8 6 . 0 3  3 0 1 . 5 1  1 3 4 . 9 9  1 8 1 . 2 7  9 3 . 6 6  4 6 . 4 2  3 8 . 7 7  4 . 1 6  1 0 . 0 6  1 3 5 . 8 0  1 6 2 . 0 6  1 4 3 . 5 1  2 4 9 . 7 7  1 7 2 . 0 8  9 8 . 0 6  3 4 . 9 8  7 . 2 6  2 2 . 0 3  6 . 5 6  1 5 . 1 6  1 0 8 . 9 6  1 2 1 . 0 6  1 4 5 . 7 8  1 9 2 . 0 0  2 3 2 . 5 3  1 0 3 . 9 6  1 2 4 . 3 8  7 9 . 7 3  1 2 . 2 3  7 1 . 2 2  1 7 . 5 5  1 3 . 9 3  2 0 9 . 4 0  1 4 3 . 6 0  1 5 6 . 3 7  2 2 9 . 2 3  1 8 2 . 1 6  3 2 4 . 5 1  1 6 3 . 4 8  1 0 9 . 9 8  8 3 . 4 5  6 3 . 5 3  3 1 . 9 8  2 5 . 2 5  9 . 1 5  1 5 3 . 6 0  1 1 3 . 6 4  1 4 4 . 6 0  2 1 9 . 4 9  1 7 6 . 0 1  2 5 4 . 0 0  1 1 3 . 6 2  1 6 0 . 6 3  4 5 . 6 6  7 . 6 6  4 0 . 4 9  9 . 8 6  1 3 . 3 2  1 1 5 . 7 4  1 7 1 . 9 4  2 0 0 . 7 2  2 4 6 . 8 8  8 6 . 1 0  6 7 . 3 3  5 7 . 3 2  2 5 . 3 3  1 0 7 . 0 3  2 7 . 3 2  2 1 . 6 3  2 9 7 . 7 0  3 2 7 . 0 7  2 7 8 . 6 8  4 4 5 . 4 2  2 3 2 . 7 2  2 4 3 . 3 5  1 4 4 . 1 2  1 0 6 . 1 3  8 2 . 9 7  6 1 . 6 1  4 2 . 5 1  2 8 0 . 6 7  2 4 1 . 0 8  2 3 1 . 5 6  2 9 5 . 0 5  1 8 2 . 8 3  2 1 4 . 0 0  1 0 9 . 4 3  7 5 . 3 1  6 6 . 9 7  5 9 . 8 3  3 7 . 3 8  2 7 9 . 9 5  2 4 9 . 6 8  1 3 8 . 0 0  3 6 8 . 7 9  1 7 5 . 3 1  1 7 9 . 1 0  1 0 3 . 1 6  1 4 . 1 6  3 7 . 2 5  7 5 . 5 9  2 5 . 4 0  7 7 . 3 5  1 5 0 . 8 0  2 2 9 . 1 3  1 7 3 . 5 6  2 8 9 . 8 8  1 1 4 . 0 2  1 7 8 . 5 5  1 4 5 . 8 1  1 5 . 6 7  1 7 . 7 3  6 3 . 3 8  2 7 . 7 3  2 1 0 . 5 4  2 4 6 . 9 2  2 9 7 . 7 0  2 0 5 . 9 7  2 7 1 . 6 2  2 4 0 . 7 9  1 6 9 . 5 2  2 0 4 . 3 6  1 2 3 . 4 0  9 7 . 4 2  4 4 . 7 0  1 3 8 . 2 6  5 7 . 7 8  2 5 5 . 6 6  1 1 4 . 1 5  1 1 1 . 0 7  2 2 6 . 0 0  2 6 1 . 7 6  1 3 7 . 7 2  2 9 4 . 5 0  1 7 9 . 9 7  2 0 1 . 5 8  1 0 9 . 7 1  2 4 . 9 8  2 2 . 9 8  3 4 . 1 8  1 4 . 2 0  1 4 0 . 3 3  2 3 8 . 1 7  1 2 4 . 5 3  1 3 2 . 0 9  1 8 6 . 5 9  2 0 6 . 1 6  1 5 2 . 1 3  3 4 4 . 1 7  1 5 1 . 7 4  1 3 5 . 3 7  6 2 . 3 9  3 4 . 1 2  7 . 0 4  3 2 . 5 6  1 3 . 0 9  1 7 0 . 8 0  1 9 1 . 6 0  2 2 2 . 1 7  2 1 6 . 5 0  1 8 7 . 5 2  2 2 2 . 4 1  2 3 9 . 6 1  2 3 5 . 4 9  2 3 6 . 9 3  1 9 3 . 3 4  2 2 3 . 0 3  1 0 1 . 0 8  7 3 . 8 4  5 6 . 7 4  2 2 . 5 2  2 6 . 7 2  6 8 . 1 2  3 0 . 3 0  1 2 7 . 8 1  1 0 1 . 7 0  7 8 . 7 2  1 1 6 . 2 2  2 0 7 . 2 8  2 4 4 . 3 0  1 7 2 . 7 9  2 9 2 . 9 8  1 7 6 . 5 0  2 1 9 . 0 8  1 0 1 . 2 4  3 5 . 4 3  2 6 . 5 2  1 3 . 3 1  1 . 1 6  4 3 . 6 5  2 7 . 6 2  8 2 . 5 2  5 6 . 2 2  3 5 . 6 6  5 3 . 9 7  1 0 9 . 5 4  2 8 5 . 3 7  1 4 6 . 4 5  1 9 5 . 4 5  1 7 9 . 8 0  1 9 1 . 1 9  1 0 4 . 4 4  4 5 . 8 4  3 6 . 4 8  1 8 . 2 9  1 . 4 9  2 2 - A u g  1 9 - S e p  2 3 0 . 1 2  3 6 2 . 2 5  2 8 7 . 4 2  2 5 1 . 6 1  2 3 7 . 0 0  1 9 1 . 8 2  X  2 4 0 . 5 0  X  X  X  X  X  X  1 2 - A p r  2 5 - A p r  0 2 - M a y  1 6 - M a y  3 0 - M a y  1 3 - J u n  2 7 - J u n  g e  2 0 6 . 6 6  2 1 9 . 1 0  1 9 4 . 1 9  3 1 4 . 7 1  2 6 8 . 6 4  3 3 3 . 8 0  1 7 8 . 5 2  1 a  1 1 8 . 9 1  1 2 1 . 1 6  1 0 6 . 5 4  3 8 . 2 3  3 4 0 . 8 3  X  X  1 b  8 2 . 6 5  8 0 . 6 6  6 3 . 5 8  3 0 . 5 7  2 9 0 . 1 2  X  X  1 c  4 4 . 6 1  6 9 . 4 4  5 0 . 6 4  2 9 . 1 0  3 2 8 . 2 9  X  2 a  7 1 . 9 7  1 4 2 . 5 6  1 6 4 . 7 2  1 7 5 . 7 4  6 3 . 9 7  2 b  8 6 . 2 4  1 2 2 . 7 8  1 4 1 . 2 1  1 3 0 . 4 2  5 3 . 1 3  2 c  5 3 . 8 6  8 9 . 9 5  1 1 4 . 8 9  9 5 . 9 6  3 3 . 4 6  3 a  5 4 . 7 3  1 1 1 . 6 3  1 6 4 . 1 2  2 5 3 . 3 6  2 2 9 . 2 6  1 7 5 . 0 6  3 b  6 6 . 1 7  7 5 . 7 4  1 3 1 . 5 4  2 2 9 . 8 6  1 6 3 . 2 6  1 3 7 . 9 4  3 c  6 3 . 7 6  9 6 . 3 5  1 4 2 . 3 5  2 3 5 . 6 8  1 3 5 . 2 9  4 a  5 8 . 9 2  9 6 . 9 9  1 8 4 . 7 2  2 7 9 . 7 7  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. 2 6  1 8 4 . 1 3  2 8 0 . 8 3  2 5 7 . 6 0  2 3 8 . 4 0  1 0 1 . 5 8  3 3 . 2 3  2 . 5 4  2 . 1 7  0 . 2 9  1 0 b  4 3 . 6 2  2 7 . 6 2  5 9 . 2 3  3 0 . 2 2  4 4 . 6 6  7 9 . 9 8  2 1 1 . 6 2  3 1 3 . 9 0  1 8 6 . 9 3  1 9 4 . 2 9  3 1 5 . 8 9  1 8 6 . 8 9  8 9 . 7 3  2 3 . 0 0  1 . 9 2  1 . 3 7  0 . 0 2  1 0 c  1 3 5 . 7 7  3 8 . 0 9  1 8 0 . 7 4  1 9 2 . 1 6  3 0 4 . 8 9  2 0 4 . 8 4  2 7 3 . 1 8  4 2 8 . 8 0  3 5 0 . 1 9  3 9 8 . 1 1  2 3 9 . 1 5  1 6 4 . 3 8  1 1 4 . 8 7  1 0 5 . 4 3  1 0 1 . 6 9  3 8 . 7 6  1 6 . 2 1  68  T o t a l O r g a n i c  C a r b o n 1 2 - A p r  ( m g / L ) 2 5 - A p r  0 2 - M a y  1 6 - M a y  3 0 - M a y  1 3 - J u n  2 7 - J u n  2 5 - J u l  0 8 - A u g  2 2 - A u g  0 5 - S e p  1 9 - S e p  0 3 - O c t  1 7 - O c t  X  3 1 - O c t  1 4 - N o v  2 8 - N o v  1 2 - D e c  3 . 7 8 6  3 . 5 0 2  0 . 5 8  0 . 7 8  1 . 6 9  1 . 4 6  1 . 8 0  1 . 1 6  1 . 0 7  2 . 0 8  1 . 8 5  1 . 5 9  2 . 2 5 6  2 . 6 0 2  6 . 2 2  3 . 1 6 5  3 . 2 9 8  g e  3 2 . 2 4  1 3 . 8 3  1 5 . 0 6  2 6 . 0 5  1 5 . 0 7  2 7 . 6 0  1 3 . 7 7  2 0 . 1 3  9 . 8 4  1 0 . 2 1  1 8 . 2 4  1 9 . 7 9  3 2 . 1 4  4 2 . 4 8  1 8 . 7 5  8 . 3 9  1 a  6 7 . 2 7  4 6 . 1 1  4 7 . 4 1  6 7 . 0 5  2 1 . 2 7  X  X  3 5 . 5 9  3 5 . 7 5  3 5 . 1 5  3 8 . 2 5  3 6 . 1 6  5 6 . 3 6  2 1 . 5 5  3 4 . 8 3  2 3 . 5 2  3 4 . 9 0  1 b  6 0 . 3 3  3 6 . 0 6  5 1 . 3 7  6 8 . 6 3  2 1 . 5 8  X  X  3 2 . 9 0  4 4 . 8 7  4 1 . 6 5  5 1 . 0 0  4 9 . 0 4  3 6 . 5 6  2 2 . 8 3  4 4 . 8 7  3 5 . 2 3  2 5 . 1 8  5 0 . 7 2  1 c  7 3 . 3 8  3 7 . 8 5  4 9 . 9 9  6 6 . 4 3  2 3 . 5 2  X  X  4 6 . 0 5  4 4 . 9 5  5 1 . 4 5  3 8 . 4 6  4 6 . 5 0  2 9 . 0 5  2 7 . 2 0  3 1 . 0 7  2 5 . 0 5  2 5 . 1 4  2 8 . 8 2  2 a  6 7 . 8 2  4 3 . 9 7  3 7 . 7 2  4 3 . 0 5  5 0 . 4 0  X  X  3 7 . 1 9  4 0 . 7 7  3 2 . 6 1  4 6 . 3 0  6 2 . 2 4  3 0 . 0 0  3 6 . 8 2  3 7 . 4 1  4 4 . 7 5  2 3 . 7 9  2 7 . 8 5  2 b  6 7 . 6 2  3 9 . 3 7  3 9 . 4 6  4 3 . 0 0  5 3 . 8 3  X  X  4 5 . 6 6  4 0 . 4 5  4 6 . 1 8  5 5 . 5 0  5 6 . 9 5  3 7 . 4 0  3 8 . 8 0  2 8 . 3 0  3 5 . 9 2  2 3 . 2 3  2 6 . 4 5  2 c  6 5 . 7 7  3 7 . 6 6  3 8 . 4 4  4 5 . 8 3  5 7 . 0 1  X  X  5 8 . 1 3  4 3 . 4 9  4 8 . 7 3  5 5 . 3 5  5 7 . 5 0  3 8 . 1 5  2 9 . 3 4  2 9 . 0 5  2 6 . 3 2  1 9 . 8 0  2 5 . 9 8  3 a  5 5 . 7 9  3 6 . 0 4  3 8 . 2 3  3 5 . 0 8  4 0 . 9 5  4 6 . 7 2  4 3 . 8 1  3 1 . 1 5  3 5 . 0 1  2 0 . 7 4  2 4 . 1 1  3 0 . 9 2  2 1 . 9 2  2 0 . 3 6  2 8 . 1 3  2 5 . 6 1  1 6 . 7 7  1 8 . 2 6  3 b  5 7 . 1 9  3 9 . 4 8  4 4 . 2 7  3 6 . 2 7  4 5 . 2 5  4 8 . 0 7  4 5 . 7 1  4 2 , 6 6  4 3 . 6 7  2 3 . 6 0  2 4 . 4 1  3 0 . 6 0  3 2 . 6 4  3 1 . 5 6  3 3 . 7 8  3 8 . 1 9  1 8 . 7 6  1 8 . 9 0  3 c  5 4 . 5 6  3 7 . 7 7  2 7 . 6 6  3 9 . 4 1  4 0 . 1 3  4 5 . 3 5  4 7 . 4 3  4 6 . 0 5  3 3 . 6 8  2 4 . 6 6  3 1 . 2 3  3 7 . 2 2  2 6 . 0 3  2 2 . 8 4  4 0 . 2 0  2 1 . 9 5  2 4 . 7 7  2 5 . 1 1  4 a  5 7 . 4 2  3 9 . 8 4  4 6 . 8 1  4 1 . 6 3  4 3 . 3 8  7 1 . 4 1  4 5 . 8 7  2 6 . 5 3  3 2 . 5 0  1 7 . 9 3  4 5 . 2 0  4 1 . 2 0  4 0 . 4 5  2 8 . 7 0  4 4 . 9 5  1 9 . 9 1  1 6 . 3 5  1 9 . 8 3  4 b  5 6 . 8 7  3 6 . 3 2  4 1 . 7 1  4 1 . 6 3  5 6 . 8 3  7 2 . 3 3  5 2 . 1 3  3 2 . 3 7  5 0 . 0 0  2 6 . 1 6  4 1 . 5 5  4 1 . 5 5  3 4 . 6 5  4 9 . 0 5  3 8 . 8 8  2 7 . 3 4  1 7 . 5 6  1 8 . 5 7  4 c  5 3 . 1 2  3 8 . 8 5  4 1 . 4 7  3 9 . 7 6  4 7 . 4 3  5 5 . 2 1  5 0 . 6 3  4 4 . 0 5  3 2 . 3 4  2 5 . 6 8  4 5 . 3 0  5 1 . 0 5  4 2 . 9 0  4 6 . 2 5  5 6 . 8 5  1 7 . 5 0  2 3 . 1 5  2 2 . 9 5  5 c  2 7 . 2 1  2 5 . 4 1  3 2 . 4 6  2 3 . 9 1  2 3 . 1 9  3 0 . 0 1  3 0 . 4 1  1 9 . 5 3  1 7 . 2 8  1 4 . 6 7  1 1 . 1 8  1 9 . 1 6  2 1 . 4 0  1 5 . 9 0  1 0 . 9 2  1 1 . 4 7  9 . 7 9  9 . 2 7  6 c  3 6 . 2 4  2 1 . 8 6  2 2 . 7 3  2 2 . 1 1  1 9 . 5 0  2 8 . 3 7  1 9 . 8 8  9 . 8 7  1 5 . 4 4  7 . 0 7  7 : 1 1  2 0 . 8 1  1 5 . 4 2  2 4 . 7 3  2 8 . 2 7  2 1 . 4 7  8 . 2 0  1 1 . 8 6  7 a  2 6 . 2 9  1 5 . 0 8  2 7 . 6 9  2 4 . 8 7  1 9 . 5 7  2 4 . 0 3  3 1 . 2 3  2 0 . 3 3  2 7 . 4 5  1 0 . 9 8  1 2 . 9 0  2 2 . 0 7  1 5 . 2 1  1 1 . 2 6  7 . 0 7  1 1 . 4 2  5 . 4 3  5 . 4 2  7 b  2 1 . 9 8  1 4 . 3 9  2 0 . 1 5  2 6 . 4 9  2 3 . 7 8  3 3 . 5 4  3 6 . 0 6  3 5 . 7 7  2 6 . 7 2  1 6 . 1 0  1 4 . 5 5  1 7 . 5 2  1 6 . 2 8  1 2 . 2 4  9 . 9 2  1 1 . 7 7  9 . 3 5  7 . 5 3  7 c  1 8 . 7 0  1 7 . 8 5  1 6 . 5 6  2 1 . 2 0  2 2 . 3 3  2 4 . 1 6  2 4 . 2 5  3 1 . 9 4  2 0 . 8 5  2 4 . 3 0  1 3 . 4 7  1 2 . 8 2  1 2 . 8 1  1 0 . 6 2  1 0 . 1 5  9 . 9 9  5 . 9 0  5 . 2 0  8 a  2 5 . 4 4  2 6 . 1 2  2 5 . 6 9  2 1 . 0 4  2 2 . 0 7  2 1 . 7 3  2 4 . 5 8  3 2 . 1 2  2 0 . 3 5  1 4 . 2 6  1 4 . 9 2  1 6 . 8 4  1 5 . 9 9  5 . 7 9  2 4 . 4 8  2 1 . 8 0  2 3 . 3 4  1 3 . 9 8  d H 2 0  X  X 3 5 . 2 6  8 b  9 . 4 6  1 2 . 6 3  2 1 . 6 0  2 1 . 8 4  2 0 . 2 1  1 9 . 0 0  1 8 . 8 0  3 2 . 4 8  3 3 . 8 0  1 7 . 2 0  1 6 . 0 9  1 4 . 3 4  1 5 . 9 7  7 . 7 2  6 . 8 4  1 3 . 2 4  9 . 9 9  8 c  1 8 . 5 4  2 4 . 4 9  2 1 . 0 4  2 3 . 9 5  1 9 . 4 0  1 9 . 6 8  2 4 . 4 6  2 6 . 0 4  3 0 . 3 4  2 4 . 3 5  1 8 . 6 6  1 3 . 4 0  1 3 . 1 4  1 0 . 1 2  9 . 1 9  1 2 . 6 4  7 . 3 7  9 a  1 8 . 0 6  1 8 . 4 3  2 2 . 1 3  1 9 . 3 1  1 8 . 2 1  1 7 . 3 7  1 9 . 2 3  2 5 . 9 5  2 4 . 2 7  1 1 . 8 3  1 3 . 4 5  2 0 . 5 2  1 4 . 7 4  1 3 . 3 4  3 1 . 2 4  1 9 . 5 2  2 4 . 5 8  2 8 . 8 4  9 b  1 5 . 1 1  1 4 . 7 0  1 9 . 8 7  1 6 . 0 3  1 7 . 1 4  1 5 . 1 1  3 3 . 5 3  3 6 . 6 2  3 5 . 9 0  2 2 . 8 8  1 3 . 4 2  1 8 . 7 7  2 0 . 5 2  1 4 . 0 1  2 2 . 9 3  2 0 . 1 9  2 5 . 1 4  2 8 . 3 6  9 c  2 0 . 8 0  2 7 . 4 0  3 1 . 5 8  2 5 . 5 8  1 5 . 8 5  2 0 . 1 0  2 4 . 1 5  2 9 . 6 8  2 5 . 8 2  1 8 . 0 9  1 3 . 9 3  1 7 . 0 5  1 6 . 6 0  1 9 . 1 6  1 0 . 4 3  1 2 . 2 3  1 5 . 0 7  1 6 . 2 8  1 0 a  1 7 . 4 6  1 7 . 6 8  2 1 . 9 4  1 8 . 2 4  1 7 . 7 5  1 6 . 4 9  2 0 . 0 4  2 3 . 9 8  2 5 . 4 7  1 3 . 9 9  1 9 . 0 8  2 9 . 4 8  2 2 . 1 4  1 6 . 6 0  3 8 . 7 2  6 0 . 0 3  6 0 . 4 5  3 3 . 7 6  6 . 4 3 ,  7 . 0 0  1 0 b  1 4 . 0 3  1 1 . 8 4  1 3 . 7 4  1 4 . 5 0  2 1 . 0 3  1 4 . 1 4  2 0 . 5 2  3 5 . 8 8  3 3 . 7 1  2 3 . 3 4  2 9 . 7 4  3 5 . 6 2  3 4 . 8 8  2 2 . 8 3  3 3 . 7 0  3 8 . 8 8  3 8 . 1 4  2 6 . 4 6  1 0 c  2 1 . 5 5  2 7 . 7 7  1 9 . 9 2  2 0 . 5 6  2 3 . 3 5  1 8 . 7 9  2 6 . 2 7  3 9 . 5 1  3 0 . 3 3  2 6 . 0 1  2 2 . 7 0  3 1 . 3 7  1 9 . 6 6  2 1 . 2 0  1 2 . 7 3  1 3 . 8 8  2 8 . 9 5  3 8 . 9 4  69  B 0 D 5  ( m g / L ) 0 3 - M a y  1 7 - M a y  3 0 - M a y  1 3 - J u n  2 5 - J u l  0 8 - A u g  2 2 - A u g  0 5 - S e p  g e  4 . 8 2  6 . 3 7  2 . 1 7  X  5 . 2 5  1 . 4 3  8 . 5 6  7 . 7 9  1 a  1 8 . 5 3  4 3 . 6 6  7 . 7 2  X  2 7 . 4 8  3 3 . 1 4  3 7 . 1 9  2 5 . 5 0  1 b  1 9 . 2 8  2 7 . 8 0  8 . 0 4  X  1 4 . 8 4  3 1 . 4 4  2 6 . 2 8  1 5 . 8 8  1 c  1 8 . 1 2  4 2 . 0 6  6 . 2 0  X  1 7 . 1 4  8 . 2 2  0 . 9 0  9 . 8 1  2 a  1 2 . 5 3  2 8 . 2 4  7 . 6 8  X  1 5 . 3 0  2 9 . 1 2  2 0 . 9 4  2 2 . 6 2  2 b  1 4 . 2 9  2 0 . 4 6  1 9 . 8 6  X  1 7 . 2 4  2 4 . 0 4  2 6 . 8 8  2 2 . 0 8  2 c  1 4 . 7 5  2 9 . 2 9  1 0 . 4 2  X  2 2 . 4 8  2 3 . 4 0  9 . 9 2  1 2 . 1 1  3 a  8 . 9 5  1 9 . 6 3  1 0 . 2 7  3 0 . 6 2  1 6 . 2 3  2 5 . 8 5  3 5 . 9 7  1 9 . 1 6  3 b  9 . 8 3  1 . 3 2  1 9 . 3 5  2 6 . 6 4  1 3 . 6 6  2 3 . 2 5  4 . 3 0  8 . 3 1  3 c  9 . 1 1  2 . 8 1  4 . 8 6  1 2 . 8 9  2 4 . 3 7  4 . 9 0  2 2 . 3 2  4 a  1 6 . 3 5  3 9 . 4 6  1 1 . 4 4  2 5 . 5 9  2 3 . 1 3  2 6 . 7 3  1 4 . 4 6  3 5 . 3 2  4 b  1 4 . 2 9  3 . 5 5  1 8 . 7 6  2 7 . 6 2  1 2 . 7 7  2 6 . 9 1  3 0 . 0 9  2 5 . 4 8  4 c  9 . 1 6  6 . 7 5  6 . 9 6  X  1 3 . 1 3  8 . 5 5  4 . 2 6  1 5 . 2 1  5 c  8 . 6 8  5 . 9 2  4 . 0 9  1 1 . 6 2  1 1 . 9 8  9 . 7 9  5 . 7 8  4 . 9 7  6 c  3 . 4 4  6 . 7 4  3 . 5 7  1 7 . 2 8  8 . 2 6  1 5 . 7 7  0 . 0 0  2 . 3 5  7 a  8 . 4 3  1 8 . 6 2  6 . 6 8  8 . 1 4  6 . 4 5  1 0 . 5 3  3 . 0 8  8 . 2 0  7 b  1 2 . 5 4  1 3 . 5 6  5 . 5 0  1 2 . 7 3  2 1 . 5 1  1 6 . 5 6  1 4 . 4 7  2 4 . 2 0  X  7 c  7 . 2 8  3 . 9 0  3 . 0 2  1 . 6 3  5 . 9 1  3 . 5 2  0 . 0 0  2 . 1 6  8 a  1 9 . 8 7  6 . 1 5  5 . 4 6  1 0 . 5 1  8 . 6 4  3 . 8 4  0 . 0 0  3 . 4 6  8 b  1 9 . 8 1  4 . 6 5  7 . 3 0  7 . 0 3  6 . 8 1  5 . 2 9  0 . 9 9  3 . 9 8  8 c  4 . 9 1  2 . 6 5  3 . 9 2  3 . 6 2  5 . 0 1  4 . 1 6  0 . 2 2  2 . 0 5  9 a  5 . 7 5  3 . 7 4  4 . 7 8  2 . 9 4  6 . 5 3  7 . 4 4  3 . 9 8  4 . 8 8  9 b  9 . 9 6  4 . 7 4  7 . 5 0  2 . 3 6  1 6 . 0 6  1 1 . 6 1  0 . 0 0  4 . 7 2  9 c  2 . 9 8  1 . 4 1  3 . 2 0  5 . 4 6  5 . 0 4  2 . 4 6  0 . 0 0  1 . 4 2  1 0 a  6 . 0 0  3 . 5 3  3 . 1 6  2 . 2 4  1 3 . 0 2  5 . 8 6  0 . 0 0  3 . 2 0  1 0 b  4 . 5 5  4 . 1 0  9 . 5 5  4 . 3 3  1 8 . 6 6  6 . 5 5  1 . 5 2  1 . 9 5  1 0 c  2 . 0 7  1 . 7 0  1 . 9 6  2 . 0 1  4 . 9 0  3 . 0 1  0 . 0 0  3 . 2 0  70  T o t a l  S o l i d s  ( g / L ) 2 5 - A p r  0 3 - M a y  1 7 - M a y  3 0 - M a y  1 3 - J u n  2 7 - J u n  0 8 - A u g  2 2 - A u g  0 5 - S e p  1 9 - S e p  0 3 - O c t  1 7 - O c t  3 1 - O c t  1 4 - N o v  2 8 - N o v  1 2 - D e c  1 a  1 . 4 2  1 . 0 8  1 . 1 2  1 . 3 4  X  X  2 . 4 4  3 . 9 6  4 . 0 2  2 . 9 6  2 . 3 8  1 . 5 4 2  1 . 0 4 2  0 . 7 5 2  0 . 6 9 2  0 . 4 1  1 b  1 . 0 2  0 . 5 2  0 . 8 8  1 . 2  X  X  2 . 8 6  3 . 4  3 . 8 7  2 . 4 8  2 . 3  1 . 4 2 4  0 . 8 2 4  0 . 6 2 8  0 . 4 0 8  0 . 4 3 8  1 c  1  0 . 7 8  - 0 . 1 6  0  X  X  2 . 8 2  3 . 5 4  2 . 6  2 . 7 4  2 . 2  2 . 1  1 . 1 6  0 . 8 3 8  0 . 7 0 6  0 . 5 4 2  2 a  1 . 6 4  0 . 9 4  2 . 2 6  1  X  X  3 . 1 4  3 . 1 2  4 . 4  2 . 2  2 . 4  0 . 8 1  0 . 8 2 2  - 0 . 5 2 2  0 . 5 0 2  0 . 4 2 6  2 b  1 . 4 8  1 . 2  1 . 9 6  0 . 7 4  X  X  2 . 5 8  2 . 5 6  4 . 7 1  1 . 7 8  1 . 8 2  0 . 9 4 2  0 . 6 3 6  0 . 5 8  0 . 3 7  0 . 3 7 4  2 c  1 . 1 6  1 . 3 8  1 . 5 4  0 . 6  X  X  2 . 1  2 . 4 8  2 . 6 7  1 . 6 4  1 . 6  1 . 6 5  0 . 8 7 6  0 . 8 6 6  0 . 7 8 6  0 . 5 8 8  3 a  1 . 1 6  1 . 2 4  1 . 7 4  1 . 6 8  2 . 4  1 . 9 4  2 . 9 8  3 . 2 8  3 . 2 4  2 . 5 2  2 . 2 8  1 . 3 2 2  0 . 8 1 2  0 . 6 4  0 . 3 3 8  0 . 3 3 6  3 b  1 . 0 2  0 . 9 4  1 . 6 4  1 . 3 2  2 . 8 2  1 . 8 8  3 . 4 6  2 . 4 4  3 . 4  3 . 1 8  1 . 3 8  0 . 7 1 2  0 . 4 1 2  0 . 7 1  0 . 3 0 8  0 . 4 2 2 0 . 6 2  3 c  2 . 2  0 . 8 8  1 . 5 4  1 . 4  1 . 8 4  1 . 3 6  3  2 . 8 2  2 . 8 4  1 . 9 4  2  1 . 3 5  0 . 6  0 . 8 5 8  0 . 5 3 4  4 a  1 . 8 6  2 . 0 4  1 . 5 8  2 . 0 6  3 . 3 8  1 . 6 6  3 . 1  2 . 9  4 . 3 3  3 . 2  2 . 2  1 . 7 6 2  1 . 6 2  0 . 8 6 4  0 . 5 9 8  0 . 3 1  4 b  0 . 7 2  1 . 3 6  2 . 1  2 . 0 6  2 . 6 8  2 . 0 4  3 . 6 4  3 . 1 6  3 . 6 7  2 . 6 8  2 . 7 4  1 . 4 3 8  0 . 5 8 2  0 . 7 6 2  0 . 3 7 4  0 . 4 2 8  4 c  1 . 3 4  1 . 3  1 . 0 2  1 . 6  1 . 3 8  1 . 8 4  1 . 5 8  2 . 8 4  3 . 3 8  2 . 5 6  2 . 1  1 . 3 2  0 . 9 3 2  1 . 1 3 8  0 . 5 9 6  0 . 6 4  5 c  1 . 2 6  6 8 . 1 2  1 . 6 8  1 . 7 8  2 . 4 2  2 . 7 4  3  2 . 6 6  3 . 1 8  3 . 0 8  2 . 4 8  1 . 9 6  0 . 9 9 6  0 . 7 7 6  0 . 5 8 6  0 . 4 5  6 c  1 . 2 6  1 . 4 4  1 . 9 4  1 . 3 4  1 . 7 6  2 . 3 8  2 . 5 6  2 . 4 4  2 . 9 3  2 . 8 8  2 . 1 2  1 . 4 4  0 . 7 9 8  0 . 6 1 6  0 . 5 7  0 . 4 1  7 a  1 . 0 8  1 . 5  1 . 8 6  1 . 6 8  1 . 8 4  2 . 8  1 . 8 6  2 . 8 6  3 . 0 9  2 . 4 6  1 . 8 8  1 . 0 7 8  0 . 3  0 . 6 2 4  0 . 9 5 8  0 . 2 9 2  7 b  1 . 0 8  1 . 5 2  2 . 1  1 . 5 2  0 . 7  1 . 6 8  3 . 4 2  3 . 2 2  3 . 0 2  1 . 9  2 . 3 2  2 . 3 7 4  0 . 6 4 6  0 . 6 3 2  1 . 2 7 2  0 . 4 3 2  7 c  1 . 2 2  1 . 4 4  1 . 4  7 . 2 6  1 . 7 4  2 . 6  3 . 0 6  2 . 1 6  1 . 9 6  2 . 4 4  2 . 2  1 . 0 7  0 . 9 5 4  0 . 5 2  1 . 2 1 4  1 . 0 6  8 a  0 . 9  1 . 5  1 . 9 6  1 . 4  1 . 1 8  2 . 9  1 . 9 4  3 . 1 4  2 . 4 9  2 . 4 6  1 . 9 2  1 . 0 2 2  0 . 4 9 4  0 . 4 6 8  0 . 5 2 4  0 . 2 8 2  8 b  0 . 8 4  1 . 2 8  1 . 7 2  1.1  1 . 0 2  2 . 0 2  - 1 0 . 7  3 . 0 4  2 . 9 3  2 . 2 6  1 . 6 8  0 . 7 0 2  0 . 4 4  0 . 3 2 6  0 . 4 6  0 . 2 1 6  8 c  1 . 5 8  1 . 4 4  1 . 8  1 . 6 6  1 . 4 8  2 . 1 2  2 . 9  3 . 1 2  3 . 6 4  2 . 6 6  2 . 0 8  1 . 3 2  0 . 6 5 8  0 . 6 5  0 . 3 1 4  0 . 6 8  9 a  0 . 4  1 . 4 4  0 . 9 4  0 . 9 6  1 . 0 8  1 . 8 4  1 . 9 6  2 . 8 8  2 . 8  2 . 3 2  2  1 . 0 4 6  0 . 5 1 2  0 . 4 4 8  0 . 3 3 2  0 . 2 2 4  9 b  0 . 3  1 . 7  1 . 3  0 . 1 4  0 . 7 6  1 . 2  2 . 3  2 . 4 8  2 . 9 3  2 . 5 2  2 . 4 8  1 . 1 4 2  0 . 6 2 4  0 . 5 1 4  0 . 5 7 4  0 . 2 3 4  9 c  1 . 5 8  1 . 8 6  1 . 0 2  1 . 5 4  1 . 2 8  1 . 7  3 . 3  3 . 0 8  2 . 9 8  2 . 7 2  2 . 2 4  1 . 0 3  1 . 0 2 8  0 . 5 3 6  0 . 5 0 6  0 . 4 1  1 0 a  0 . 5  1 . 3 8  1 . 1 6  1 . 3  1 . 8  2 . 6 4  2 . 3  3 . 0 4  3 . 4 9  3 . 3 6  1 . 8 6  1 . 1 0 4  0 . 5 3 8  0 . 4 1 4  0 . 4 2 2  0 . 2 3  1 0 b  0 . 1 8  0 . 9 8  0 . 5 2  0 . 4 4  1 . 3 8  2 . 1 2  1 . 7 2  2 . 5 4  4 . 0 2  4 . 4 6  3 . 7  1 . 0 7 2  0 . 4 8 8  0 . 3 8 6  0 . 3 2 4  0 . 1 9 6  1 0 c  1 . 5 8  1 . 1 8  1 . 4 2  2 . 2 2  1 . 4 6  2 . 5 2  3 . 7  3 . 6 6  3 . 6 4  3 . 4  1 1 . 6 4  1 . 2 2  0 . 9 8 6  0 . 9 9 2  0 . 6 4 4  G E  1 . 4 4  1 . 4 2  2 . 5 6  1 . 3  2 . 7 2  1 . 4 2  2 . 4 4  3 . 8 6  2 . 6 7  2 . 3 6  1 . 4 6  1 . 2 7  1 . 4 2 2  0 . 2 3 6  X  71  0 . 4 7 X  T o t a l K j e l d a h l N i t r o g e n  ( T K N )  ( m g / L ) 3 1 - O c t  2 8 - N o v  1 2 - D e c  2 5 - A p r  1 6 - M a y  3 0 - M a y  1 3 - J u n  0 8 - A u g  2 2 - A u g  0 5 - S e p  g e  6 6 . 8 6 3  4 . 0 6 0 7 5  3 . 5 0 7 6 3  4 . 6 3 0 5  1 . 8 9 3 5  7 . 7 6  1 1 . 5 0 5  2 3 . 4 9  9 . 9 1 1  2 . 3 1 6  3 . 4 3 3  1 a  3 0 . 2 8 3  1 2 . 8 5 0 9  1 4 . 1 0 9 8  6 . 4 9 9  X  7 . 2 8  5 . 4 0 4  3 . 3 8  4 . 9 3 4  5 2 . 2 0 3 5  5 . 4 1 0 5  8 . 3 4 8 5  9 . 9 0 2 5  1 b  4 2 . 1 6 7  8 . 1 7 0 6 3  7 . 3 5 0 8 8  2 . 5 2 7  X  1 1 . 5 7  5 . 4 9 6  1 . 9 1 2  1 . 0 7 6  1 2 . 1 9 7  1 0 . 8 7 1  4 . 1 8 5  1 6 . 1 7 3 5  1 c  4 3 . 5 3 3 5  9 . 8 9 9 2 5  9 . 3 9 4 1 3  3 . 8 8 5 5  X  1 . 7 3  X  1 . 6 3 8  0 . 8 9 6  1 3 . 6 2 1  5 . 0 0 3  4 . 9 4 4  4 . 8 3 7 5  2 a  4 1 . 5 2 6 5  4 . 7 1 8 1 3  1 . 3 7 5 8 8  3 2 . 6 8 9  X  0 . 1 3  6 . 7 2  6 . 9 5 6  3 . 4 7 4  8 . 0 5 6 5  8 . 7 5 5  6 . 5 9 6  6 . 2 9 4 5  2 b  4 6 . 2 1 5  1 1 . 5 9 7 1  1 . 8 1 7 8 8  1 7 . 5 4 1  X  6 . 7 9  5 . 1 9 6  X  8 . 5 4 2  1 2 . 6 1 4 5  7 . 5 6 2  4 . 5 0 1 5  6 . 7 6 5  2 c  4 3 . 0 8 2 5  1 1 . 6 5 6 4  1 . 5 2 7 8 8  1 3 . 9 8 9  X  1 1 . 6 7  5 . 4 1 4  1 . 1 8 6  4 . 6 8 8  4 . 7 9 4 5  4 . 1 2  4 . 1 2 7  4 . 3 7  3 a  4 1 . 3 0 8 5  5 . 9 4 9 3 8  2 . 3 4 0 1 3  1 7 . 3 2 7 5  3 . 5 3  7 . 1 6 2  8 . 5 4 6  3 . 8 8 4  8 . 5 1 6 5  9 . 1 7  4 . 5 8 2 5  6 . 3 9 4  3 b  4 1 . 3 2 7 5  1 6 . 3 8 3 5  4 . 9 1 4 2 5  8 . 3 4 9 5  2 . 0 7 7  0 . 0 0  9 . 8 3 2  1 . 3 6 2  2 . 2 5 8  7 . 7 5 6 5  1 2 . 1 5 8  3 . 8 0 9 5  1 1 . 0 5 1  3 c  3 4 . 5 4 5 5  8 . 3 6 1 3 8  2 . 0 5 3 2 5  9 . 2 3 7  2 . 0 1 0 5  4 . 7 0  1 . 0 5 6  7 . 0 1 4  1 . 3 5 6  9 . 0 5 7  5 . 6 0 3  6 . 2 4 2 5  7 . 3 1 3 5  4 a  4 7 . 9 6 1 5  6 . 0 4 7 1 3  1 . 3 9 9 7 5  1 2 . 8 8 4 5  1 . 8 3 7 5  4 . 5 6  5 . 4  3 . 5 9  1 5 . 6  7 . 9 2 1 5  1 0 . 5 1 3 5  5 . 4 4 4 5  6 . 2 4 8 5  4 b  3 8 . 6 4 5 5  1 0 . 8 0 6 5  3 . 1 2 7 1 3  1 6 . 3 8 0 5  1 . 9 5  0 . 0 0  9 . 0 1 8  1 . 4 2 8  1 . 6 8 4  9 . 3 4 4 5  8 . 8 3 2 5  5 . 2 5 1 5  5 . 0 3 0 5  4 c  3 3 . 4 9 7  4 . 8 7 5  1 . 7 9 7 1 3  9 . 0 6 3 5  2 . 1 3 2 5  3 . 6 9  2 . 0 8 6  8 . 8 1 4  0 . 9 3 4  8 . 6 7 5 5  3 . 7 9 9 5  5 . 4 8 8  7 . 0 4 0 5  5 c  4 0 . 3 1 1 5  8 . 8 8 5  2 . 3 2 1 6 3  1 7 . 4 3 3  1 . 9 3 6 5  0 . 0 0  X  1 . 4 9 6  3 . 3 4 8  1 . 8 2 8  2 . 0 3 2 5  0 . 3 0 6  0 . 2 6 6  6 c  2 9 . 2 5 6  6 . 5 3 9 2 5  0 . 6 8 9 2 5  7 . 9 4 1 5  1 . 7 9 1  0 . 0 0  X  X  0 . 9 0 6  1 1 . 2 3 2  4 . 2 5 9  0 . 3 4 8  2 . 1 3 6 5  7 a  4 6 . 7 1 7  4 . 4 7 0 3 8  0 . 6 8 9 2 5  1 4 . 0 7 5  1 . 8 9 6 5  2 . 2 1  5 . 2 2 8  9 . 1 6  4 . 1 5 6  5 . 7 2 7 5 _  6 . 1 1 1 5  1 . 7 2 5 5  2 . 1 6  7 b  4 5 . 3 4 6 5  1 3 . 2 8 2  6 . 2 5 8 7 5  7 . 4 7 4 5  1 . 8 6 1  7 . 7 2  0 . 4 3 6  0 . 4 7 6  3 . 4 0 4  6 . 2 0 7 5  5 . 3 4 7 5  1 . 4 7 6  0 . 2 7 5 5  7 c  3 5 . 9 9 5  5 . 6 2 0 8 8  0 . 6 8 9 2 5  1 1 . 9 3 2  1 . 7 3 2  1 0 . 5 6  4 . 2 5 4  7 . 8 0 8  1 . 9 2 8  7 . 7 8 2 5  4 . 6 0 4 5  2 . 1 1 0 5  X  8 a  3 1 . 3 7 1 5  1 0 . 7 5 7 3  1 . 1 6 6 8 8  5 . 1 9 7  1 . 7 6 4 5  0 . 0 0  0 . 4 2 6  5 . 2 0 6  3 . 2 1 2  7 . 0 3 2  5 . 1 1 0 5  1 . 7 2 7 5  0 . 9 2 9  8 b  2 8 . 6 0 2 5  4 . 5 0 9 1 3  0 . 9 8 2 2 5  5 . 9 4 7 5  1 . 7 9 3  0 . 0 0  2 . 6 5  2 . 4 8 4  2 . 7 2  5 . 2 4 4  3 . 9 6 7 5  1 . 8 7 4 5  X  8 c  3 3 . 0 3 5  9 . 1 4 0 1 3  1 . 0 5 9 6 3  6 . 0 3 4 5  1 . 7 4 9  6 . 0 0  0 . 7 1 6  5 . 0 9 6  0 . 9 7 2  6 . 3 0 7 5  2 . 6 0 2  0 . 5 6 6 5  9 a  2 5 . 4 7 9  7 . 2 1 9 7 5  1 . 8 6 7 1 3  3 . 6 5 4  1 . 9 7 4 5  1 3 . 0 4  7 . 3 7  8 . 0 1 6  5 . 5 9 2  6 . 4 9 2  4 . 7 6 8 5  4 . 2 5 2  1 . 8 3 3 5  1 9 - S e p  1 4 - N o v  1 2 - A p r  X  X  X 2 . 3 1 1  9 b  2 8 . 5 3 5  3 . 9 3 2 2 5  1 . 7 0 6 8 8  1 3 . 1 6 2 5  1 . 8 4  1 6 . 7 0  9 . 5 1  6 . 3 9 4  6 . 4 2 4  5 . 4 6 4  4 . 2 7 5  4 . 3 5 5  1 . 8 5 2  9 c  3 1 . 7 0 6 5  4 . 4 9 4 7 5  2 . 2 8 3  1 5 . 5 2 7  1 . 8 9 6  3 . 6 9  0 . 8 9 4  4 . 3 5 8  1 . 4 7 2  2 . 3 0 4  3 . 7 1 1  1 . 7 8 4 5  3 . 5 8 7 5  1 0 a  3 5 . 8 9 0 5  3 . 8 5 9  1 . 4 9 6 8 8  7 . 8 9 6 5  1 . 6 6  9 . 8 0 2  9 . 3 5 8  2 . 4 4  6 . 2 1 5  7 . 0 5  6 . 1 5 9 5  3 . 2 5 4  1 0 b  3 2 . 4 8  3 . 8 5 9  1 . 4 4 1 5  2 2 . 8 5 3 5  1 . 9 0 7 5  2 . 4 0  1 1 . 7 1 8  2 . 4 5  0 . 9 3 8  6 . 7 3 9  5 . 5 2 3  4 . 3 5 3  2 . 1 8 2  1 0 c  3 4 . 6 4  3 . 8 5 9  2 . 1 1 4 6 3  1 6 . 2 5 4  0 . 8 6 6  0 . 0 0  3 . 1 3 8  2 . 5 8 8  2 . 6 9 2 5  2 . 8 6 2  3 . 9 4  4 . 5 6 1  X  72  X  O r t h o - p h o s p h a t e  ( m g / L ) 3 1 - O c t  1 4 - N o v  6 5 . 3 5  9 0 . 7 6  4 9 . 1 6  3 7 . 5 5  4 3 . 6 6  8 3 . 7 2  7 8 . 2 6  3 7 . 1 6  3 4 . 3 9  6 8 . 3 6  4 5 . 3 6  3 5 . 2 4  8 5 . 2 0  2 8 . 5 3  5 2 . 1 1  4 8 . 2 7  4 8 . 1 8  4 5 . 9 5  6 8 . 6 9 8 0 . 2 9  1 4 8 . 9 4  5 7 . 8 6  1 0 0 . 7 2 1 3 1 . 4 8 9 8 . 9 3  0 5 - S e p  1 9 - S e p  1 1 6 . 0 5  9 8 . 3 1  7 1 . 5 5  1 5 9 . 4 9  1 0 9 . 0 2  7 0 . 2 4  1 1 2 . 4 1  6 7 . 6 9  9 5 . 2 7  5 6 . 3 2  1 0 5 . 8 2  6 7 . 8 2  1 5 3 . 7 9  1 1 8 . 8 7  6 3 . 1 9  7 6 . 4 0  5 0 . 7 9  X  1 5 5 . 9 8  1 2 1 . 9 7  7 2 . 9 2  1 0 3 . 3 2  X  1 0 0 . 8 2  9 6 . 3 0  6 1 . 1 9  6 2 . 0 3  9 2 . 7 4  1 4 2 . 7 6  7 7 . 5 9  6 3 . 0 4  1 5 6 . 2 4  9 5 . 2 5  9 3 . 8 7  9 8 . 1 2  7 1 . 0 8  1 6 9 . 2 3  9 8 . 7 5  9 4 . 0 3  8 6 . 6 2  1 2 8 . 0 7  7 2 . 1 4  9 3 . 9 5  1 2 3 . 4 1  8 6 . 5 2  1 5 6 . 6 0  9 4 . 7 1  1 2 2 . 6 0  8 6 . 7 3  1 2 5 . 1 8  9 6 . 8 2  1 4 3 . 1 8  1 2 2 . 3 1  9 4 . 3 4  1 0 9 . 7 1  8 5 . 9 3  1 5 1 . 3 3  7 3 . 8 1  1 1 7 . 3 2  1 4 1 . 2 7  1 4 6 . 8 5  1 4 8 . 0 2  8 8 . 0 4  5 3 . 3 6  7 1 . 7 5  1 0 6 . 5 4  1 1 7 . 2 5  1 1 8 . 5 2  4 1 . 9 8  7 . 9 4  5 . 9 3  1 1 . 2 0  4 1 . 1 4  1 4 . 3 3  6 . 2 9  5 . 1 0  1 . 9 0  1 6 . 6 7  4 . 7 5  4 . 8 1  4 8 . 7 4  7 1 . 5 7  9 6 . 2 0  1 2 1 . 5 3  8 7 . 2 7  7 8 . 8 4  1 3 3 . 4 0  9 2 . 0 7  4 0 . 6 1  1 8 7 . 4 5  7 2 . 9 2  6 8 . 0 3  4 7 . 8 9  3 3 . 6 4  7 2 . 5 7  3 1 . 1 1  6 1 . 8 1  4 5 . 5 4  6 1 . 0 2  7 6 . 3 3  9 3 . 3 0  6 4 . 1 4  5 4 . 3 8  3 8 . 2 6  6 9 . 6 1  5 6 . 9 2  1 6 2 . 3 7  7 5 . 9 1  6 6 . 1 1  6 5 . 0 7  2 9 . 2 9  9 4 . 2 6  2 4 . 0 3  5 7 . 5 0  4 5 . 3 4  5 6 . 7 3  7 0 . 3 5  9 3 . 7 7  1 0 1 . 2 5  8 1 . 0 5  4 7 . 8 5  1 0 6 . 3 0  4 3 . 3 8  1 1 1 . 8 9  7 4 . 4 9  7 2 . 1 1  5 4 . 7 8  2 5 . 3 6  1 0 0 . 1 0  2 8 . 4 6  7 6 . 8 8  2 2 . 6 9  4 8 . 3 7  7 2 . 6 1  1 0 6 . 6 2  7 9 ^ 5 3  6 8 . 8 3  7 2 . 3 0  3 6 . 3 1  7 1 . 7 1  4 2 . 0 8  1 4 7 . 4 9  7 6 . 2 5  7 4 . 5 8  4 2 . 1 9  6 . 3 1  8 1 . 6 8  1 5 . 4 8  4 2 . 5 4  8 b  7 . 1 1  2 9 . 9 0  5 0 . 5 4  1 0 3 . 8 0  6 8 . 9 2  5 2 . 4 1  4 5 . 5 0  1 3 . 8 1  2 8 . 2 7  4 1 . 7 3  8 4 . 6 0  6 5 . 5 3  5 9 . 3 5  3 1 . 3 8  6 . 5 4  7 5 . 7 4  2 3 . 4 0  4 7 . 2 9  8 c  1 5 . 9 8  5 7 . 6 0  6 3 . 3 4  8 3 . 4 3  7 5 . 7 0  6 3 . 8 8  5 7 . 2 7  3 9 . 0 4  4 2 . 3 3  4 4 . 7 4  6 1 . 7 7  5 0 . 4 6  5 6 . 4 7  4 4 . 5 0  3 . 0 8  1 0 6 . 7 3  2 6 . 1 6  7 4 . 0 0  9 a  1 0 . 4 9  3 7 . 4 3  6 3 . 7 9  4 5 . 0 7  3 3 . 9 8  3 9 . 4 0  3 4 . 1 9  9 8 . 0 8  7 7 . 5 8  4 8 . 4 6  1 7 7 . 4 6  7 7 . 2 2  7 6 . 1 6  3 6 . 2 2  7 . 3 6  7 6 . 2 4  2 9 . 4 2  5 9 . 1 2  9 b  1 2 . 1 1  1 3 . 0 1  4 4 . 1 7  2 9 . 0 6  1 8 . 3 0  1 8 . 5 6  2 9 . 7 7  3 . 5 3  5 0 . 8 1  4 9 . 4 0  1 2 3 . 8 9  7 2 . 5 3  6 4 . 8 0  4 5 . 4 3  4 4 . 2 9  7 2 . 0 9  3 1 . 0 0  6 1 . 8 6  9 c  3 2 . 8 9  7 0 . 6 0  8 0 . 2 2  6 6 . 6 2  5 5 . 0 0  6 7 . 3 8  6 0 . 7 3  2 1 . 4 2  1 2 0 . 7 6  6 9 . 1 9  1 1 5 . 7 4  6 7 . 4 4  6 6 . 2 2  4 7 . 4 6  2 4 . 2 2  9 4 . 3 1  3 3 . 5 7  7 9 . 6 0  1 0 a  1 2 . 0 0  4 0 . 0 2  6 5 . 5 6  6 3 . 0 2  7 6 . 4 5  9 0 . 4 1  1 0 5 . 9 4  1 0 9 . 7 5  9 2 . 9 4  4 9 . 2 8  1 1 7 . 1 9  5 3 . 1 6  4 7 . 0 1  4 0 . 4 4  2 2 . 8 3  9 0 . 8 2  3 7 . 3 4  6 6 . 6 8  3 0 - M a y  1 3 - J u n  2 7 - J u n  1 4 2 . 9 7  1 5 5 . 2 6  1 4 8 . 3 8  9 1 . 3 9  4 8 . 3 9  1 3 5 . 5 4  X  X  5 0 . 6 1  4 2 . 5 4  1 2 4 . 6 7  X  X  4 8 . 1 9  3 3 . 0 4  1 1 5 . 6 5  X  X  7 4 . 1 6  1 0 6 . 7 1  4 0 . 0 0  X  7 3 . 7 3  7 5 . 4 3  8 8 . 5 0  2 8 . 8 0  6 0 . 2 2  6 5 . 9 6  7 5 . 0 4  0 . 9 3  6 8 . 0 7  8 1 . 1 7  1 2 0 . 1 2  5 9 . 8 6  1 3 3 . 3 5  5 5 . 6 4  7 1 . 5 0  1 2 0 . 9 0  6 7 . 6 1  1 2 7 . 0 5  3 9 . 5 5  6 4 . 5 6  7 3 . 3 1  1 2 1 . 6 8  6 8 . 1 5  4 a  3 0 . 4 8  6 7 . 7 0  8 6 . 6 4  1 1 9 . 8 3  4 b  4 3 . 7 3  3 8 . 0 7  6 6 . 1 6  4 c  3 9 . 7 9  7 3 . 8 0  7 6 . 5 3  5 c  1 7 . 4 2  5 3 . 3 3  6 c  2 0 . 4 9  7 a  2 5 . 4 4  7 b  1 7 . 6 2  7 c  1 8 . 9 4  8 a  1 2 - A p r  2 5 - A p r  0 2 - M a y  1 6 - M a y  g e  1 0 6 . 6 8  1 2 2 . 1 6  8 0 . 3 3  1 a  4 5 . 4 4  6 8 . 4 9  6 5 . 0 9  1 b  6 7 . 7 0  5 8 . 4 1  1 c  2 3 . 5 6  5 2 . 0 3  2 a  3 2 . 6 0  7 4 . 1 4  2 b  4 0 . 4 4  2 c  2 7 . 7 7  3 a  2 9 . 1 4  3 b  5 5 . 4 0  3 c  2 5 - J u l  0 8 - A u g  2 2 - A u g  1 3 2 . 9 1  1 2 0 . 1 6  1 5 1 . 5 7  9 4 . 5 2  1 2 3 . 2 4 1 2 5 . 8 2  X  X X  0 3 - O c t  1 7 - O c t  4 2 . 4 3  1 9 . 6 9  7 8 . 6 3  9 1 . 3 1  2 8 - N o v  X  1 2 - D e c  X  2 6 . 2 0  5 9 . 7 4  5 9 . 4 5  1 6 . 7 6  5 7 . 3 4  8 1 . 4 8  2 2 . 8 8  5 8 . 3 0  3 2 . 3 3  4 5 . 4 6  1 2 . 3 1  3 7 . 4 2  3 7 . 0 1  3 3 . 9 2  6 2 . 9 5  1 4 . 0 3  3 7 . 9 8  5 5 . 1 4  3 5 . 7 7  9 1 . 5 4  2 7 . 1 4  4 6 . 3 4  8 2 . 9 7  4 0 . 6 0  3 8 . 6 3  7 0 . 9 4  1 5 . 7 0  4 8 . 6 7  5 9 . 7 1  2 9 . 6 4  3 2 . 1 0  8 0 . 6 5  1 7 . 1 8  6 2 . 1 8  6 8 . 6 5  6 6 . 8 6  4 1 . 2 7  4 1 . 7 4  9 9 . 6 2  2 9 . 8 2  8 0 . 7 1  8 4 . 2 3  5 0 . 0 5  4 2 . 8 5  3 5 . 9 2  4 9 . 6 2  6 3 . 5 0  2 3 . 3 7  4 8 . 6 9  6 0 . 6 3  8 1 . 8 4  4 4 . 2 5  5 0 . 4 6  3 8 . 5 2  4 2 . 4 8  7 7 . 8 1  2 3 . 3 4  5 8 . 1 7  6 1 . 2 0  9 1 . 9 2  4 7 . 5 8  3 5 . 1 7  4 2 . 9 4  4 2 . 4 8  1 1 0 . 7 6  2 8 . 8 6  7 6 . 6 5  5 3 . 8 5  1 1 2 . 5 3  6 5 . 9 8  6 7 . 0 7  3 6 . 2 7  2 5 . 0 5  6 9 . 5 0  1 7 . 9 9  4 0 . 4 7  1 0 b  1 1 . 1 2  7 . 3 7  3 0 . 8 8  1 6 . 8 7  3 0 . 7 1  4 2 . 7 0  6 6 . 3 9  3 . 4 4  7 4 . 1 7  5 5 . 3 4  1 4 4 . 0 3  5 0 . 6 8  3 1 . 9 5  4 2 . 2 0  3 1 . 5 6  7 0 . 3 6  2 5 . 5 2  4 0 . 6 6  1 0 c  2 9 . 3 6  6 7 . 1 6  7 3 . 4 2  7 9 . 7 6  9 8 . 4 3  4 6 . 9 2  8 6 . 7 5  5 . 2 4  9 3 . 7 5  1 0 2 . 6 9  1 3 4 . 5 4  4 7 . 7 3  4 7 . 7 2  4 1 . 0 8  2 1 . 3 2  1 1 0 . 4 5  4 9 . 2 1  1 0 5 . 6 2  73  T o : Ward Prystay Bio-Resource Engineering Room 76A-2357 Main Hall Van, B.C. V6Z 1T5 Phone:264-9793 822-6642 Fax:  1 6 5 0  S t r e e t  B . C . V 5 L  P h : ( 6 0 4 ) 2 5 1 - 4 4 5 6  CAVENDISH LABORATORY LTD.  P r o j e c t : W a r d  CERTIFICATE  C e r t i f i c a t e : 9 7 0 3 1 9 1  D a t e  OF ANAL YSIS  S a m p l e s :  7 5  Sample  PPM  PPM  PPM  PPM  PPM  PPM  PPM  PPM  RPM  PPM  PPM  RPM  PPM'  PPB  Ag  Al  As  B  Ba  Be  Bi  Ca  ca  Co  Cr  Cu  Fe  Hg  MAY 30 G E < 0 0 3  .40  <02  .26  .013  .002  <.04  52.4 <.002  <005  .010  ,068  .57  .004  Name  P a n d o r a  V a n c o u v e r ,  D a t e T y p e  RPM •PPM .  PPM  PPM  PRM, PRM  PPM  'RPM  K  La  Mg  Mn  Mo  Na  Nl  <02  88.9  .038  8.8  .26  .043  4  <005  19.71  RPM  PPM: PPM  PRM Si  s  -Sb  Se  <02  16  <.03  .010.  • •• P. P b  I n :  3 / 1 9 / 9 7  O u t :  3 / 2 7 / 9 7  o f A n a l y s i s :  PPM  1 L 6 F a x : 2 5 8 - 9 4 9 7  PPM-  W I C P 3 0 - D I S PPM.  PPM  PPM'  Sn  Sr  Ti  V  W  Zn  <.01  <.01  .451  <.005 <005  <.03  .16 .26  PPM .PRM  .004  .84  < 02  .29  .022  <04  108.0 <002  <.005  .014  .075  .79  <.02  157.9  .027  21.5  .35  .050  6  <.005  24.26  .03  35  <03 <.005  .1  <.01  1.005  <.005 <,005  <03  C E L L 2 <.003  .11  <02  .30  .006 <.001  <.04  23.3 <002  <.005  <005  .106  .16  <02  81.7  <.005  19.9  .13  .030  14  <005  2.88  <02  25  <.03 <.005  1.4  <01  .248  <.005 <.005  <.03  .65  CELL 3 <003  .65  <.02  .34  .014  .001  <.04  85.8 <002  <.005  <.005  .112  .42  <02  150.9  .019  21.5  .36  .044  8  <005  10.74  <.02  32  <.03 <.005  <.01  <.01  .763  <005 <005  <.03  .23  CELL 4 <003  .88  .03  .38  .013  .003  <04  114.8 <002  <.005  <.005  .146  .67  <02  202.9  <.005  33.2  .53  .059  13  <.005  10.65  <02  41  <03 <.005  <.01  <01  1.121  <005 <005  <.03  .31  CELL 5  .007  .94  .03  .30  .026  .003  <.04  124.4 <.002  .011  .008  .148  .06  <.02  159.3  .031  27.1  .77  .035  22  .020  28.43  .03  32  .06 <.005  <.01  .03  1.168  <005 <.005  <.03  .21  CELL 6  .004  .91  .05  .32  .026  .002  <04  122.7 <002  .007  .005  .126  .07  <.02  173.1  .026  29.6  .16  .045  15  .024  22.36  <02  29  .08 <.005  <01  .04  1.217  <005  .005  <03  .17  CELL 7  .014  1.58  .15  .61  .110  .006  <04  224.0  .005  .046  .015  .482  2.02  <02  320.7  .041  53.0  .95  .112  14  .042  37.42  .07  49  .17 <.005  3.3  .13  2.186  <005  .014  .09  .46  CELL 8  .024  1.75  .17  .69  .201  .009  .11  260.0  .010  .037  .029  .400  1.49  <02  379.4  .072  67.7  .97  .103  16  .041  35.99  .11  >50  .23  .036  5.5  .15  2.445  <.005  .023  .14  .66  CELL 9  .010  1.13  .07  .42  .135  .005  <.04  155.0  .003  .010  .012  .176  1.53  <02  188.1  .030  35.3  .84  .036  9  .038  26.18  .05  34  .11  <005  2.2  .06  1.510  <.005  .009  .03  .22  57.3 <002  CELL 1  .42  <.02  .13  .065  .002  <.04  J U L Y 25 G E  .014  1.51  .13  .17  .046  .006  <.04  J U L Y 25 1C  .012  1.11  .09  .38  .017  .005  .08  J U L Y 25 2 C  .004  .93  .07  .31  .017  .003  <.04  J U L Y 25 3C  .003  .56  <02  .20  .009  .002  <.04  ' C E L L 10 <.003  J U L Y 25 4C < 0 0 3  <005  <.005  .074  .69  <02  62.6  .020  11.9  .28  .016  6  .018  8.96  <.02  15  <.03 <:005  <-01  .504  <.005  .006  <.03  .11  .003  .012  .011  .047  .62  <02  132.4  .041  34.0  .12  .046  5  .008  31.66  .05  >50  .22 <.005  .2  .12  2.647  <.005  .007  .08  .22  151.8 <.002  .026  .015  .080  .24  <.02  248.0  .062  55.9  .25  .057  42  .021  3.47  .07  >50  .18 <.005  2.0  .07  1.481  <.005  .022  .05  .31  .003  <.005  .008  .061  .20  <.02  216.2  .045  46.2  .42  .041  19  .012  5.77  .05  >50  .07 <005  1.7  <.01  1.282  <.005 <005  <.03  .26  80.5 <002  <005  .008  .069  .14  <.02  96.0  .037  22.5  .03  .031  13  <.005  3.34  <.02  38  <.03 <.005  2.1  <01  .720  "<:6o5 <.005  <.03  .19  .20  .05 <.005  .6  200.4  128.2  .59  <.02  .21  .012  .003  <.04  84.1  <.0O2  <005  .009  .063  <02  120.3  .023  27.9  .19  .038  15  .015  4.07  .02  39  .004  1.22  .12  .30  .021  .004  <.04  174.1  <002  <.005  <.005  .067  <01  <02  195.4  .053  38.3  .09  .051  44  .006  17.29  <02  >50  J U L Y 25 6C <.003  .46  <.02  .18  .018 <.001  <.04  62.2 <.002  <.005  <005  .022  <.01  <.02  121.4  .019  18.8  .02  .022  9  <.005  .70  <.02  J U L Y 25 7C < 0 0 3  .44  <02  .13  .026  .002  <.04  64.9 <002  <005  <.0O5  .088  .08  <.02  99.4  .019  15.2  .25  .031  5  .010  5.59  162.2 <002  .014  .009  .211  .46  <.02  187.7  .035  39.2  .77  .047  9  .024  .002  <005  .014  .078  .39  <.02  50.9  .033  13.0  .32  .020  5  .025  J U L Y 25 5C  <01  <.01  .807  .008  <.03  .20  <.005  <01  .08  1.569  <.005 <.005  <.03  .07  . 29  <.03 <.005  .5  <.01  .679  <.005 <.005  <.03  .06  . .02  24  <.03 <005  1.2  <.01  .582  <.005 <.O05  <.03  .13  11.27  .06  >50  .08 <.005  1.1  .02  1.476  <.005  .006  .05  .22  7.05  .06  19  .04 <.005  .1  <.01  .547  <005  .024  .04  .07  <.005  .005  <.03  .07  <005 <.005  <.03  .11  .11  <005  J U L Y 25 8C  .009  1.14  .12  .21  .102  .004  <.04  J U L Y 25 9C  .009  .49  <.02  .09  .038  .003  .14  J U L Y 25 10C  .006  .92  .05  .19  .055  .004  <04  128.9 <.002  <005  .007  .082  .50  <02  52.7  .036  24.1  .39  .025  6 • .014  6.08  .06  40  .08 <.005  2.9  .01  1.086  OCT 3 G E < 0 0 3  .29  <.02  .10  .009 <.001  <.04  46.6 <.002  <.005  .006  .035  .21  <.02  68.6  <005  9.9  .20  .026  3  <.005  6.48  <02  21  < 0 3 <.005  <01  <.01  .496  OCT 3 1A < 0 0 3  .20  <.02  .08  .008 <001  <.04  35.1  <002  <005  <005  .020  .05  <.02  70.4  .011  10.4  .04  .016  5  <005  5.40  <.02  15  <.03 <005  <01  <.01  .471  <.005 <005  <.03  .08  OCT 3 1B < 0 0 3  .42  <.02  .16  .011  <.001  <04  58.7 <.0O2  <005  <.005  .039  .08  <.02  105.7  .029  19.4  .16  .026  11  <0O5  6.35  <02  27  <03 <.005  <.01  <01  .761  <.005 <.005  <.03  .12  O C T 3 1C <.003  .44  <.02  .17  .010 <001  <.04  61.4 <.002  .006  <.005  .034  .03  <.02  90.6  .015  18.2  .04  .028  14  <.005  3.08  <.02  35  .03 <.005  2.1  <.01  .758  <.005 <.005  <.03  .13  O C T 3 2A < 0 0 3  .71  <.02  .20  .014  <.04  93.4 <.002  <.005  <.005  .048  .12  <.02  160.9  .036  29.8  .28  .057  12  <.005  6.40  <.02  45  .05 <.005  .1  <.01  1.212  <.005 <.005  <03  .19  O C T 3 2B <.003  .14  <.02  .08  .007 <001  <.04  27.9 <.002  <.005  <.005  .023  <01  <.02  96.5  .039  12.6  .01  .011  10  <.005  3.18  <.02  17  <.03 <.005  .8  <.01  .455  <.005 <.005  <.03  .10  OCT 3 2C <.003  .09  <.02  .17  .006 <001  <.04  24.6 <002  <.005  <.005  .027  <01  <.02  202.6  .044  26.4  .05  .014  21  <.005  4.80  <02  35  <03 <005  4.5  <.01  .406  <.005 <005  <.03  .15  O C T 3 3A < 0 0 3  .42  < 02  .10  .014  .001  <.04  59.8 <.002  <005  <.005  .035  .08  < 02  94.0  .028  17.2  .02  .038  8  <005  8.27  <02  27  < 0 3 <.005  <01  < 01  .778  <.005 <.005  <.03  .12  .002  71.5  O C T 3 3B < 0 0 3  .26  <.02  .09  .009 <001  <04  41.7 <.002  <.005  <.005  .030  .05  <.02  104.7  .029  13.7  .05  .036  6  <.0O5  4.17  <.02  20  <.03 <.005  <.01  .547  <.005 <005  <.03  .11  OCT 3 3C <.003  .34  <.02  .06  .011  <.04  50.5 <002  <.005  <.005  .046  .08  <.02  104.8  .010  16.7  .09  .034  9  <.005  5.77  <02  25  < 0 3 <.005  <01  <.01  .673  <.005 <.005  <.03  .12  OCT 3 4A < 0 0 3  .50  <.02  16  .011  .002  <.04  63.2 <002  <.005  <005  .040  .13  <.02  206.8  .023  35.6  .03  .034  31  <.005  5.84  <.02  >50  <03 <.005  1.9  <.01  1.212  <.005 <,005  <.03  .21  O C T 3 4B <.003  .78  <02  .21  .014  .002  <04  96.2 <002  <.005  <.005  .061  .19  <.02  227.0  .068  51.3  .14  .044  54  .006  4.27  <,02  >50  .07 <.005  3.3  <.01  1.601  <.005 <.005  <.03  .28  O C T 3 4C <.003  .14  <.02  .08  .008 <001  < 04  25.4 <002  <005  <.005  .022  .05  <.02  119.7  .039  16.0  .04  .008  18  .008  3.68  <.02  24  <.03 <.005  .8  <01  .487  <.005 <.005  <.03  .11  O C T 3 5C  .006  .99  <.02  .20  .025  .004  <04  126.0 <.002  <.005  .008  .057  <.01  <.02  165.4  .044  35.5  .21  .063  19  .008  14.82  <02  >50  .08 <.005  <.01  .06  1.692  <.005 <.005  <.03  .09  O C T 3 6C <.003  .48  <02  .15  .017  .001  <.04  63.9 <002  <.005  <.005  .034  <01  <02  111.2  .024  22.7  .02  .025  9  <005  1.99  <02  32  <.03 <.005  .2  <.01  .938  <.005 <.005  <03  .09  OCT 3 7A <003  .53  <02  .13  .015  .002  <.04  71.6 <.002  < 005  <005  .057  <.02  113.1  .014  21.9  .24  .050  4  .011  8.06  .02  27  <03 <.005  <01  <.01  .945  <.005 <.005  <.03  .15  OCT 3 7B <.003  .34  <02  .10  .012 < 001  <.04  50.0 <002  <005  <.005  .045  .06  <.02  74.8  .011  15.2  .08  .030  4  < 005  5.03  <.02  21  <.03 <.005  .2  <01  .647  <.005 <005  <.03  .10  OCT 3 7C <.003  42  <.02  .11  .018  <04  58.4 <002  <005  <005  .047  .13  <02  86.0  <,005  16.7  .15  .039  4  < 005  8.24  <.02  22  <.03 <.005  .1  <01  .781  <.005  <.03  .11  File Name:War0319Ifin.xls  <.001  .001  .16  Pagel  74  .2  CERTIFIED BY:  .007  wdeKcms  o-Resource Engineering T o Ward Prystay Bi Room 76A-2357 Main Hall Van, B.C. V6Z 1T5 Phone:264-9793 822-6642 Fax: Project: W  a  r  1 6 5 0  D a t e  CERTIFICA TE OF ANAL YSIS  D a t e T y p e  Samples: 7 5 PPIyi  PPM  RPM  PPM  PPM  PPM  PPM  PPM  PPM  PPM  PPM  PPM.  Ag  Al  As  B  Ba  Be  Bi  Ca  Cd  Co  ' Cr  Cu;  Fe  Hg  .003  .81  .03  .23  .016  .003  <04  104.6 <002  <.005  .007  .077  .29  O C T 3 8B <003  .20  <.02  .07  .010 <001  <04  34.9 <.002  <005  <.005  .038  O C T 3 8C <.O03  .60  .03  .14  .028  .002  <04  82.7 <.002  <.005  <.005  O C T 3 9A <O03  .61  <.02  .15  .024  .002  <.04  81.8 <.002  <005  O C T 3 9B <003  .28  <02  <.05  .018 <.001  <04  43.6 <.002  O C T 3 9C <003  .41  <02  .08  .030  .001  <.04  58.5 <002  .004  .67  <.02  .30  .026  .002  <04  86.8 <.002  O C T 3 10B < 003  .46  <02  .15  .027  .001  <.04  64.2 <.002  .014  1.42  .11  .33  .135  .006  .06  D E C 12 1A <003  .05  <.02  .06  .005 <.001  <.04  Name O C T 3 8A  O C T 3 10A  O C T 3 10C  S t r e e t  B . C . V 5 L  P h : ( 6 0 4 ) 2 5 1 - 4 4 5 6  CAVENDISH LABORATORY LTD.  d  Certificate: 9 7 0 3 1 9 1  Sample  P a n d o r a  V a n c o u v e r ,  P P M . PPB  • PPM PPM, PPM  PPM  PPM RPM  PPM  RPM,RPM PPM PPM  Mo, .Na  Ni  P  PD  .s  1 L 6 F a x : 2 5 8 - 9 4 9 7  I n :  3 / 1 9 / 9 7  O u t :  3 / 2 7 / 9 7  o f A n a l y s i s :  W I C P 3 0 - D I S  PPM  PPM  PPM  PPM  PPM  PPM  Se"  Si  Sn  Sr  Ti  V  PPM PPM  K  La  Mg  Mn  W  • Zn  <02  146.2  .022  32.5  .15  .072  14  .008  10.23  .04  42  .05 <005  .1  <.01  1.400  < 0 0 5 <.005  <.03  .20  .06  <.02  74.4  .025  14.5  .08  .014  8  <005  4.77  <.02  17  <.03 <.005  <01  <01  .502  <.005 <.005  <.03  .09  .058  .12  <02  118.9  .014  24.0  .20  .044  7  <005  4.57  <.02  39  <.03 <.005  1.9  <.01  .995  <005 <.005  <.03  .16  <.O05  .061  .41  <02  111.5  .028  21.0  .28  .054  5  <.005  13.92  <02  32  <.03 <.005  .1  <.01  1.065  <.005 <.005  <.03  .16  <.005  <.005  .039  .09  <02  64.5  .020  10.7  .02  .026  3  <005  9.54  <.02  17  <.03 <.005  <01  <.01  .598  <.005 <.005  <.03  .11  <,005  <005  .045  .24  <.02  76.8  .010  15.3  .09  .029  4  <005  8.45  <.02  22  <.03 <005  .2  <.01  .722  <.005 <.005  <.03  .12  <005  <.005  .069  .19  <.02  134.3  .028  23.9  .02  .064  13  .009  8.69  .04  38  <.03 <.005  1.0  <01  1.136  <.005 <005  <.03  .21  <.005  <.005  .077  .06  <.02  146.5  <.005  20.2  .01  .049  18  .013  5.16  <.02  30  <.03 <.0O5  .1  <.01  .817  <005  .006  <.03  .15  .003  .022  .008  .171  .55  <.02  220.6  .015  55.6  .43  .039  34  .028  10.88  .06  >50  .12 <.005  2.2  .07  2.237  <.005  .008  .09  .16  11.7 <.002  <005  <.005  .023  .03  <.02  56.0  <.005  4.3  <.01  .004  8  <005  5.50  <.02  5  .009  <.01  <.01  .148  <.005 <.005  .17  <01  192.8  .  -Sb  <.03  D E C 12 1B <003  .05  <.02  <.05  .006 <001  <04  <002  •=.005  <.005  .031  .04  <.02  42.0  .017  3.3  <005  4.67  <.02  <.03 <.005  <.01  <.01  .118  <.005 <.005  <.03 <.01  D E C 12 1C <003  .07  <.02  .06  .010 <.001  <.04  21.2 <.002  <.005  <.005  .031  .07  <02  52.6  .040  10.2  <01  .003  .017  4.38  <.02  <.03 <.005  <.01  <.01  .267  <.005 <.005  <.03  .05  D E C 12 2A <003  .05  <.02  <.05  .006 <001  <.04  13.3 <002  <.005  <.005  .025  .03 < 0 2  38.1  .026  6.3  <01  <.002  .013  3.14  <.02  <.03 <.005  .2  <.01  .176  <.005 <.005  <.03  .02  D E C 12 2B <003  .05  <.02  <.05  .006 <.001  <.04  9.7 <.002  <.005  <.005  .018  <.01  <.02  26.3  .022  3.4  <.01  <.002  .008  2.68  <.02  <.03 <.005  <.01  <.01  .121  <.005 <.005  <.03  .06  D E C 12 2C <.003  .05  <.02  <.05  .008 <.001  <.04  16.4 <.002  <.005  <:005  .034  .02  <.02  49.9  .022  10.2  <.01  .002  .012  2.83  <02  <.03 <.005  <.01  .239  <.005 <.005  <03  .05  D E C 12 3A <003  .09  <.02  <.05  .010 <.001  <.04  22.9 <.002  <.005  <.005  .033  .07  <.02  59.9  <.005  8.1  <.01  .012  <.005  6.49  <02  <.03 < 0 0 5  =.01  •=.01  .300  <005  <.03  D E C 12 3B <003  .08  <.02  <.05  .008 <001  <.04  22.7 <.002  <.005  <.005  .047  .06 <.02  61.0  <.005  7.6  <.01  .007  <005  5.93  <.02  <.03 <.005  =.01  <.01  .297  <.005 <.0O5  <.03  D E C 12 3C <.003  .05  <.02  <.05  .008 <001  <.04  16.7  <002  <.005  <.005  .045  .06 <.02  94.0  <005  12.7  <01  .007  <.005  4.37  <.02.  <.03 <.005  .4  <.01  .236  <.005 <005  <.03  D E C 12 4A <003  .05  <02  <05  .006 <.001  <.04  19.0 <.002  <.005  <.005  .030  .06 <.02  58.6  <.005  6.3  <01  .003  <.005  5.85  <.02  <.03 <.005  =.01  <.01  .263  <.005 <.005  <.03  D E C 12 4B <003  .05  <02  <.05  .007 <.001  <.04  17.5 <002  <.005  <.005  .032  .07  <.02  67.9  «.005  8.6  <.01  .005  <005  3.82  <.02  <.03 <.005  =.01  •=.01  .257  <.0O5 <.005  <.03  .06 <.02  9.7  <01 <002  <.005  D E C 12 4C  = 003  .10  <.02  .012 <001  <.04  23.0 <.002  <.005  <.O05  .036  85.3  .031  12.7  <01  .011  20  <.005  4.42  <02  <.03 <.O05  .5  <.01  .368  <005  <.005  <.03  D E C 12 5C  =.003  .06  <02  <.05  .008 <.001  <.04  21.1 <002  <.005  <.005  .032  <.01  <.02  57.2  .021  8.2  <.01  .007 ' 15  <005  2.79  <,02  <.03 <.005  <.01  <.01  .284  <.005 <.005  <.03  D E C 12 6C  =.003  .05  <02  .06  .008 <.001  <.04  15.4 <002  <.005  <.005  .037  <.01  <.02  59.6  .017  7.8  <.01  .015  9  <.005  .80  <.02  <.03 <.005  .1  <.01  .243  <.005 <.005  <.03  D E C 12 7A = 003  .05  <.02  <.05  .006 <.001  <.04  13.6 <.002  <.005  <.005  .040  <.01  <.02  46.1  .017  4.8  <01  .008  7  <005  5.08  <.02  <.03 <.005  <01  <01  .193  <.005 <.005  <03  D E C 12 7B =.003  .05  <02  .06  .007 <.001  <04  12.1 <002  <.005  <.005  .045  <.01  <02  38.6  .022  4.1  <.01  .004  9  <.005  3.46  <.02  <03  <.005  <.01  <.01  .153  <005  D E C 12 7C <003  .11  = 02  <.05  .013 <001  <.04  25.1  <.002  <.005  <.005  .041  <01  <.02  60.1  .026  8.4  <01  .003  <.005  2.32  <02  <.03 <.005  =.01  <01  D E C 12 8A <.003  .05  =.02  D E C 12 SB <003  .05  =.02  D E C 12 8C <.003  .05  D E C 12 9A <003  .05  D E C 12 9B <003  .05  <02  D E C 12 9C <003  .05  .004  .003 <001  <04  12.7 <.002  <.005  <.005  .041  <.01  <.02  32.1  .022  6.3  <.01  .007  .009  4.60  <.02  <.03 < 0 0 5  .6  <.01  <.002 <.001  <04  12.2 <.002  <005  •=.005  .034  <.01  <.02  30.5  <005  4.2  <.01  .002  •=.005  4.79  <.02  <.03 <.005  =.01  <.01  .153  = 02  .008 <.001  <.04  19.1 < 0 0 2  <005  <005  .042  <.01  <.02  56.4  .017  8.0  <01  .007  <005  2.95  <.02  <.03 <.005  =.01  <.01  = 02  <.002 <.001  <.04  7.9  <002  <.005  <.005  .033  <.01  <.02  56.6  .017  3.6  .02 <.002  <.005  7.43  <.02  <.03 <.005  =.01  <.01  <05  .004 <001  <04  5.7  <002  <005  <.005  .081  .04  <02  54.7  <.005  2.2  <.01  .011  6  <.005  6.12  <02  <03 <.005  <01  <02  <.05  .006 <.001  <04  13.9 <.002  <.005  <.005  .076  .04  <.02  75.2  .012  5.8  <.01  .027  15  <.005  6.82  <02  <.03 <,005  .05  <02  <.05  .005 <001  .07  4.9  <002  <005  .007  .051  .08  <.02  63.3  .008  1.9  <01  .010  4  .014  6.93  .03  D E C 12 10B <003  .05  <02  <.05  .007 <.001  .10  7.0 <.002  <.005  .013  .050  .16 < 0 2  56.2  <.005  2.4  <.01  .009  5  .006  6.28  D E C 12 10C  .07  <.02  .09  .012 <.001  <.04  16.8 <002  <.005  .005  .110  .10  96.7  .017  7.1  .01  .046  14  .015  8.82  D E C 12 10A  .003  .14  F i l e Name:War0319Ifin.xls  <.02  Page2  75  <.005  <.03  <.005 .006  <.03  <.005 .006  <.03  <.005 .008  <.03  .269  <.005 .008  <.03  .092  <,005 .010  <03  <.01  .074  <.005 <005  <03  <.01  <01  .184  •=.005 <005  <.03  <.03 <.005  <.01  <.01  .061  <.005 .019  <.03  .03  <.03 < 0 0 5  <.01  <.01  .079  <005  .023  <.03  .04  <.03 <.005  .4  <.01  .186  <.005 .022  <.03  CERTIFIED BY: wdeKteveF  APPENDIX 2. CHARTS AND GRAPHS  76  15 cm SF Wetlands; 0-P04 1 4 0 . 0 0  1 2 0 . 0 0  1 0 0 . 0 0  E a. a  c o c o o c o o  8 0 . 0 0  6 0 . 0 0  4 0 . 0 0  2 0 . 0 0  0 . 0 0  Distance Through Wetlands (m)  I  • A p r i l - J u n e  July-Sept.  } Y e a r  A O c t . - D e c .  30 cm SF Wetlands; 0-P04 1 4 0 . 0 0  1 2 0 . 0 0  1 0  1  5  2  0  2  5  Distance Through Wetlands (m)  • A p r i l - J u n e  I  A O c t . - D e c .  July-Sept.  77  © Y e a r  Unplanted SSF Wetlands; 0-P04 140.00 j 120.00 •  20.00 0.00  J  1  0  1  5  1  10  15  1  1  1—•  1  20  25  30  35  Distance Through Wetlands (m)  • A p r i l - J u n e  • J u l y - S e p t .  ± O c t . - D e c .  © Y e a r  Planted SSF Wetlands; 0-P04 140.00  T  0.00 -I 0  1  1  1  5  10  15  •  1  1  1  1  20  25  30  35  Distance Through Wetlands (m)  •April-June  • July-Sept.  AOct.-Dec. 78  ©Year  15 cm SF Wetlands; Total Phosphorus 160.00  0.00 -I 0  t—•  5  1  1  10  15  H 20  1  1  25  30  Distance Though Wetlands (m) •April-June  BJul-Sept  ©Year  AOct-Dec  30 cm SF Wetlands; Total Phosphorus  160.00  10  15  20  25  Distance Though Wetlands (m) •April-June  AOct-Dec  Uul-Sept  79  ©Year  35  Unplanted SSF Wetlands; Total Phosphorus 160.00 T  '  Distance Through Wetlands (m) •April-June  • Jul-Sept  AOct-Dec  O Year  Planted SSF Wetlands; Total Phosphorus  160.00  Distance Through Wetlands (m) • April-June  • Jul-Sept  AOct-Dec  80  ©Year  15 cm SF Wetlands; Ammonia  35.00  0  5  10  15  20  25  30  35  Distance Though Wetlands (m) •April-June  aJul-Sept  AOct-Dec  ©Year  30 cm SF Wetlands; Ammonia  35.00 T  0.00 -I 0  :  1  1  5  10  • April-June  1  1  15 20 Distance Though Wetlands (m) BJul-Sept  AOct-Dec  81  1  25  ©Year  1  1  30  35  Unplanted SSF Wetlands; Ammonia  Planted SSF Wetlands; Ammonia  35.00  0.00 0  1  1  1  1  1  1  5  10  15  20  25  30  Distance Through Wetlands (m) • April-June  • Jul-Sept  AOct-Dec  82  ©Year  35  15 cm SF Wetlands; Nitrate 300.00  250.00  30 cm SF Wetlands; Nitrate  83  Unplanted SSF Wetlands; Nitrate 300.00  50.00 -  0.00 4 0  1  1  \-  1  1  1  1  5  10  15  20  25  30  35  Distance Through Wetlands (m) • April-June  • Jul-Sept  AOct-Dec  ©Year  Planted SSF Wetlands; Nitrate  400.00 j 350.00 --  0.00 -I 0  1  1  1  1  1  1  1  5  10  15  20  25  30  35  Distance Through Wetlands (m) • April-June  B Jul-Sept  AOct-Dec  84  ©Year  15 cm SF Wetlands; Total Kjeldahl Nitrogen 2 5  1 0  1  5  2  0  2  5  Distance Through Wetlands (m) • April-June  iJul-Sept  AOct-Dec  ©Year  30 cm SF Wetlands; Total Kjeldahl Nitrogen  ~  E Q. a  c o  1 2  1 0  c o  o  6  1 0  1  5  2  0  2 5  Distance Through Wetlands (m) • April-June  jJul-Sept  AOct-Dec  85  ©Year  3 0  3 5  Unplanted SSF Wetlands; Total Kjeldahl Nitrogen  0  5  10  15  20  25  30  Distance Through Wetlands (m) •April-June  HJul-Sept  AOct-Dec  ©Year  Planted SSF Wetlands; Total Kjldahl Nitrogen  Distance Through Wetlands (m) •April-June  BJul-Sept  AOct-Dec  86  ©Year  35  15 cm SF Wetlands; Total Orgaic Carbon 60.00 n  10.00  0.00 -I 0  1  1  5  10  1 15  1 20  1 25  Distance Through Wetlands (m) • A p r i l - J u n e • J u l - S e p t  AOct-Dec  © Y e a r  30 cm SF Wetjands; Total Organic Carbon  87  1 30  35  Unplanted SSF Wetlands; Total Organic Carbon 30.00  5.00  0.00  10  15  20  30  25  35  Distance Through Wetlands (m)  •April-June  • Jul-Sept  ©Year  AOct-Dec  Planted SSF Wetlands; Total Organic Carbon  40.00 35.00  5.00 0.00  10  15  20  25  30  Distance Through Wetlands (m)  • April-June  I Jul-Sept  88  AOct-Dec  ©Year  35  15 cm SF Wetlands; Total Solids  3.50  0.00 10  15  20  25  Distance Through Wetlands (m)  •April-June  Uul-Sept  AOct-Dec  ©Year  30 cm SF Wetlands; Total Solids  3.50  10  15  20  Distance Through Wetlands (m)  •April-June  gJul-Sept  AOct-Dec  89  ©Year  90  Ortho-phosphate Concentrations; Unplanted SF Wetlands 1 6 0 . 0 0  1 2 - A p r  0 2 - M a y  3 0 - M a y  2 7 - J u n  0 8 - A u g  0 5 - S e p  0 3 - O c t  3 1 - O c t  2 8 - N o v  Sampling Date (1996) G r e e n h o u s e E f f l u e n t  — H — 3 0 c m  U n p l a n t e d S F ( c e l l# 5 )  91  A  3 0 c m  U n p l a n t e d S F ( c e l l # 6 )  APPENDIX 3. STATISTICAL ANALYSES  92  Analysis of Variance Results N03-N  by  DATE REPLICATEE TYPE UNIQUE sums of squares  Source of Variation Main Effects DATE REPLICATE TYPE Explained Residual Total  Sum of Squares 1123583.667 888590.326 2299.705 209239.564 1123583.667 323799.078 1447382.746  All effects entered simultaneously DF 21 16 1 4 21 144 165  Mean Square 53503.984 55536.895 2299.705 52309.891 53503.984 2248.605 8772.017  F 23.794 24.698 1.023 23.263 23.794  Sig ofF 0.000 .000 .314 .000 .000  180 cases were processed. 14 cases (7.8 pet) were missing. Due to empty cells or a singular matrix, higher order interactions have been suppressed. 0_P04  by  DATE REPLICATE TYPE UNIQUE sums of squares  Source of Variation Main Effects DATE REPLICATE TYPE Explained Residual Total  Sum of Squares 113238.957 95676.978 6086.859 10912.540 113238.957 99485.501 212724.459  All effects entered simultaneously DF 22 17 1 4 22 153 175  Mean Square 5147.225 5628.058 6086.859 2728.135 5147.225 650.232 1215.568  F 7.916 8.655 9.361 4.196 7.916  Sig ofF .000 .000 .003 .003 .000  180 cases were processed. 4 cases (2.2 pet) were missing. Due to empty cells or a singular matrix, higher order interactions have been suppressed.  93  TKN  by  DATE REPLICATE TYPE UNIQUE sums of squares  Source of Variation  Sum of Squares 998.886 855.350 10.679 112.923 998.886 982.839 1981.726  Main Effects DATE REPLICATE TYPE Explained Residual Total  All effects entered simultaneously DF 18 13 1 4 18 117 135  Mean Square 55.494 65.796 10.679 28.231 55.494 8.400 14.679  F 6.606 7.833 1.271 3.361 6.606  Sig ofF .000 .000 .262 .012 .000  180 cases'were processed. 44 cases (24.4 pet) were missing. Due to empty cells or a singular matrix, higher order interactions have been suppressed. by  TOC DATE REPLICATE TYPE UNIQUE sums of squares  Source of Variation Main Effects DATE REPLICATE TYPE Explained Residual Total  Sum of Squares 23876.399 6609.883 306.478 17503.349 23876.399 9307.825 33184.224  All effects entered simultaneously DF 22 17 1 4 22 153 175  Mean Square 1085.291 388.817 306.478 4375.837 1085.291 60.835 189.624  F 17.840 6.391 5.038 71.929 17.840  Sig ofF .000 .000 .026 .000 .000  180 cases were processed. 4 cases (2.2 pet) were missing. Due to empty cells or a singular matrix, higher order interactions have been suppressed.  94  NH4  by  DATE REPLICATE TYPE UNIQUE sums of squares  Source of Variation  Sum of Squares  Main Effects DATE REPLICATE TYPE Explained Residual Total  7537.499 6757.611 16.055 723.532 7537.499 2864.832 10402.331  All effects entered simultaneously DF 22 17 1 4 22 152 174  Mean Square 342.614 397.507 16.055 180.883 342.614 18.848 59.784  F 18.178 21.091 1.852 9.597 18.178  Sig ofF .000 .000 .375 .000 .000  180 cases were processed. 5 cases (2.8 pet) were missing. Due to empty cells or a singular matrix, higher order interactions have been suppressed. T_SOLIDS  by  DATE REPLICATE TYPE UNIQUE sums of squares  Source of Variation Main Effects DATE REPLICATE TYPE Explained Residual Total  Sum of Squares 120.144 111.417 .000 8.541 120.144 155.304 275.447  All effects entered simultaneously DF 20 15 1 4 20 135 155  Mean Square 6.007 7.428 .000 2.135 6.007 1.150 1.777  F 5.222 6.457 .000 1.856 5.222  Sig ofF .000 .000 .985 .122 .000  170 cases were processed. 14 cases (8.2 pet) were missing. Due to empty cells or a singular matrix, higher order interactions have been suppressed.  95  TOTALP  by  DATE REPLICATE TYPE UNIQUE sums of squares  Source of Variation Main Effects DATE REPLICATE TYPE Explained Residual Total  Sum of Squares 201845.026 184169.500 341.496 16216.028 201845.026 72929.111 274774.137  All effects entered simultaneously DF 19 14 1 4 19 126 145  Mean Square 10623.422 13154.964 341.496 4054.007 10623.422 578.802 1894.994  F 18.354 22.728 .590 7.004 18.354  Sig ofF .000 .000 .444 .000 .000  170 cases were processed. 24 cases (14.1 pet) were missing. Due to empty cells or a singular matrix, higher order interactions have been suppressed.  96  Paired-Sample T-Test Results  Mean influent concentration and mean effluent concentration for each water quality parameter analyzed for each of the ten wetlands were used. Wetland cell numbering follows the numbering in Section 5 of the report body. Highlighted t-values indicate that there was no statistically defensible treatment effect observed. Paired-Sample T-tests to Determine Presence of Treatment Effect (a = 0.05) Cell# d.f.  1 2 3 4 5 6 7 8 9 10  10 10 12 12 12 12 12 12 12 12  Cell#  13 13 15 15 15 15 15 14 15 15  Cell# d.f.  1 2 3 4 5 6 7 8 9 10  -3.06 -2.70 -1.85 -1.77  -2.32 -4.03 -3.00 -3.13 -2.66 -2.44 NH -N t-value  11 11 13 13 13 13 13 13 13 13  -3.28 -3.06 -2.79 -2.79 -3.48 -3.97 -1.60  -2.34 -2.36 -2.57 TS t-value -1.25  -2.62 -1.14 -0.84 1.16 -0.71 0.42 -0.22 -0.45 1.16  0-P0 t-value 4  t-crit.  d.f.  -1.812 -1.812 -1.782 -1.782 -1.782 -1.782 -1.782 -1.782 -1.782 -1.782  13 13 15 15 15 15 15 15 15 15  -2.25 -2.81 -1.52  -1.88 -1.56  -6.54 -2.48 -3.81 -2.56 -2.41  t-crit.  d.f.  -1.771 -1.771 -1.753 -1.753 -1.753 -1.753 -1.753 -1.753 -1.753 -1.753  13 13 15 15 15 15 15 15 15 15  t-crit.  d.f.  NO3-N  4  d.f.  1 2 3 4 5 6 7 8 9 10  TP t-value  t-crit.  -1.771 -1.771 -1.753 -1.753 -1.753 -1.753 -1.753 -1.761 -1.753 -1.753  d.f.  12 12 14 14 14 14 14 14 14 14  t-value  -3.57 -5.86 -4.92 -4.91 0.07 -1.75  -1.79 -2.12 -1.69 -0.30  t-crit.  -1.796 -1.796 -1.771 -1.771 -1.771 -1.771 -1.771 -1.771 -1.771 -1.771  97  -1.782 -1.782 -1.761 -1.761 -1.761 -1.761 -1.761 -1.761 -1.761 -1.761  8 8 10 10 10 10 10 10 10 10  TOC t-value  4.84 5.93 4.91 9.15 0.24 -0.07 -0.63 -0.26 0.10 1.03 TKN t-value -0.02 0.11 -0.55 -0.91 -0.47 -1.11 -0.04 -1.40 -1.05 -1.02  t-crit.  1.771 1.771 1.753 1.753 1.753 1.753 1.753 1.753 1.753 1.753 t-crit.  -1.860 -1.860 -1.812 -1.812 -1.812 -1.812 -1.812 -1.812 -1.812 -1.812  Sheffe Test Results  Scheffe Tests to Determine if Treatment Effects Observed Are Different (a=0.05) Basin # 2 4 5 3. 6 7 8 9 1 0.764 2.395 2.364 1.551 9.384 0.070 1.390 0.003 2 6.004 5.956 4.615 4.668 1.364 0.076 0.913 3 0.000 0.091 21.261 1.644 7.434 2.235 4 0.085 21.170 1.619 7.380 2.205 5 18.566 0.961 5.877 1.423 6 1.080 3.551 9.710 7 2.086 0.045 8 1.517 9  O-PO4  10 0.208 1.847 1.191 1.169 0.623 12.388 0.036 2.674 0.163  Total P  Basin # 2 4 3 5 1 0.002 6.975 8.207 1.529 2 6.732 7.943 1.416 3 0.050 1.973 4 2.651 5 6 7 8 9  6 0.427 0.490 10.856 12.380 3.573  8 0.489 0.556 11.158 12.703 3.748 0.002 0.554  9 0.011 0.022 7.527 8.805 1.793 0.304 0.022 0.356  10 0.575 0.507 3.545 4.438 0.229 1.994 0.508 2.124 0.741  NH  Basin # 2 4 3 5 1 0.737 1.243 1.362 0.080 2 4.007 4.218 0.366 0.003 1.952 3 4 2.100 5 6 7 8 9  7 8 6 1.079 13.236 2.627 0.023 20.476 6.288 4.640 6.366 0.256 4.866 6.106 0.206 0.573 15.369 3.621 21.876 7.074 4.070  9 1.121 3.785 0.003 0.012 1.798 4.400 6.654 0.316  10 1.542 4.531 0.016 0.006 2.322 5.202 5.743 0.144 0.034  4  98  7 0.002 0.000 6.738 7.950 1.419 0.489  N0 -N 3  TOC  Fcritical  Basin # 1 2.453 0.031 0.141 2 3.230 3.986 3 0.040 4 5 6 7 8 9 Basin # 3 1 1.769 1.479 1.006 2 6.706 0.137 3 4.924 4 5 6 7 8 9  34.569  14.533 14.925  56.259  29.520  32.530  13.221 13.595 11.812 12.165 4.274 4.065 0.003  30.296  30.078  6  8 7.958  10 10.561  27.920  19.731  23.725  47.679  6.995 5.980 9.355 0.983 1.087  9.448 8.262 6.916 0.316 0.376 0.184  26.090  8  9  24.094  0.355 2.166 2.018 6.067 4.138 10  45.885  48.442  51.792  48.571  42.187  18.442  66.383  69.452  73.452  69.606  61.919  32.127  30.890  32.994  35.769  33.101  27.870  9.477  60.480  63.411  67.236  63.559  56.224  28.063  0.035  0.179 0.056  0.038 0.000 0.052  0.078 0.216 0.492 0.225  6.148 7.106 8.423 7.155 4.843  17.1  Highlighted F-values indicate that there was a statistically defensible difference in the treatment effect observed.  99  

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