SEASONAL IN-SITU AERATION IN CONSTRUCTED WETLANDS TO FACILITATE NITRIFICATION By Omar Al-Shafie A Project Presented to The Faculty of Humboldt State University In Partial Fulfillment of the Requirements for the Degree Master of Science In Environmental Systems; Environmental Resources Engineering Committee Membership Dr. Brad Finney, Committee Chair Dr. Margaret Lang, Committee member Dr. Robert Gearheart, Committee member Dr. Christopher Dugaw, Graduate Coordinator December 2014 ABSTRACT SEASONAL IN-SITU AERATION IN CONSTRUCTED WETLANDS TO FACILITATE NITRIFICATION Omar Al-Shafie Throughout most of the year, Arcata California is home to approximately 18,000 residents who are served by an innovative wastewater treatment plant that utilizes constructed wetlands to treat a range of flows from 1.0 MGD to 13 MGD. The City of Arcata is required to renew its National Pollutant Discharge Elimination System (NPDES) permit through the North Coast Regional Water Quality Control Board (NCRWQCB), which will dictate the need to reduce nitrogen levels compared to current effluent values. This project explores facilitating the nitrification and denitrification process with an in-situ aeration system, which has the potential to reduce nitrogen levels to assumed requirements on the next NPDES permit issued by the NCRWQCB. The City of Arcata is required to comply with the renewed NPDES permit standards by January 27, 2017. The primary objective of this study is to determine the nitrogen removal efficiency of a small-scale in-situ aeration system for the Arcata Wastewater Treatment Facility (AWTF). The aquaphyte, a scaled down treatment marsh was built, planted, and aerated to observe the nitrification and denitrification process, which converts ammonia nitrogen ii in the wastewater to di-nitrogen in the atmosphere. Design parameters were altered to determine which variables have the greatest influence on the conversion of ammonia to nitrate (nitrification) and nitrate to di-nitrogen (denitrification). Aerating the aquaphyte proved to be an effective method to reduce ammonia concentrations. This experiment was scaled up to a larger system in Treatment Wetland - 4 (TW- 4) to determine if the 98% reduction of ammonia concentrations seen in the aquaphyte could be replicated. There were many variables that created a divergence of similitude between the Aquaphyte and TW–4, and the results observed in the aquaphyte did not translate to the aeration system installed in TW-4. Operating conditions in the aeration system and inflows into TW-4 were altered to find similar operating parameters as the aquaphyte. TW-4 has been operating as a treatment marsh for approximately 35 years and has developed a substantial volume of nitrogen in the form of biomass from plant growth and senescence cycles, accreted ammonia that has precipitated into the wetland soil, and settled algal solids. The accumulation of biomass was the primary difference between the aquaphyte and TW-4. Influent loading into both systems was pumped from the same source (Oxidation pond 2). Nonetheless, the oxygen that was transferred into TW-4 to facilitate nitrification appeared to be consumed by the carbonaceous oxygen demand that was created from the accumulation of biomass throughout its operation. Therefore, the larger scale TW-4 nitrification system experiment resulted in little to no ammonia reduction. iii NOMENCLATURE AWTF Arcata Wastewater Treatment Facility BOD Biological Oxygen Demand CBOD Carbonaceous Biological Oxygen Demand DO Dissolved Oxygen EPA Environmental Protection Agency gpm Gallons per minute HRT Hydraulic Retention Time MGD Million Gallons per Day mg/L Milligrams per liter NBOD Nitrogenous Biological Oxygen Demand NCRWQCB North Coast Regional Water Quality Control Board NPDES National Pollution Discharge Elimination System SCFH Standard Cubic Feet per Hour SCFM Standard Cubic Feet per Minute TSS Total Suspended Solids TW- 4 Treatment Wetland – 4 iv ACKNOWLEDGEMENTS I want to thank Dr. Brad Finney, Dr. Bob Gearheart, Dr. Margaret Lang, Dr. Eileen Cashman, Dr. Stewart Oakley, Dr. Peter Rohloff, Britany MacFarlane, Mary Burke, Charles Swanson, Heidi Halverson, Lauren Adabie, William Karis, Cody Bowers, Meagan Butler, Nicole, Mama J, Mama Hen, Pachamama, Mama Aya, Machute, Sitee, Abuelito, Tata, Pops, Papa J, Brendo, Jaymes, Kriz, Bo Beau, Deepah, Shani, the family of river otters that live at the Marsh, and all my plant allies for your support and guidance. v TABLE OF CONTENTS ABSTRACT........................................................................................................................ ii NOMENCLATURE .......................................................................................................... iv ACKNOWLEDGEMENTS ................................................................................................ v TABLE OF CONTENTS ................................................................................................... vi LIST OF TABLES ........................................................................................................... viii LIST OF FIGURES ........................................................................................................... ix INTRODUCTION .............................................................................................................. 1 REVIEW OF LITERATURE ............................................................................................. 3 Global Nitrogen Cycle .................................................................................................... 3 Conventional Wastewater Treatment.............................................................................. 5 Oxygen Transfer ............................................................................................................. 7 Submerged Diffused Bubble Systems ............................................................................ 9 Wetlands for Wastewater Treatment ............................................................................ 10 Wetland Nitrogen Cycle ............................................................................................... 12 Ammonification ............................................................................................................ 14 Nitrification and Denitrification ................................................................................... 15 Vegetation Effects......................................................................................................... 17 Temperature Effects ...................................................................................................... 21 Artificial Aeration ......................................................................................................... 22 METHODology ................................................................................................................ 24 Aquaphyte ..................................................................................................................... 24 vi Treatment Wetland Four ............................................................................................... 30 Monitoring and Laboratory Analysis ............................................................................ 38 RESULTS and Discussion ................................................................................................ 39 Aquaphyte ..................................................................................................................... 39 Effects of temperature on the rate of nitrification. .................................................... 39 Effects of aeration on nitrification. ........................................................................... 49 Media and contact time. ............................................................................................ 58 Scale Up: Treatment Wetland 4 .................................................................................... 62 Water quality analysis. .............................................................................................. 62 DO and BOD. ............................................................................................................ 64 Nitrogen dynamics. ................................................................................................... 72 Media and fouling. .................................................................................................... 76 Quantifying internal load contribution...................................................................... 77 COMPARISON ............................................................................................................ 80 Conclusion ........................................................................................................................ 82 Recommendation .......................................................................................................... 83 REFERENCES ................................................................................................................. 86 Appendix A ....................................................................................................................... 91 Operational parameters ................................................................................................. 91 Aquaphyte water quality data ....................................................................................... 95 Treatment Marsh 4 water quality data ........................................................................ 101 Normalized calculations tables ................................................................................... 106 vii LIST OF TABLES Table 1: Devices for aeration systems (adapted from Metcalf and Eddy, 2003) ................ 9 Table 2: Primary nitrogen pathways in constructed wetlands (adapted from Vymazal, 2007) ................................................................................................................................. 14 Table 3: Nutrient removal potential of common treatment wetland plant species (adapted from Kadlec and Knight, 1996) ........................................................................................ 19 Table 4: aquaphyte dimensions and hydraulic retention time .......................................... 24 Table 5: Water flow and typical loading into aquaphyte .................................................. 25 Table 6: Estimated available surface area for a submerged depth of 0.6 m, bolded numbers were used in calculations (adapted from Lagace, 2000). ................................... 29 Table 7: Estimated surface area of submerged plant biomass in aquaphyte within the volume of water containing DO concentrations above 1.0mg/l (using data from Lagace, 2000). ................................................................................................................................ 29 Table 8: Dimensions and HRT of one channel in Treatment Wetland 4. ......................... 30 Table 9: Water flow rate, typical ammonia loading, typical BOD loading, airflow, and HRT into experimental cell of Treatment Wetland – 4 .................................................... 32 Table 10: Estimation of available surface area on the additional plastic media; it is assumed that 70% of area is available. ............................................................................. 37 Table 11: Percent removal of ammonia, NBOD, CBOD with average temperatures above and below 10oC (based on 21 samples) ............................................................................ 46 Table 12: Aquaphyte performance winter of 2010; average temp 10.5oC, average influent concentration 32.5mg/l, with aeration .............................................................................. 49 Table 13: Reaction of water quality parameters throughout the period of aeration ......... 50 Table 14: Residence time within media, mass of oxygen within contact volume, and mass of oxygen per square foot of surface area on 3/20/14 ....................................................... 61 Table 15: Comparison of results; normalized values between the two systems; a transfer efficiency of 20% was assumed; 20.95% oxygen concentration in air was assumed....... 81 viii LIST OF FIGURES Figure 1: Overhead view of Arcata Wastewater Treatment facility (AWTF) indicating component locations. .......................................................................................................... 1 Figure 2: Oxidation/reduction pathways available for Nitrogen (image from: Reddy, 2008) 1. Ammonification 2. Immobilization 3. Nitrification 4. Denitrification 5. Dissimilator nitrate reduction to ammonia, 6. Di-nitrogen fixation, 7. Ammonia volatilization. ...................................................................................................................... 5 Figure 3: Nitrogen pathways within Wetland system (adapted from Kadlec, 2008)........ 12 Figure 4: Photo of aquaphyte adjacent to oxidation pond 2 ............................................. 26 Figure 5: Diagram of aquaphyte with sample ports and equipment. ................................ 27 Figure 6: Existing plant growth within aquaphyte water column. .................................... 28 Figure 7: Aeration system installed in Treatment Wetland 4. .......................................... 33 Figure 8: Diagram of Treatment Wetland 4 aeration system, sample ports, and pier. Water flows in from the bottom right corner of the diagram and past the sample ports indicated in red with distance from aeration system. ....................................................................... 34 Figure 9: Left photo indicates the wooden frame containment and media. Right photo was the chicken wire “bags” that contained large honey comb media and strapping material. Both were installed into Treatment Marsh 4 to facilitate nitrification.............................. 35 Figure 10: Operation of the aeration system installed in Treatment Marsh 4 downstream of the constructed pier. ...................................................................................................... 36 Figure 11: Aquaphyte performance with no aeration and cold temperatures 1/4/13; average temperature 7.4oC. Sample ports are equally spaced along the length of the aquaphyte .......................................................................................................................... 41 Figure 12: Total BOD characterized as NBOD and CBOD, average temp 7.4oC (01/04/13).......................................................................................................................... 42 Figure 13: Total BOD average temp 6.9oC 1/11/13 ......................................................... 43 ix Figure 14: Ammonia reduction in the aquaphyte on 4/12/14; average temp 12.6oC ........ 45 Figure 15: Temperature vs. Ammonia removal over time; large increase in removal efficiency is a result of operating the aeration system. ..................................................... 47 Figure 16: Constant head flow regulation; average temp 8.1oC; 34% ammonia reduction (2/08/13)............................................................................................................................ 51 Figure 17: Total BOD concentrations during period of aeration; average temp. 12.3oC (2/17/13)............................................................................................................................ 52 Figure 18: One week after install of peristaltic pump flow regulation; average temp 7.9oC; (2/22/13), 28 days after aeration began ................................................................. 55 Figure 19: (3.10.13); 100% reduction in NBOD, 50% reduction in CBOD ..................... 56 Figure 20: 4.05.13; 70 days of aeration operation; average temperature 13.3oC; 50 scfh 57 Figure 21: Garrison, average temp 12.5oC, with plastic media, influent concentration of 27.21ppm, air flow 70 scfh ............................................................................................... 59 Figure 22: Nitrogen dynamics on 3.20.14; average temperature 12.2oC, no installed plastic media ..................................................................................................................... 60 Figure 23: The initial pilot project, Treatment Marsh 4, on September 3, 1980. The system was designed and operated in series with 10 separate treatment cells (W= 20' x L = 200' x D = 2') Initially, the treatment cells alternated plantings from Bulrush to Cattail. Plant biomass was still sparse and developing. ................................................................ 63 Figure 24: TW-4 in the Summer 2013 after 35 years of loading with municipal wastewater. Biomass development is extensive when compared to Figure 23. It now operates in parallel with a sinusoidal flow pattern. Cattail has emerged as the dominant macrophyte. ....................................................................................................................... 64 Figure 25: Total BOD reduction of 30% on 5/22/13 indicating that the DO was being consumed .......................................................................................................................... 65 Figure 26: Total BOD reduction with DO consumption on 6/6/13 .................................. 66 Figure 27: Total Biological Oxygen Demand (BOD) reduction (6.26.13); with wooden frames and two weeks after installation of wire bags ....................................................... 68 Figure 28: 7/17/13; 68% reduction in NBOD, 74% reduction CBOD ............................. 69 Figure 29: Dissolved oxygen concentration TW 4 after removal of wire bags (7.25.13). 70 x Figure 30: 50% reduction of total BOD 9.17.13, final media configuration, installed downstream of aeration system. ........................................................................................ 71 Figure 31: 5/30/13 ammonia reduction of 32% (2.8mg/l), peak DO concentration 2.5mg/l, slight increase in nitrate (1.6mg/l) within the zone of elevated DO ................................. 72 Figure 32: Performance two weeks after installation of wire bags (6/26/13). .................. 74 Figure 33: Nitrogen dynamics of system 22 days after final configuration of media (wire bags) downstream of aeration system; 9.09.13 ................................................................. 75 Figure 34: Microbial growth on membrane diffusers; half brushed off to observe extent of fouling ............................................................................................................................... 77 Figure 35: Ammonia concentrations throughout the year for all treatment marshes and pond 2................................................................................................................................ 78 Figure 36: Ammonia effluent concentrations throughout 2012 ........................................ 79 xi 1 INTRODUCTION Arcata California is located on the coast in the Pacific Northwest approximately 100 miles south of the Oregon border. To treat the City’s wastewater, the Arcata Wastewater Treatment Facility (AWTF) utilizes conventional headworks technology, which consists of a bar screen, grit chamber, and primary clarifier to mitigate the loading of solids to secondary treatment processes. The total footprint of AWTF is approximately 90 acres. Two oxidation ponds, totaling 40 acres, have been in operation since the 1950s, and for about the past 30 years, AWTF has been using treatment marshes for their secondary and tertiary treatment. The existing area of treatment marshes is approximately 10 acres, and the enhancement marshes have an area of 30 acres (Figure 1). Headworks Previous Hatchery Ponds Figure 1: Overhead view of Arcata Wastewater Treatment facility (AWTF) indicating component locations. 2 Humboldt State University is within the city limits of Arcata and effectively doubles the population to approximately 18,000 residents while school is in session. The flow rates into the treatment plant have large fluctuations, seasonally from a 1.0 MGD summer time low to a 13 MGD winter high. The city of Arcata needs to renew its NPDES permit, which will require them to reduce effluent ammonia nitrogen levels compared to current discharge concentrations during cold weather months. The standards set by the NCRWQCB will likely target effluent limits on ammonia concentrations; however, the limits and timeline for Arcata to comply are uncertain. The purpose of this project is to investigate a system Arcata can implement, which will reduce ammonia concentrations through nitrification and denitrification during cold weather months when the natural processes of the oxidation ponds and treatment marshes are inhibited. 3 REVIEW OF LITERATURE Global Nitrogen Cycle Nitrogen is one of the most abundant elements on this planet and is a critical nutrient for all life. The nitrogen cycle is intimately linked to the carbon cycle to effectively regulate primary biomass production of aquatic and terrestrial ecosystems (Thamdrup, 2012). Both cycles have been drastically altered with the increase of human population, development of infrastructure, and industrialization. Agriculture is the greatest contributor of nitrogen to the environment. The discovery and invention of providing ammonia from atmospheric nitrogen has created an on going source for use as a fertilizer. This has allowed humans to dramatically increase food production, bypassing cover crops and microbial communities (Vymazal, 1995). The consequence of this method of food production creates an imbalance in the nitrogen cycle. Accordingly, human influenced alterations to the global nitrogen cycle have generated results such as; increased nitrogen input into the land based nitrogen cycle, increased emissions of nitrous oxide (N2O), reduction of soil nutrients (calcium and potassium), significant changes to aquatic and terrestrial ecosystems, and alterations to the carbon cycle (Vitousek, 1997). Excess nitrogen leaches from agriculture runoff into surface waters resulting in a modification of nutrient ratios and ultimately eutrophication. Blooms of particular phytoplankton will dramatically affect the water chemistry and can be detrimental to aquatic life, due to changes in pH, fluctuations in dissolved oxygen concentrations, and increased 4 accumulation of organic material (Eilers, 2008). Additionally, civil infrastructure contributes to these alterations through nitrogen loading of surface waters. High-density developments and industry production generate concentrated point source waste streams and emissions. Consequently, municipal wastewater contains pollutants and nutrient concentrations that are toxic to aquatic life if directly discharged to surface waters. Vitousek (1997) suggests that human influence on the nitrogen cycle has environmental consequences related to soil health, aquatic ecosystem health, and alterations to atmospheric composition. As the understanding of the nitrogen cycle increases, it becomes more evident that it is necessary to reduce loading to aquatic ecosystems. Fortunately, nitrogen speciation has become better understood and technology has advanced to facilitate nitrogen removal of infrastructural waste streams. Municipal wastewater treatment plants typically utilize two methods for removal, biological or physical treatment. Biological treatment and removal of nutrients relies on microbial communities to convert nitrogen into its many different forms (Davis, 2011). These different forms of nitrogen are dependent upon microbial metabolisms that influence the nitrogen cycling, which are dictated by the oxidation-reduction potential of the wastewater (Figure 2) (Reddy, 2008). 5 Figure 2: Oxidation/reduction pathways available for Nitrogen (image from: Reddy, 2008) 1. Ammonification 2. Immobilization 3. Nitrification 4. Denitrification 5. Dissimilator nitrate reduction to ammonia, 6. Di-nitrogen fixation, 7. Ammonia volatilization. Conventional Wastewater Treatment Environmental engineers and wastewater treatment plant operators design and control reaction chambers that remove nitrogen from municipal wastewater. This can be accomplished by creating ideal conditions for the microbial communities existing within wastewater to remove nitrogen. Autotrophic bacteria utilize carbon dioxide for cell creation and are much slower growing than the heterotrophs that use organic carbon for 6 cell development; both of which can be further classified as chemo-autotroph or chemoheterotrophs that derive their energy from the oxidation of inorganic and organic compounds, respectively (Metcalf and Eddy, 2003). Typically, suspended growth or attached growth systems are utilized when reducing nutrient loads of municipal wastewater in conventional wastewater treatment facilities. Activated sludge systems are a very common application of suspended growth design in the treatment of wastewater for nutrient reduction. Suspended growth systems retain and feed microorganisms through energy intensive aeration systems creating active microbial cultures that are recycled to break down nutrient inflows (Davis, 2011). Effluent from the reaction chamber flows into a clarifier where the solids (microbial biomass) settle and condense into what is known as activated sludge due to the high concentrations of micro-organisms and diverse microbial ecology (Davis, 2008). This culture is recycled back to the reaction chamber as Return Activated Sludge (RAS) where it meets influent flows with high concentrations of nutrients and is supplied with sufficient oxygen to facilitate the process of converting ammonia to nitrate (nitrification) (Metcalf and Eddy, 2003). Although effective, this process is typically the highest consumer of energy in wastewater treatment plant operations due to the mixing and aeration requirements. Alternatively, attached growth systems do not require as much energy to operate. These designs utilize the same microorganisms as suspended growth systems; yet provide physical substrate for the formation of microbial biomass or biofilm (polysaccharides concentrated microbial communities) (Metcalf and Eddy, 2003). The higher the surface 7 area of substrate, the more available sites for attachment. Conventional technologies like Trickling filters or Bio-towers are the most common method for treatment plants to utilize the attached growth process (Nourmohammadi, 2012). Influent flows are directed through a distribution mechanism that sprays the wastewater over the packing material (plastic media) and as the water moves down through the media it is passively aerated. Through the consumption of ammonia ions and the presence of oxygen, biofilm is created and accumulates, eventually detaching and flowing out with the effluent (Davis, 2008). Due to the volume of biofilm that is generated, clarifiers are constructed downstream of the trickling filter to settle out the accumulated solids. Energy requirements for trickling filters are generally lower than that of suspended growth designs such as activated sludge; however, they require a longer period of time to develop biofilm in order to meet effluent quality standards. If maintenance issues occur and loading ceases, the biofilm will die. This can cause operational problems, a period of decreased effluent quality, and potential regulatory violations. To effectively facilitate nitrification, both suspended growth and attached growth systems rely on the transfer of oxygen into the water column, either passively or actively. Oxygen Transfer Transferring oxygen into wastewater requires a substantial and continuous energy investment or a large area of land to utilize solar radiation. An aerobic environment will initiate the metabolism of microorganisms that breakdown organic material (EPA, 1999). 8 Oxidation ponds are very effective in transferring oxygen through algal photosynthesis, and this method is typically used in alternative treatment systems, such as AWTF. Oxygen transfer will vary depending upon the characteristics of the wastewater, method of aeration, and parameters of the reaction chamber (Metcalf and Eddy, 2003). The latter two dependencies can be controlled by design and operation of the wastewater treatment facility. Conventional treatment utilizes active aeration to transfer oxygen, which is typically the most energy intensive activity in wastewater treatment plant operations. In order to reduce costs, dissolved oxygen concentrations are measured at the water surface of the reaction chamber and operations are adjusted to keep those concentrations below or approximately1.0 mg/l. There are generally two types of aeration systems: submerged and surface (EPA, 1999). Submerged aeration systems are installed below the water surface where air is pumped through diffusers. Surface aeration systems generally rely on mixing at the water surface to facilitate oxygen transfer. Some commonly used aeration devices are presented in Table 1. 9 Table 1: Devices for aeration systems (adapted from Metcalf and Eddy, 2003) Classification Diffused fine bubble system Description Submerged Ceramic, plastic, and flexible membranes Diffused course bubble system Orifices, injectors, nozzles, or shear plates Sparger turbine low speed turbine and compressed air injection Tubes with internal baffles, air injected and retained at the bottom of tube Surface Large diameter turbine which exposes liquid to atmosphere propeller expose liquid to atmosphere Inclined propeller assembly Water flows over steps Static tube mixer Low speed turbine aerator High speed floating aerator Aspirating Cascade Application Activated sludge process Activated sludge, channel or grit chamber aeration, and anaerobic digestion Activated sludge and aerobic digestion Aerated lagoons and activated sludge Activated sludge, aerated lagoons, and aerobic digestion Aerated lagoon and aerobic digestion Aerated lagoons Post-aeration Submerged Diffused Bubble Systems There are many systems available for oxygen transfer in wastewater treatment, yet submerged diffused bubble systems will be used in this investigation. Submerged diffused bubble systems can be categorized into fine or coarse bubble diffusion, usually depending upon bubble size and therefore transfer efficiency; however, the exact definitions between the two systems are still ambiguous (Metcalf and Eddy, 2003). 10 Porous diffusion systems are generally characterized as using a disk, dome, membrane, or panel to transfer oxygen into liquid (Davis, 2011). These can come in many configurations and are generally designed for conventional activated sludge chambers that are typically 12-15 ft in depth. The materials used to manufacture these diffusors range from: rigid ceramic/plastic, flexible plastic, rubber or cloth (Metcalf and Eddy, 2003). Membrane diffusers are fine bubble diffusers that are designed to transfer oxygen into the water column in addition to mixing and circulating air at the surface of the open water to promote the transfer of oxygen into solution (Metcalf and Eddy, 2003). These oxygen transfer systems are typically used in conventional wastewater treatment systems that have limited space and available capital for operation. Small communities, with limited capital, often have access to available land for alternative systems that utilize solar radiation to generate necessary oxygen requirements. Wetlands for Wastewater Treatment Treatment wetlands have been used for water quality improvements throughout the world since the 1950’s and usage in the United States has increased in the past 35 years (Verhoeven, 1999; Kadlec, 2009). These natural systems provide an alternative passive option to energy intensive conventional methods for small municipalities to treat their 11 wastewater, which also provides community resilience to large climate and energy market fluctuations. Oxidation ponds are typically used in alternative wastewater treatment systems to fulfill the oxygen demand of municipal wastewater. When combined with treatment wetlands, the two can produce enhanced effluent quality. The algae produced within oxidation ponds flow into treatment wetlands planted with emergent macrophytes. Solar radiation is reduced and the algae die and settle to form a layer of decomposing algal biomass. Constructed wetlands have proven to be an effective method to improve municipal wastewater quality when combined with primary treatment mechanisms (EPA, 1999). Engineers and scientists are still attempting to understand and determine what parameters of design are needed to facilitate an increase in effluent water quality. Two general configurations that have been studied, Free Water Surface (FWS) wetlands and Subsurface Flow Wetlands (SFW); both types have proven to be effective mechanisms to improve water quality (Kadlec, 2008). Conventional biological treatment can control the types of dominant microorganisms through slight variation in design parameters and inputs. Constructed wetlands utilize natural ecosystems that perform relative to the climate, temperature, and concentration of dissolved oxygen. In order to meet discharge requirements, constructed wetland systems in cold climates require operational schedules that differ according to seasonal changes in effluent quality. There is opportunity for innovation in the design and operation of constructed wetlands and their capacity for nitrogen speciation and reduction. 12 Wetland Nitrogen Cycle Innovation in treatment wetland design has been spurred by the need for nitrogen reduction (Austin, 2002). The nitrogen cycle in wetlands is very complex and is not fully understood (Figure 3). Figure 3: Nitrogen pathways within Wetland system (adapted from Kadlec, 2008) Nitrogen has many pathways within a constructed wetland system. Typical nitrogen sources of input into an engineered wetland system are atmospheric nitrogen fixation by algal microorganisms, agriculture/urban (stormwater) runoff, and human waste (Reddy, 13 2008). Physical transportation of nitrogen within wetland systems can be broken down into the following seven pathways: particulate settling and re-suspension, diffusion of dissolved forms, plant uptake and translocation, litter fall, ammonia volatilization, adsorption of soluble nitrogen on substrates, and organism migration (Kadlec, 2008). Treatment wetlands receive the majority of nitrogen from nutrient enriched municipal wastewater. Organic forms of nitrogen enter the system within municipal wastewater predominately in the form of Urea, a by-product of human waste, which can be hydrolyzed and changed into different valence states (Vymazal, 1995). There are five primary processes of nitrogen speciation: ammonification (mineralization), nitrification, denitrification, nitrogen fixation, and nitrogen assimilation (Kadlec and Knight, 1996). Primary nitrogen pathways within constructed wetlands are summarized in Table 2. 14 Table 2: Primary nitrogen pathways in constructed wetlands (adapted from Vymazal, 2007) Process Transformation Ammonification Organic-N (urea) -> ammonia-N Nitrification Ammonia-N -> nitrite-N -> nitrate-N Nitrate-ammonification Nitrate-N -> ammonia-N Nitrate-N -> nitrite -> gaseous N2, N20 Ammonia-N (aqueous) -> ammonia-N (gas) Ammonia, nitrite, nitrate-N -> organicN Denitrification Volatilization Plant/microbial uptake (assimilation) ANAMMOX (anaerobic ammonia oxidation) Ammonia-N -> gaseous N2 Ammonification Organic nitrogen enters and cycles within the system as a byproduct of human waste (Urea) or plant and animal biomass (Vymazal, 1995). The majority of organic nitrogen entering a wetland system is converted to ammonium (inorganic nitrogen). This process is called ammonification, which is dependent on the rate that existing organic material is being degraded (Kadlec, 2008; Reddy, 2008). The chemical process of Urea transformation is presented in equation 1 (Kadlec, 2008): 𝑁𝑁𝐻𝐻2 𝐶𝐶𝑂𝑂𝑂𝑂𝑂𝑂 + 𝐻𝐻2 0 2𝑁𝑁𝑁𝑁4 + 𝐶𝐶𝐶𝐶2 (1) 15 Ammonium is the initial conversion of nitrogen within municipal wastewater treatment. However, during laboratory analysis ammonium is converted to ammonia with a buffer solution that dramatically increases pH and converts all ammonium in the wastewater sample to ammonia. This report will now refer to ammonium concentrations as ammonia (NH4). Nitrification and Denitrification To effectively remove nitrogen from the system it is necessary to promote the processes of nitrification and denitrification. Parameters that influence the nitrification process include temperature, hydraulic retention time, type and density of plant species, existing microbial communities, climate, and wastewater characteristics (Chang-gyun, 1990). Nitrifying bacteria (Nitrosococcus, Nitrospira, Nitobacter, Nitrosomonas) are characterized as autotrophic that utilize ammonia ions for energy and require an aerobic environment to convert ammonia to nitrite (Reddy, 2008; Nogueira et al., 2000). The conversion of ammonia to nitrate is primarily generated by chemolithotrophic bacteria that are only capable of respiring under aerobic conditions (Vymazal, 2007). Additionally, heterotrophic bacteria are facultative and also have the ability to nitrify (Chang-gyun, 1990; Vymazal, 1995). Nitrite (NO2-) is the interim product of the nitrification process, however it is typically short lived and a variety of bacteria can convert the nitrite to nitrate. Many microbial communities, and some fungi, have the 16 capability to denitrify in facultative conditions (Wallace, 2006). Stoichiometries in equations 2-4 show the transformation of nitrogen in the nitrification and denitrification processes (Medcalf and Eddy, 2008). Nitrification: Ammonia to nitrite (Nitrosonomonas) 3 𝑁𝑁𝑁𝑁3 + �2� 𝑂𝑂2 𝐻𝐻𝐻𝐻𝐻𝐻2 + 𝐻𝐻2 𝑂𝑂 (2) Nitrite to nitrate (Nitrobacter) 3 𝑁𝑁𝑁𝑁3 + �2� 𝑂𝑂2 𝐻𝐻𝐻𝐻𝐻𝐻2 + 𝐻𝐻2 𝑂𝑂 (3) Denitrification: Nitrate to di-nitrogen 1 3 2 1 �3� 𝑁𝑁𝑁𝑁2− + �2� 𝐻𝐻 + + 𝑒𝑒 − �3� 𝐻𝐻2 𝑂𝑂 + �6� 𝑁𝑁2 (4) Heterotrophic bacteria are facultative and can function with anaerobic or aerobic respiration depending upon the environmental conditions. These bacteria exist in the microbial communities of wastewater and they are the initial consumers of existing oxygen if excessive organic carbon is present (Gearheart, 1965). Due to the higher energy content of oxidized organic carbon, the heterotrophs are stimulated to reduce the 17 carbonaceous load (CBOD). In addition to dissolved oxygen concentrations and temperature, nitrification of ammonia is dependent upon the amount of available organic carbon (Wallace, 2006). Heterotrophic bacteria require carbon to facilitate the denitrification process, yet if excessive carbon is present they will dominate the microbial consumption of available oxygen. If sufficient oxygen is not supplied to the system then the heterotrophic bacteria inhibit the process of the autotrophs necessary to initiate the reduction of the nitrogenous load (NBOD), and ultimately ammonia conversion (Nogueira et al., 2000). These processes naturally occur within the rhizome region of plant growth where there is potential for an oxygenated environment (Kadlec, 2008). Accordingly, wetland vegetation plays a role in the influence on nitrification in wetland systems. Vegetation Effects Wetland ecologies have an assortment of different flora. Treatment mechanisms utilize vegetation for physical, ecological, and biological functions. Constructed wetland ecosystems have a multitude of ancillary benefits that are primarily associated with the abundant vegetation: wildlife habitat creation, recreational use, and beneficial economic externalities. The primary benefit of the wetland biota is its innate ability to improve degraded water quality (Maltais-landry, 2009). Accordingly, orientation of planting regimes and types of plants used can have an effect on the effluent quality of constructed wetlands. Nitrogen can be stored and essentially remain in the system through the 18 process of plant uptake and senescence where it becomes a part of nutrient cycling, peat formation and burial, and settled algae biomass (Kadlec, 2008). Harvesting the plants is required to fully remove nitrogen that is locked in the plant nutrient cycling. As in nature, plants in constructed wetlands can also act as surface area for the attachment of nitrifying bacteria to better facilitate the nitrification process. This surface area would reduce the need for additional plastic media when considering design for nitrogen removal. Table 3 indicates biomass development and nitrogen uptake of common plants found in a treatment wetland. In temperate climates, such as those in Arcata, the typical successional species of plants that eventually dominate the wetland ecosystem are Typha spp. and Scirpus spp. (Verhoeven, 1999). Burke (2011) found that Typha latifolia and Scirpus acutus at AWTF together accumulated a combined 996 kg/ha of nitrogen and 159 kg/ha of phosphorous. 19 Table 3: Nutrient removal potential of common treatment wetland plant species (adapted from Kadlec and Knight, 1996) Species Nitrogen Phosphorus Stock Growth Stock Growth (kg/ha) (kg/ha/year) (kg/ha) (kg/ha/year) Typha 250-1,560 600-2,630 45-375 75-403 Juncus 200-300 800 40 110 Scirpus 175-530 125 40-110 18 Phragmites 140-430 225 14-53 35 Eichhornia craspies 300-900 1,950-5,850 60-180 350-1,125 pistia stratiotes 90-250 1,350-5,110 20-57 300-1,100 90-300 540-3,200 23-75 130-770 240-425 1,400-4,500 30-53 175-570 Lemna minor 4-50 350-1,200 1-16 116-400 Salvinia 15-90 10.4-213 4-24 92-450 Hydrocotlye Alternanthera Philoxeroids In northern climates the rate of nutrient uptake by macrophytes within a constructed wetland system varies with seasonal growth and senescence. As indicated in Table 3 20 plant species can have large differences in nutrient accumulations. Harvest of the dominant emergent macrophytes is an effective method to remove nitrogen from the system, although this would increase operation and maintenance costs. Orientation of planting regimes can also have an influence on total nitrogen concentration within the wastewater effluent. Garcia-Lledo (2011) found that macrophyte coverage at the inlet achieved higher removal efficiencies of nitrate and ammonia when compared to vegetation coverage at the outlet. Through photosynthesis, plants and algae transfer oxygen into the water column, the concentration of dissolved oxygen is subject to diurnal and seasonal changes, especially in cold climates. During the warmer months, higher temperatures and increased solar radiation stimulate algal blooms in oxidation ponds or any exposed water surface in treatment marshes. Algal blooms super saturate the wastewater with DO to reduce the ammonia concentration through nitrification for a part of the year. Constructed wetlands in cold climates cannot sustain high dissolved oxygen concentrations throughout the year and may require mechanical aeration units to ensure total nitrogen removal. In addition to oxygen limitations and vegetation effects, temperatures regulate the nitrification process due to the reduced microbial activity during winter months (Wallace, 2006). 21 Temperature Effects Temperature may have the greatest effect on the nitrification process. Microorganisms that facilitate nitrification have varying sensitivities to temperature, and each metabolism is affected differently. Ideal temperature ranges that energize biological processes depend upon the characteristics of the wastewater, operation of the treatment facility, and the wetland ecosystem (soil, vegetation, and climate) (Kadlec, 2001). Compared to most places on this planet, Arcata, CA experiences small fluctuations in ambient temperature, which lowers water temperatures below 10oC. Kadlec (2001) suggests that nitrification is seriously inhibited at temperatures below 10oC; however, it is difficult to project if wastewater at the AWTF will generate the same temperature thresholds. Werker (2002) found that the rate of nitrification quickly declines to zero as water temperatures drop below 6oC, which can also be sporadically experienced at AWTF. Accordingly, to generate appropriate levels of nitrification in constructed wetlands during cold periods and slow biological reaction rates of microbial processes, it is necessary to design treatment wetland cells with a higher capacity for nutrient and BOD removal. However, many municipalities like Arcata have limited land area available to increase treatment capacity. In-situ aeration could be a viable option if temperature doesn’t substantially inhibit nitrification during operation of the aeration system. 22 Artificial Aeration The ammonia removal capacity in a constructed wetland system can be directly facilitated through artificial aeration and the nitrification and denitrification speciation pathway. Seasonal variations in climate and solar radiation in colder regions reduces the rate of algal and macrophyte photosynthesis, thereby reducing oxygen production. Input of oxygen through an aeration system can provide sufficient transfer to initiate the metabolism of nitrifying bacteria. Aeration systems may be useful within many regions of the world where temperature fluctuations inhibit the nitrification process. Cottingham (1998) indicates that an aeration unit can increase ammonia transformation from 18% to 68% with dissolved oxygen concentrations ranging from 2.8 to 4.6 mg/l. This experiment was tested in a horizontal subsurface flow treatment cell that had 3 years of plant growth and was 30m long, 5m wide, and 0.6m deep. There were low rates of denitrification in this treatment cell because of the lack of existing organic carbon (Cottingham, 1998). Due to the age of the system the results indicated might not transfer to wetland cells that have substantially more internal load associated with the time of operation. Since the treatment cell was designed with a 7mm gravel bed matrix, Cottingham (1998) did not introduce any additional media. 23 Alternative designs were studied in order to determine the performance of ammonia removal. Jamieson (2003) found that laboratory scale containers with 1 year of plant growth and length to width ratio of 4:1 achieved substantial removal of ammonia concentrations. This system treated dairy waste and removal efficiencies increased from 50% before aeration to 93% approximately 16 days after the start of aeration (Jamieson, 2003). Performance of this system is desirable for ammonia removal rates; however, it was studied in a greenhouse under a controlled environment, which is unlike typical wetland conditions. Innovative wetland designs have been altered and tested with the intention of nitrogen removal. Performance of these innovative systems has generated similar removal efficiencies as seen by Jamieson (2003). Xianqiang (2007) showed that vertical subsurface flow wetlands generated 77.8%, 92.2%, and 67.1% ammonia removal depending on the flow regime. These systems show that in-situ aeration has the potential to reduce ammonia concentration, although no studies have shown that this level of performance can be achieved in a wetland cell that has been in operation for an extended period of time. 24 METHODOLOGY Aquaphyte Initial aeration studies were conducted in the aquaphyte at the AWTF. The aquaphyte is an elevated transparent Plexiglas flume that attempts to represent a scaled down treatment wetland. The sidewalls were lined with black covering to obstruct exposure to solar radiation and inhibit algal blooms. Dimensions and hydraulic retention time of the aquaphyte are presented in Table 4. Filling and draining the aquaphyte measured porosity, and plant biomass occupied approximately 55% of subsurface volume. Table 4: aquaphyte dimensions and hydraulic retention time Dimension Cross section (ft2) 3.375 Height (ft) 1.5 Width (ft) 2.25 Length (ft) 32 Volume (ft3) 108 Volume (gal) 808 Porosity 55% Theoretical HRT (days) 2.33 25 The aquaphyte received influent from a sump pump triggered by a float switch that intermittently pulled water from Oxidation Pond 2 where it collected in a 50 gallon barrel. A peristaltic pump was installed to regulate and ensure consistent water flow into the aquaphyte. Typical water flow rates, ammonia loading, and BOD loading rates that the aquaphyte received are represented in Table 5. Table 5: Water flow and typical loading into aquaphyte Water Flow (Gal/day) 190.5 (L/min) 0.5 Typical loading Ammonia loading (lbs N/day) 0.03 BOD loading (lbs BOD/day) 0.19 Plant species in the aquaphyte predominately consist of bulrush (Scirpus acutus), water celery (Vallisneria americana), and morning glory (Cressa truxillensis) (Figure 4). Plants were taken from the edges of the oxidation ponds and transplanted in the summer of 2010. There has been 3 years of plant growth and senescence, which created an observable layer of accreted peat combined with settled algal biomass. 26 Figure 4: photo of aquaphyte adjacent to oxidation pond 2 Prior to any inputs, performance of the aquaphyte was analyzed to determine if any nitrification occurred with low dissolved oxygen content, low water temperature, or during the seasonal period of plant senescence. Oxygen was then introduced by an aeration system installed approximately 10 feet downstream of the influent to observe how an increase in DO would affect ammonia removal. The 10-psi, 1/10 horsepower compressor pushed air into the system through a pumice stone aquarium diffuser. Manufacturer specifications for the air diffusor were unavailable so, 20% transfer efficiency was assumed. 27 The air stone diffuser was housed in a wooden frame constructed of 2in x 4in lumber. Airflow was measured and regulated using a traditional rotameter with an operating range from 0 to 100 SCFH. The components of the aquaphyte are represented in Figure 5. Samples ports are equally space along the length of the system at approximately 4 ft. increments. Stabilization Tank - from Oxidation Pond 2 Sample port (Influent) (Effluent) Peristaltic pump Aeration Air Pump Rotometer Figure 5: Diagram of aquaphyte with sample ports and equipment. Before this experiment, the aquaphyte was previously tested with plastic media to house nitrifying bacteria. However, the introduction of plastic media on a large scale may have issues with operation and maintenance or potentially harmful effects on the existing bird populations. Birds and mammals within the wastewater ecosystem may mistake the plastic media for food, which would have detrimental effects if ingested. To avoid this 28 potential issue, it was assumed that there would be sufficient surface area on existing plant biomass to harbor microbial communities and no additional plastic media was necessary. As the aquaphyte aged, the macrophyte plant species (bulrush) occupied the entire water column (Figure 6). Figure 6: Existing plant growth within aquaphyte water column. Lagace (2000) determined the submerged surface area of bulrush in different planted densities (Table 6). Available surface area to harbor nitrifying microbial communities in the aquaphyte was estimated from existing plant density (Table 6) within the reach of DO concentrations > 1.0mg/l (Table 7). 29 Table 6: Estimated available surface area for a submerged depth of 0.6 m, bolded numbers were used in calculations (adapted from Lagace, 2000). Submerged plant biomass Area Units m2/m2 Low density Medium density 3.79 High density 7.58 11.37 Extremely compact 15.16 Submerged plant biomass volume m3/m2 0.021 0.042 0.063 0.084 ft3/ft2 0.066 0.131 0.197 0.263 Table 7: Estimated surface area of submerged plant biomass in aquaphyte within the volume of water containing DO concentrations above 1.0mg/l (using data from Lagace, 2000). Surface area 13.49 m2 136.44 ft2 Volume of submerged biomass 0.075 m3 2.41 ft3 56.74 ft2/ft3 30 Treatment Wetland Four Treatment wetland four (TW-4) was the original pilot project at the AWTF and was used to demonstrate that wastewater “enhancement” could be achieved with constructed wetlands. TW-4 has been in operation for approximately 35 years and the vegetation has never been harvested, which has generated a substantial internal load of nitrogen, phosphorous, and carbon associated with the time of operation and plant life cycles. TW4 consists of ten adjacent cells with a trapezoidal cross section operated in series. Each treatment cell has a width of 20 ft, and length of 200 ft for a total system length of 2000 ft (Table 8). Testing was conducted on one cell during the summer of 2013 to determine if the results seen in the aquaphyte can be repeated in a larger scale system. Table 8: Dimensions and HRT of one channel in Treatment Wetland 4. Treatment Wetland 4 Cross Sectional Area ft2 Height (ft) 42.75 2.25 Top width (ft) 20 Bottom width (ft) 18 Length (ft) 200 Volume ft3 8550 Volume (gal) 63958 31 TW-4 was initially planted with Bulrush and Cattail (Typha latifolia) in alternating channels to determine if the dominant vegetation would influence treatment. Although bulrush still exists in the system, cattail has established itself as the dominant species in all channels. Operating water depth is higher than the original value in all of the treatment wetlands and has generated enough buoyant force on the root system to dislodge the rooted plants and create a floating mat of detritus and plant vegetation. Macrophytes created a layer of degrading biomass at the water surface that provides sufficient substrate for the existing rhizome systems, which has essentially enabled them to survive without soil substrate. Wastewater is pumped from Oxidation Pond 2 (ox-pond 2) into a stilling tower and then loaded into TW-4. Flow rates into TW- 4 started at approximately 0.2 MGD, which is the flow under normal operation. These flows were reduced after initial testing in an attempt to converge towards greater similitude between the aquaphyte and TW-4 (Table 9). 32 Table 9: Water flow rate, typical ammonia loading, typical BOD loading, airflow, and HRT into experimental cell of Treatment Wetland – 4 Water flow Air flow Reduced water flow (gal/day) 22300.0 CFM 8.00 Normal water flow (gal/day) 200,000 O2 transfer efficiency 0.2 Typical Loading HRT Nitrogen loading (lbs N/day) 3.72 HRT (days) reduced flow 2.87 BOD loading (lbs BOD/day) 27.88 HRT (days) normal flow 0.32 The aeration system was installed at approximately half the length of the entire treatment wetland or 11.5 days into the HRT (with the reduced flow rate), where one of the 200 ft channels was analyzed for nitrification and denitrification. The aeration system consisted of a 0.75 hp compressor, PVC piping, rubber hose, and eight 9 inch diameter membrane diffusers. Fine bubble membrane diffusers were chosen instead of stone diffusers to reduce required maintenance and inhibit flooding of the conveyance system if the compressor was shut down. Piers and platforms were constructed to access the aeration system for maintenance and to gather samples (Figure 7). 33 Figure 7: Aeration system installed in Treatment Wetland 4. Sample ports were installed in order to observe the transformation of ammonia as it advects along the length of the treatment cell (Figure 8). 34 Figure 8: Diagram of Treatment Wetland 4 aeration system, sample ports, and pier. Water flows in from the bottom right corner of the diagram and past the sample ports indicated in red with distance from aeration system. Samples were analyzed from TW-4 with no plastic media installed to test the hypothesis that there would be sufficient surface area within the existing plant biomass; however, there is a substantial difference in the configuration of the emergent macrophytes between the aquaphyte and TW-4. Consequently, plastic media was installed to determine if surface area for microbial attachment was a parameter that would increase ammonia reduction. Wooden frames with plastic mesh (Figure 9 left) were constructed 35 and installed to contain the plastic media. Additionally, laundry bags and chicken wire “bags” were filled with Bio-Pac honey comb media and plastic strapping (Figure 9 right). Figure 9: Left photo indicates the wooden frame containment and media. Right photo was the chicken wire “bags” that contained large honey comb media and strapping material. Both were installed into Treatment Marsh 4 to facilitate nitrification. Eight wooden frames were installed adjacent, on the downstream (left) side, of the aeration system (indicated by the multiple PVC pipes sticking out of the water in Figure 10). 36 Figure 10: Operation of the aeration system installed in Treatment Marsh 4 downstream of the constructed pier. Additional media, in laundry bags, was installed directly above the aeration unit and the system was tested. These bags were replaced with chicken wire “bags” in an attempt to allow for more mixing to occur on the water surface and the system was retested. An estimation of the available surface area in TW-4 is presented in Table 10. These values approximate the media surface area that was added to the system and does not consider any other available surface area in the form of chicken wire, plastic mesh on wooden frames, or plant biomass. 37 Table 10: Estimation of available surface area on the additional plastic media; it is assumed that 70% of area is available. Surface area TM 4 Strapping (ft2) Strapping volume (ft3) 540 3 Strapping (ft2/ft3) Strapping (ft2) * 70% 180 378 Biopac (ft3) Biopac (ft2) Biopac (ft2/ft3) Biopac (ft2)* 70% 47.04 1411.2 30 987.84 Poly Pall rings ft2/ft3 Volume of poly pall rings ft3 Surface area (ft2) Total media volume (ft3) 45.59 10 456 60.04 Total media surface area (ft2) 1822 Performance of the aeration system installed in TW-4 was analyzed during the summer months by observing the internal load being released from the wetland. The turbulence created by the aeration system stirred accreted ammonia that has accumulated over the past 35 years of operation. This was evident by observing excessive organic content in the samples taken directly above the aeration system, which did not exist in samples taken further downstream. 38 Monitoring and Laboratory Analysis Samples from each of the installed sample ports monitored performance of both the aquaphyte and TW-4 on a weekly or bi-weekly schedule. The aquaphyte had ten sample ports with the additional samples from the influent and effluent. Samples in the aquaphyte were extracted using a PVC pipe with a connected container, which was rinsed three times with surface water in each associated port before each sample was bottled – the bottles were also rinsed three times. A hand pump was used to extract the samples from TW-4 to get a representative sample at the same depth in each sample port. Water quality conditions were determined from laboratory testing that included: ammonia, nitrate, NBOD, CBOD, and TSS. Additionally, in-situ field tests of DO, pH, and temperature were taken while samples were being extracted. Laboratory analysis of BOD, ammonia, nitrate, and TSS were conducted according to procedures presented in AWWA (2005). 39 RESULTS AND DISCUSSION The aquaphyte has proven to have an effective design that facilitates nitrification. This chapter will discuss the variables and observations relative to temperature, aeration, media and contact time that appeared to affect the rate of nitrification in the aquaphyte. Additionally, relevant data recorded for TW- 4 will also be presented and discussed in this chapter. Aquaphyte Effects of temperature on the rate of nitrification. Located in the Pacific Northwest, Arcata experiences coastal climate effects of mild temperature fluctuations and high rates of precipitation. Ambient temperatures can reach below freezing, which lowers water temperatures down to approximately 4oC at the wastewater treatment facility. These low temperatures occur during periods when ammonia concentrations are high, and the natural treatment capability of wetland ecologies cannot reduce the effluent ammonia to acceptable values. Reduction in performance of constructed wetland systems during the winter months is attributed to water temperature, plant dormancy, and reduced oxygen transport (Werker, 2001). Water temperature is an important variable when designing an in-situ aeration system. Understanding how water temperature affects nitrification at AWTF will help avoid an 40 unnecessary economic burden during periods when lower water temperatures inhibit microbial metabolisms. Throughout the year, and especially during the winter months, sections of the AWTF operate as an oxygen deficient system with DO concentrations below 1.0mg/l. However, some nitrification occurs under these conditions throughout cold periods of the year. Laboratory analysis was performed during the cold winter months to determine how temperature affects the capacity of the aquaphyte to nitrify without any inputs. The aquaphyte reduced ammonia levels by 44% without any mechanical input during cold weather months (Figure 11). Nitrate concentration increased by about half compared to the ammonia reduction. It is possible that some of the ammonia volatilized, however this would require an increase in pH that wasn’t observed. Additionally, although short lived, some of the difference between the reduction in ammonia and the increase in nitrate could be accounted for by an increase in nitrite, which wasn’t measured in the laboratory analysis. Ultimately, it is likely that denitrification is occurring at about half the rate of nitrification. 41 20 NH3-N Conc. (ppm) NO3-N Conc. (ppm) 18 Observed Value (mg/L) DO (ppm) 16 Temp (Celcius) 14 pH 12 10 8 6 4 2 0 Sample Ports Figure 11: Aquaphyte performance with no aeration and cold temperatures 1/4/13; average temperature 7.4oC. Sample ports are equally spaced along the length of the aquaphyte (4 ft increments). There is evidence that microbial metabolism is still active at some of the lowest temperatures (7.4oC) of the season (Figure 11). During the same week of testing, NBOD was reduced by 25% of the initial load, while CBOD was reduced by 27% (Figure 12). Heterotrophic bacteria, typically dominating the microbial populous, are capable of facilitating nitrification under anoxic conditions, which may indicate that ammonia ions 42 are utilized as a source of energy when oxidized organic carbon is not available. Autotrophic bacteria are more dormant and far slower growing, which leads to the conclusion that heterotrophic bacteria are degrading the NBOD during cold winter months. Observed value (mg/L) 20.00 CBOD NBOD 18.00 16.00 14.00 12.00 10.00 8.00 6.00 4.00 2.00 0.00 SP 1 SP 2 (INF) SP 3 SP 4 SP 5 SP 6 SP 7 Sample Location SP 8 SP 9 (EFF) Figure 12: Total BOD characterized as NBOD and CBOD, average temp 7.4oC (01/04/13) Similar reductions were seen when average temperatures reached 6.9oC, generating a 52% decrease in ammonia, most converting to nitrate, some of which was then converted to di-nitrogen. This indicates that nitrification does occur at colder temperatures without any assistance. However, the BOD trend in Figure 12 doesn’t continue as cold temperatures prevailed. With an average temperature of 6.9oC, NBOD increases by 75% 43 while the CBOD was reduced by 69% (Figure 13). It is uncertain why such an increase in NBOD was observed. Observed Value (mg/L) 25.00 20.00 15.00 10.00 NBOD 5.00 CBOD 0.00 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 SP 6 SP 7 Sample Location SP 8 SP 9 (EFF) Figure 13: Total BOD average temp 6.9oC 1/11/13 The increase of NBOD and reduction of CBOD continued as water temperatures remained below 10oC. This trend approximates the dynamics of oxygen demand during the cold-water temperatures and low rates of solar radiation throughout the testing period. Typically an increase in NBOD can be attributed to the breakdown of organic material, which is unlikely due to the low temperatures and inhibited microbial processes. It is difficult to determine why NBOD increases so dramatically. 44 Seasonal changes, dictated by higher levels of solar radiation, gradually increase water temperatures as the calendar moves into the spring months. By the middle April, the average water temperature was approaching 13oC, which is near the threshold where a significant increase in the rate of nitrification occurs (Kadlec and Reddy, 2001). The nitrogen dynamics of the system in the middle of April, with an average temperature of 12.6oC, showed a 45% reduction in ammonia concentrations (similar to that seen with temperatures of 6.9oC). However, there is not a corresponding increase in nitrate concentrations suggesting that nitrification may not be occurring. An alternative nitrogen pathway may be reducing the ammonia concentrations. For instance, the reduction of ammonia could be attributed to plant uptake. Solar radiation and plant growth were observed during this period of the year, which could explain why nitrate concentrations did not increase. Otherwise, anoxic zones may exist within the aquaphyte where denitrification can occur, which is not detected by the existing sample port orientation. 45 Observed value (mg/L) 25.00 DO Ammonia Nitrate 20.00 15.00 10.00 5.00 0.00 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 SP 6 Sample Location SP 7 SP 8 SP 9 (EFF) Figure 14: Ammonia reduction in the aquaphyte on 4/12/14; average temp 12.6oC The average removal of ammonia, NBOD, and CBOD relative to temperatures above and below 10oC is presented in Table 11. There are slightly higher rates of ammonia removal when water temperatures are greater than 10oC. However, the rate of ammonia removal is not dramatically different so temperature may only have a slight effect on the rate of nitrification with loading rates near 20 mg/l at the AWTF. 46 Table 11: Percent removal of ammonia, NBOD, CBOD with average temperatures above and below 10oC (based on 21 samples) Constituent Ammonia Average cold temp removal (<10oC) Average warm temp removal (>10oC) Percent Removal 56% 68% NBOD Average cold temp removal (<10oC) Average warm temp removal (>10oC) 564% (increase) 72% CBOD Average cold temp removal (<10oC) Average warm temp removal (>10oC) 56% 68% Throughout the testing period, NBOD shows a dramatic change as temperatures increase. Below 10oC, the aquaphyte contributes nitrogen from the internal load of previous ammonia accretion, but as the temperature increases NBOD is removed from the system. Coincidentally, the removal rates for CBOD and ammonia are the same, supporting the theory that heterotrophic bacteria dominate microbial populous under cold water conditions. Other environmental variables confound the interpretation of the removal presented in Table 11. For instance, 70% of the data was measured under conditions of aeration, making the direct effect of temperature more difficult to isolate. Low temperature is known to inhibit microbial processes and reaction kinetics. However, Figure 15 indicates that high rates of nitrification occur at temperatures below ideal ranges for nitrifying bacteria reported in the literature. Ammonia removal rate reaches 47 approximately 100% nearly two months before average water temperatures are in the ideal ranges. Removal of ammonia approaches 100% while the temperature average is still only 9oC. The average influent ammonia concentration was 23.3 mg/l during this winter season. Such high removal rates at low temperatures suggest that low water temperatures with average ammonia influent concentrations of 23.3 mg/l do not seriously influence rates of nitrification. However, AWTF has seen ammonia concentrations three times higher than observed during this study. If loading rates approach those levels and water temperatures are below 10oC the system may have difficulty achieving desired removal. 16.0 100% 14.0 80% 10.0 60% 8.0 6.0 40% 4.0 20% 2.0 0.0 12/17/12 temp 1/6/13 1/26/13 ammonia removal % 2/15/13 3/7/13 3/27/13 0% 4/16/13 date Figure 15: Temperature vs. Ammonia removal over time; large increase in removal efficiency is a result of operating the aeration system. percent removal Temperature oC 12.0 48 Garrison (2011) observed a period of influent concentrations that averaged approximately 32 mg/l with an average water temperature of 10.5oC. The aquaphyte performed very well with influent concentrations 50% higher than observed during this study. However, there seemed to be an initial adjustment period for the system to adapt to the increased loading (Table 12). Temperatures during Garrison’s study were slightly higher than observed during this study, but still below the temperature threshold of 13oC. Between 11/27/10 and 12/03/10 water temperatures averaged approximately 7.7oC (lowest temperatures of the season) and ammonia removal efficiencies of 99%. The influent concentrations during these two weeks averaged approximately 20 mg/l, which were very similar to the conditions and results observed during this study (winter 2012/2013). The 50% increase of ammonia loading with a corresponding 4.3oC increase in temperature on 12/10/10 reduced ammonia removal from 99% to 53%. It appears that the low temperatures inhibit the rate of nitrification and biofilm development, but don’t eliminate it completely. Due to the low water temperatures the system potentially required more time for the microbial ecology to adjust to the new loading conditions. 49 Table 12: Aquaphyte performance winter of 2010; average temp 10.5oC, average influent concentration 32.5mg/l, with aeration Date Influent ammonia concentration (mg/L) 11/27/10 12/3/10 12/10/10 12/17/10 1/19/11 1/22/10 1/26/10 2/11/10 3/1/10 18.5 22.3 31.9 34.5 28.9 29.4 32.2 30.9 32.5 Ammonia removal (%) 99% 100% 53% 92% 99% 98% 94% 94% 79% Average temp (C) 6.6 8.8 12.0 8.9 12.5 11.3 10.3 9.4 11.9 With the loading rates seen during this study, low water temperatures don’t appear to drastically effect the rate of nitrification as observed by Garrison (2011). However, for the performance of the system to reach above 90% removal with cold-water temperatures, artificial aeration is necessary. Effects of aeration on nitrification. The aeration system was installed in the aquaphyte and the system performance was analyzed. One week after the aeration system started operating, the nitrogen speciation dynamics resulted in a sharp increase in nitrate (ammonia probe malfunctioned this week), indicating that the start up time for removal of ammonia may be fairly short. However, high rates of nitrification don’t become consistent until approximately 28 days of aeration (Table 13). Additionally, NBOD wasn’t reduced until 35 days of aeration and 50 a full reduction did not occur until 45 days of aeration. Correspondingly, temperature was gradually increasing during this period, which might account for some of the delay. Table 13: Reaction of water quality parameters throughout the period of aeration Date 1.25.13 2.01.13 2.08.13 2.15.13 2.22.13 3.01.13 3.10.13 3.20.13 3.29.13 4.05.13 Days of aeration 0 7 14 21 28 35 45 55 64 71 Ammonia reduction (%) 40% NA 34% 38% 98% NA NA 99% 99% 98% NBOD reduction 830% (increase) 362% (increase) 8% (increase) 319% (increase) NA 52% 100% 94% 94% 93% CBOD reduction 42% NA 41% 78% NA 71% 96% 73% 81% 87% Ammonia reduction in the aquaphyte increased during the period of aeration. The system responded to aeration with a sharp decrease in ammonia concentrations and a corresponding increase in nitrate concentrations as the flow approaches the plume of DO saturated water (Figure 16). With these rapid changes in concentration, it is evident that the system quickly responded to the influx of oxygen and nitrification is occurring. 51 Observed value (mg/L) 30.00 DO Ammonia Nitrate 25.00 20.00 15.00 10.00 5.00 0.00 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 Sample Location SP 6 SP 7 SP 8 SP 9 (EFF) Figure 16: Constant head flow regulation; average temp 8.1oC; 34% ammonia reduction (2/08/13) Denitrification is also seen in the oxygen deficient zones of the aquaphyte downstream of sample port 5 as nitrate concentrations decrease. During this period (2/08/14, Figure 16) there is a slight 8% increase of NBOD, CBOD was reduced by 40%, and the DO concentrations remain at near saturated levels within the region of sample port 3. Additionally, the spatial zone between sample port 5 and 9 allow observation of the ammonia internal load contributions. The following week of aeration (2/17/13) was unusually warm with an average temperature in the system of 12.3oC. The first significant drop in DO concentration in the 52 aeration zone occurred during this period, from 9.5 ppm (the first week of operation) to 6.0 mg/l, which resulted in an 80% reduction in CBOD concentrations (Figure 17). However, due to the increase in NBOD from the internal load of the system, the reduction of total BOD was only 20%. 35.00 CBOD NBOD Observed value (mg/L) 30.00 25.00 20.00 15.00 10.00 5.00 0.00 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 SP 6 Sample Location SP 7 SP 8 SP 9 (EFF) Figure 17: Total BOD concentrations during period of aeration; average temp. 12.3oC (2/17/13) Some ammonia conversion by nitrification was offset by the aeration unit, which stirred up ammonia-laden peat and decomposing algal biomass that has settled to the bottom of the aquaphyte over the past three years of operation. The stirring of peat and algal biomass became apparent when observing the samples extracted directly above the 53 aeration system. These samples contained visible organic matter that wasn’t observed in samples downstream of the aeration unit. Soil is where the highest concentrations of ammonia are stored within wetland ecosystems (Bowden, 1987). This can be a significant contribution of ammonia as wetland cells age and store nutrients, which would increase demand for oxygen and operational energy requirements. To avoid this economic burden, it may be necessary to harvest live and decomposing biomass every 3-5 years of operation. This frequency can change depending upon the loading received during that operational period. Soon after aeration began, the peristaltic pump that regulated influent flow required maintenance and the system reverted to constant head flow regulation for the first three weeks. The constant head flow regulation is easily clogged with debris and showed consistent diurnal fluctuations of flow through the system. The first 21 days of aeration generated an average ammonia reduction of 36%. The peristaltic pump was reinstalled on 2/16/13, which once again supplied a constant influent flow rate. After 21 days of aeration, during the seven-day period following the reinstallation of the peristaltic pump, and a 4.6oC decrease in water temperature, ammonia reduction increased from 37% (2/15/2014) to 98% (2/22/13). The high rates of nitrification with the corresponding drop in temperature also helps justify the conclusion that in-situ aeration to facilitate nitrification is insensitive to low 54 water temperature with the loading rates seen during this study. In addition, lower water temperatures potentially inhibit biofilm development at the AWTF enough that approximately 28 days of growth within an aerobic environment is required to achieve desired rates of removal. After 28 days of aeration, the aquaphyte facilitated a 98% reduction of ammonia concentrations together with an 80% increase in nitrate concentrations (Figure 18). The remaining 18% could have taken multiple pathways within the system. Findings from Shammas (1986) indicate that some of the ammonia could remain in the form of nitrite, because the biological processes of Nitrobacter, bacteria that convert nitrite to nitrate, is slightly more sensitive to cold than Nitrosomonas (bacteria that convert ammonia to nitrate). Considering what the low temperature was that week, some of the ammonia could be in the form of nitrite. The 98% reduction in ammonia concentration (Figure 18) continued until 4/05/13 when the aeration system shut down, 70 days after start up. 55 Ovserved value (mg/L) 30.00 DO Ammonia Nitrate 25.00 20.00 15.00 10.00 5.00 0.00 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 SP 6 Sample Location SP 7 SP 8 SP 9 (EFF) Figure 18: One week after install of peristaltic pump flow regulation; average temp 7.9oC; (2/22/13), 28 days after aeration began Performance of the system for the first and nearly coldest month of aeration (between 1/12/13 – 2/22/13) showed that NBOD increased from the internal load resulting in a higher concentration in the effluent than that of the influent with concurrent reductions seen in CBOD concentrations. Forty-five days after the installation of the aeration unit, a 100% reduction in the NBOD concentration in the aquaphyte is observed, in addition to 50% reduction in CBOD (Figure 19) indicating that the microbial population appeared to be dominated by nitrifying bacteria. 56 Observed value (mg/L) 40.0 CBOD NBOD 35.0 30.0 25.0 20.0 15.0 10.0 5.0 0.0 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 SP 6 Sample Location SP 7 SP 8 SP 9 (EFF) Figure 19: (3.10.13); 100% reduction in NBOD, 50% reduction in CBOD Concentrations of BOD drastically increase in the spring as the water starts to warm. Figure 20 shows how the system handles high BOD loading, which increased approximately fivefold. The NBOD was reduced by 96% and CBOD was reduced by 92% with an airflow rate of 50 SCFH and an average temperature of 13.3oC. This shows that the system can sufficiently reduce high loading rates of BOD. 57 250.00 Observed Value (mg/L) CBOD NBOD 200.00 150.00 100.00 50.00 0.00 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 SP 6 Sample Location SP 7 SP 8 SP 9 (EFF) Figure 20: 4.05.13; 70 days of aeration operation; average temperature 13.3oC; 50 scfh Ultimately, the effective performance of the aquaphyte appears to be attributed to the operation time of the aeration unit, but may also be dependent upon temperature, and the total age of the system. Due to the slow growth of nitrifying bacteria, it may take up to 28 days to achieve reductions in NBOD. Additionally, the CBOD may need to be degraded sufficiently for the microbial population dynamics to be dominated by nitrifying bacteria. 58 Ammonia removal efficiencies continue at these rates throughout the cold weather months and remain consistent as temperature increases. Media and contact time. Basviken (2003) suggests that media plays an important role in nitrification by providing a substrate for biofilm to develop in attached growth reactions. Increasing the density of biofilm will produce high rates of nitrification, assuming that surface area is a limiting factor. Surface area of the substrate can come in many forms. Plastic media has been used in conventional wastewater treatment systems to provide substrate for nitrifying bacteria to attach. Garrison (2011) performed a previous analysis on the aquaphyte from 20102011. During Garrison’s study, the aquaphyte was approximately one year old, and the plant density was comparably sparse. With the addition of media, Garrison observed that the aquaphyte removed 99% of the ammonia and there was an approximately 82% increase in nitrate (Figure 21). Garrison (2011) did not analyze the system without media so it is difficult to determine if the system would have achieved the same levels of removal without the installation of plastic media. 59 35 DO Observed value (mg/L) 30 Ammonia Nitrate 25 20 15 10 5 0 Pt 1 (in) Pt 2 Pt 3 Pt 4 (air) Sample Location Pt 5 Pt 6 Pt 7 pt 8 (out) Figure 21: Garrison, average temp 12.5oC, with plastic media, influent concentration of 27.21ppm, air flow 70 scfh This study of the aquaphyte has shown that nitrification (ammonia reduction and conversion to nitrate) occurs without the addition of plastic media (Figure 22). Arcata operates a natural treatment system that is constantly changing and adapting to variations in climate and time of operation. It was determined that the aquaphyte, after three years of growth, contained sufficient submerged plant surface area for microbial attachment and no additional media was installed. Approximately 99% conversion of ammonia to nitrate was observed without the use of plastic media (Figure 22). 60 30.00 DO Ammonia Nitrate Observed value (mg/l) 25.00 20.00 15.00 10.00 5.00 0.00 SP 1 (INF) SP 2 SP 3 SP 4 SP 5 SP 6 Sample Location SP 7 SP 8 SP 9 (EFF) Figure 22: Nitrogen dynamics on 3.20.14; average temperature 12.2oC, no installed plastic media This study measured a porosity of approximately 55% that provided sufficient surface area of microbial attachment; however, it appears that the amount of surface area may not be as important as the location of this surface area within the system. Figure 21 and Figure 22 illustrate how the nitrogen dynamics change as the flow approaches the aeration zone of the aquaphyte where dissolved oxygen concentration is above 1.0mg/L. Newly constructed systems with sparse plant density may require the use of plastic media. If necessary, plastic media needs to be installed within the reach of DO concentrations > 1.0 mg/l to achieve appropriate ammonia removal efficiencies. After 61 three years of operation, the aquaphyte has extremely dense bulrush growth within the zone of aeration, so additional surface area added by plastic media was unnecessary. Residence time and plant growth within elevated levels of DO could also be of some significance when designing in-situ aeration systems for constructed wetlands (Table 14). Table 14: Residence time within media, mass of oxygen within contact volume, and mass of oxygen per square foot of surface area on 3/20/14 Contact time within media (Hrs) 12.72 Mass of oxygen available within contact volume (g) 2.02 mg O2 / ft2 surface area 1.32 Contact time in the emergent plant substrate within the region of DO concentrations above 1 mg/l is approximately 1/4 of theoretical HRT. Design of in-situ aeration systems should incorporate the type of media appropriate for constructed wetland waste treatment systems. It is recommended to use plant surface area as a substrate due to the complications that could arise when using plastic media in an in-situ design. However, if plants are utilized for substrate, specific operational parameters need to be strictly followed. For instance, periodic harvesting of biomass is necessary to avoid accumulation of organic carbon in addition to accreted ammonia, reducing the effect of the seasonally compounding internal load. Ultimately, periodic harvesting is a necessary parameter of 62 operation in any constructed wetland system or the system will eventually reduce its own capacity to improve water quality as it fills with decomposing plant and algal biomass (Kadlec, 2008). Scale Up: Treatment Wetland 4 Water quality analysis. The rate of ammonia conversion observed in the aquaphyte was desired in a full-scale system. Aeration equipment was installed into TW-4 and operated during the summer months when ammonia concentrations at the treatment plant are typically low, but the internal loading of ammonia from decomposing plant and algal biomass made it feasible to test the scaled up aeration system. There are some major observable differences between TW-4 and the aquaphyte. TW-4 has been loaded with municipal wastewater for approximately 35 years and has had a tremendous amount of biomass accumulation and ammonia accretion throughout that period of operation (Figure 23 and Figure 24). Additionally, the emergent macrophytes established in TW-4 have become dominated by cattail, which have uprooted and float on a one-foot thick mat of peat on the water surface. These differences were considered when establishing the aeration system. The aquaphyte water column is dense with bulrush and additional media for nitrifying bacteria attachment was unnecessary. Due to the floating vegetation mat in TW-4, media was added to the system in an attempt to 63 generate uniform loading of media through the entire cross section of the treatment cell and aeration system. Figure 23: The initial pilot project, Treatment Marsh 4, on September 3, 1980. The system was designed and operated in series with 10 separate treatment cells (W= 20' x L = 200' x D = 2') Initially, the treatment cells alternated plantings from Bulrush to Cattail. Plant biomass was still sparse and developing. 64 Figure 24: TW-4 in the Summer 2013 after 35 years of loading with municipal wastewater. Biomass development is extensive when compared to Figure 23. It now operates in parallel with a sinusoidal flow pattern. Cattail has emerged as the dominant macrophyte. DO and BOD. The installed aeration system produced a peak DO concentration of 5.2 mg/l directly above the aeration system, which is well below the near saturation levels (9.5 mg/l) that were recorded in the aquaphyte. Peak DO concentrations, near 5 mg/l, remained for approximately 22 days after the installation of the aeration system with no visible response in the concentration of ammonia. Following this 22 day period, while the air 65 flow rate stayed constant, DO concentration decreased by 15% (from 5.2 mg/l to 4.4 mg/l) that reduced total BOD in TM – 4 by approximately 30%, which could be due to the break down of the extensive carbonaceous load (Figure 25). Observed value total BOD (mg/L) 140 120 100 80 60 40 20 0 P2 Pre-Air Air 5 ft 10 ft 15 ft 20 ft 25 ft 30 ft 35 ft 40 ft Sample Location Figure 25: Total BOD reduction of 30% on 5/22/13 indicating that the DO was being consumed DO concentrations continued to decline as the oxygen demand was reduced. The system generated a 25% reduction in total BOD, which may indicate that the performance is oxygen limited (Figure 26). Potentially, if the DO concentrations were near saturated levels, the necessary reductions in CBOD would occur and degradation of the nitrogenous load would begin. However, due to the design of the membrane diffusers and the depth of water in the treatment cell, it is difficult to artificially achieve high rates of 66 oxygen transfer. Membrane diffusers are typically installed in activated sludge reaction chambers, which are designed with depths of approximately 12-15ft. Oxygen transfer is reduced when the depth of the water column is reduced, as is the case when installing diffusors in a treatment wetland. DO (mg/L) 130.0 1.6 120.0 1.4 1.2 110.0 1 100.0 0.8 90.0 0.6 80.0 0.4 70.0 0.2 0 60.0 -5 5 15 25 35 Distance from aerator (ft) Figure 26: Total BOD reduction with DO consumption on 6/6/13 In an attempt to increase performance of the aeration system to reduce ammonia and BOD, different orientations and volumes of media were added and the system was Dissolved Oxygen (mg/L) Observed BOD value (mg/L) Biological Oxygen Demand 67 retested. Chicken wire “bags” filled with plastic media were installed to replace the laundry bags to promote more mixing at the water surface with the intention of increasing oxygen transfer. Laundry bags had mesh walls that appeared to clog with biofilm accumulation and reduce the aeration through the media, thereby inhibiting oxygen interaction on the media surface area. Replacing laundry bags with wire “bags” did not generate elevated DO concentrations as no change was seen after their installation. Although, three days prior to the installation of the chicken wire bags NBOD and CBOD were reduced by 30% and 25%, respectively. Interestingly, three days following (6/13/13) the replacement of laundry bags with wire, CBOD reduction essentially doubled to 54%, while NBOD remained at a 30% reduction, totaling 41%. The most significant reduction in total BOD occurred two weeks after the installation of the wire bags with a reduction of 68% (Figure 27). It is assumed that the reduction of BOD could be attributed to the work of the heterotrophic bacteria and the decrease of the carbonaceous demand (CBOD), as there was no reduction in ammonia. 68 140 Total BOD Observed value (mg/L) 120 100 80 60 40 20 0 P2 Pre-Air Air 5 ft 10 ft 15 ft 20 ft Sample Location 25 ft 30 ft 35 ft 40 ft Figure 27: Total Biological Oxygen Demand (BOD) reduction (6.26.13); with wooden frames and two weeks after installation of wire bags Additionally, water flow rate was reduced from 200,000 gal/day to 22,300 gal/day in an attempt to generate a greater similitude between TW-4 and the aquaphyte. Changing the flow rate generated no observable difference in the nitrogen dynamics, yet reduction in BOD concentrations continued (Figure 28). Under those circumstances, HRT within the aeration zone increased, which helped contribute to reductions in BOD. 69 120 CBOD NBOD 100 Observed value (mg/l) 80 60 40 20 0 P2 -15 ft -5 ft Air 5 ft 10 ft 15 ft 20 ft 25 ft 30 ft 35 ft 40 ft 200 ft Sample Location Figure 28: 7/17/13; 68% reduction in NBOD, 74% reduction CBOD The sample port at 10ft consistently had high levels of visible organic material, which was obviously stirred up by the aeration system. The organic material may have eventually settled, giving the appearance that the aeration system generated the high rates of reduction. If the effluent is compared to Oxidation Pond 2 concentrations and not sample port 10ft, there is approximately a 12% increase in NBOD. On the contrary, effluent CBOD samples compared to ox-pond 2 concentrations were reduced by approximately 74%. Concern about the low oxygen concentrations dictated the removal of the wire bags that were installed directly above the aeration system. It was observed that the wire bags 70 allowed biofilm growth during the period of operation when installed above the air diffusers; although, the growth of biofilm was sparse. DO levels were recorded after the wire bags were removed and the highest concentrations of DO seen in this system were observed (Figure 29). 7.0 6.0 4.0 3.0 2.0 Disolved Oxygen (mg/L) 5.0 1.0 0.0 -15 -5 0 5 10 15 20 25 30 35 40 Distance from Aerators (ft) Figure 29: Dissolved oxygen concentration TW 4 after removal of wire bags (7.25.13). DO concentrations observed in TW-4 after the removal of media prompted a new configuration of the aeration system and media. The media was re-installed just downstream from the aeration system with the assumption that higher DO concentrations would advect through the media bags. Peak DO concentration seen on 7/25/13 (Figure 71 29) and gradually decreased as the system remained in operation, eventually dropping back down to previous levels, 1.5-2.5 mg/l. The final configuration of the aeration system in the TW-4 experimental cell generated no new trend in ammonia reduction; reduction in DO concentrations appears to be a result of CBOD degradation. TW-4 generated a 50% reduction of BOD on 9/17/13 (Figure 30). Observed Total BOD value (mg/L) 80 BOD 70 60 50 40 30 20 10 0 -15 ft -5 ft Air 5 ft 10 ft 15 ft 20 ft 25 ft 30 ft 35 ft 40 ft Sample Location Figure 30: 50% reduction of total BOD 9.17.13, final media configuration, installed downstream of aeration system. It is evident that the microbial communities in TW-4 are utilizing the DO to reduce BOD. However, it appears that the DO is primarily being consumed to reduce existing organic carbon sources available for biological degradation. 72 Nitrogen dynamics. Laboratory analysis has indicated that the in-situ aeration system installed in TW-4 did not facilitate rates of nitrification seen in the aquaphyte. Of the 30 data points collected, within the five months of aeration, there were only two days where ammonia concentration was reduced and nitrate concentrations increased (Figure 31 and Figure 32). Ammonia (NH3-N) Nitrate (NO3-N) DO (O2) 8.0 3.0 2.5 7.0 6.0 2.0 5.0 1.5 4.0 3.0 1.0 2.0 0.5 1.0 0.0 0.0 P2 -15 -5 0 5 10 15 20 25 30 35 40 Observed Nitrate-N & DO values (mg/L) Observed Ammonia-N value (mg/L) 9.0 Distance From Aerators (ft) Figure 31: 5/30/13 ammonia reduction of 32% (2.8mg/l), peak DO concentration 2.5mg/l, slight increase in nitrate (1.6mg/l) within the zone of elevated DO Ammonia concentrations showed very little response to the influx of oxygen through the aeration system. Following the installation of the chicken wire bags, there was a 2-mg/l drop in ammonia levels, which may indicate that nitrification occurred (Figure 32). This 73 reduction is insignificant when considering that ammonia concentrations during recent winter months typically averaged approximately 20-30mg/l. As previously stated, the aeration system appeared to be oxygen limited with an extensive internal load of organic carbon that was consuming the available DO. Nutrient rich peat and decomposing algal biomass that had settled throughout the operation of TW-4 was stirred up by the aeration system and increased oxygen demand as well as reduced the potential for nitrification of the influent loads. A decrease of ammonia concentrations within the reach of DO concentrations > 0.2 mg/l (Figure 32) resembles the nitrogen dynamics seen in the aquaphyte. However, nitrate concentrations don’t reflect the 2 mg/l decrease in ammonia, which could be due to an insufficient number of samples ports. 74 Ammonia (NH3-N) 12.0 Nitrate (NO3-N) DO (O2) 1.2 10.0 1.0 8.0 0.8 6.0 0.6 4.0 Nitrate-N & DO (mg/L) Ammonia-N (mg/L) 1.4 0.4 2.0 0.2 0.0 0.0 -5 0 5 10 15 20 25 30 35 40 Distance From Aerators (ft) Figure 32: Performance two weeks after installation of wire bags (6/26/13). Placing the media just downstream (Figure 33) of the aeration system proved to have no apparent influence on ammonia concentration relative to the previous configuration of media directly above (Figure 32) the aeration system. Ammonia concentrations decreased by 32% within the volume of water that contained DO concentrations above 1 mg/l (Figure 33). The aeration system appeared to be reducing a fraction of the ammonia that was added from the internal load. However, the influent and effluent concentrations are approximately equal. 75 16.0 Ammonia (NH3-N) Nitrate (NO3-N) DO (O2) 2.5 2.0 12.0 10.0 1.5 8.0 1.0 6.0 4.0 0.5 2.0 0.0 Observed Nitrate-N & DO (mg/L) Observed Ammonia-N (mg/L) 14.0 0.0 -15 -5 0 5 10 15 20 25 30 35 40 100 TW 4 Eff Distance From Aerators (ft) Figure 33: Nitrogen dynamics of system 22 days after final configuration of media (wire bags) downstream of aeration system; 9.09.13 Nitrate concentrations decreased through the plume of DO so it is difficult to determine if nitrification occurred. Further research may benefit from an increased number of sample ports to better characterize the nitrogen dynamics. The TW-4 aeration system proved to be an ineffective method to facilitate nitrification. However to fully realize the potential of in-situ aeration design, it would be advantageous to install the system within a younger treatment cell with less accumulation of decomposing biomass. 76 Media and fouling. Reorientation of the wire bag media, moving the media from above the aerator to just downstream of the aerators, proved to have no consistent affect on ammonia concentrations. Upon further observation, the media downstream of the aeration system appeared to generate less biofilm than when installed directly above the diffusors. There was a strip of biofilm that had accumulated in the areas where the media was in direct contact with the turbulent zone of aeration. Biofilm accumulation was solely based on observation of the media, no volume or weight measurements were collected. The aeration system was raised out of the water column and a significant amount of microbial growth was observed on the membrane diffusers, although the fouling did not appear to reduce the flow of air into the system but could have changed the bubble size and therefore aeration efficiency. Accumulation of biofilm on the membrane diffusers could be a result of operating the diffusers at the lower threshold of the manufacturers recommended airflow range. A compressor with higher capacity or less diffusers may provide enough agitation to prevent microbial growth accumulation. This could also generate a more uniform DO concentration throughout the cross section of the treatment cell, which would prevent potential short circuiting through areas of low DO concentrations. When examining the aeration system and media containers, the majority of biofilm growth was generated on the wooden frames holding media in addition to the membrane diffusers (Figure 34), which is not ideal. 77 Figure 34: Microbial growth on membrane diffusers; half brushed off to observe extent of fouling After the reorientation of the wire bags, further examination of the installed media revealed that the strapping material and Bio Pac Honey Comb had little to no biofilm accumulation. Quantifying internal load contribution. The internal load within TW-4 was subsequently increased throughout the period during aeration. The system was shut down at the end of September where the effluent ammonia 78 concentration recorded in TW- 4 was reduced to levels comparable to the other treatment marshes (Figure 35). 35.0 Pond 2 TM1 TM2 TM3 TM4 TM5 TM6 Observed Amonia Value (mg/l) 30.0 25.0 20.0 15.0 10.0 5.0 0.0 12/7/12 1/26/13 3/17/13 5/6/13 6/25/13 8/14/13 10/3/13 11/22/13 Date of sample Figure 35: Ammonia concentrations throughout the year for all treatment marshes and pond 2 In-situ aeration in a marsh system that has been in operation for approximately 35 years contributes ammonia to the water column at a higher rate due to the stirring of decomposing algae and plant detritus. This is evident when observing ammonia effluent concentrations from the previous year (Figure 36). TW-4 follows similar performance 79 trends as the other treatment marshes, although there is a slightly higher internal load observed. Ammonia from decomposing plant and algal biomass leaches from the system and is easily observable in the summer months when ammonia concentrations in oxidation pond 2 (TW-4) are nearly zero. TW-4 has the highest average internal load likely due to the age of the system and time of operation. 90.0 Pond 2 TM1 TM2 TM3 TM4 80.0 Observed Ammonia Values(mg/l) 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 11/3 -10.0 12/23 2/11 4/1 5/21 7/10 8/29 Date of Sample Figure 36: Ammonia effluent concentrations throughout 2012 10/18 12/7 1/26 80 Comparison Normalized values were calculated for both systems to elucidate why the results seen in the aquaphyte did not translate to TW- 4. Oxygen transfer efficiency was assumed to be 20% due to lack of information on diffuser specifications, and the depth of the treatment marsh relative to conventional activated sludge chambers. Calculated values provide some insight into the divergence of results that were observed between the aquaphyte and TW - 4 (Table 15). In particular, contact time within the water containing levels of DO > 1.0 mg/l is substantially higher in the aquaphyte than that of TW-4. This difference could indicate that the system in TW-4 is oxygen limiting and may require increased compressor capacity to generate a plume of DO large enough to reach a volume that is approximately 25% of its HRT. However, increased oxygen input doesn’t necessarily facilitate high rates of nitrification if excessive organic carbon is available. Furthermore, the volume of media for microbial attachment within the DO plume in the aquaphyte was about 50% of available volume, compared to the 10% in TW-4, indicating that volume of media may need to occupy at least half the volume within the oxygenated zone. 81 Table 15: Comparison of results; normalized values between the two systems; a transfer efficiency of 20% was assumed; 20.95% oxygen concentration in air was assumed. Comparison values Contact time within reach of oxygen volume (hrs) Contact time within media (HRT) Media surface area/ volume of DO water Volume of media/volume of DO water aquaphyte 12.72 25% 8.1 48% TW-4 3.9 6% 2.0 9% The plant biomass in the aquaphyte exists within the entire reach of dissolved oxygen. Additionally, TW-4 has lower concentrations of dissolved oxygen as well as lower volume (by percentage) of available media within the oxygen advection zone. Ultimately, the long operational history of TW-4 contributes to the divergence in performance between the two systems. Plant cycles and high ammonia loading over the past 35 years have negatively impacted performance of the wetland cells and the capacity to increase water quality. 82 CONCLUSION The aquaphyte pilot project has shown that in-situ seasonal aeration to facilitate nitrification can be a potentially viable option for AWTF to reduce ammonia concentrations, despite full-scale designs proving to be ineffective. Water temperature did not fully inhibit rates of nitrification in the aquaphyte with the loading seen over the winter of 2011 and 2013. Additionally, no media was necessary due to the density of plants that existed within the water column. Ultimately, the aquaphyte required approximately 28 days to generate consistent ammonia reduction and BOD removal. This operational startup period may depend on the water temperature and loading rates. In conclusion, with the loading rates and water temperatures observed, in-situ aeration can facilitate nitrification in young wetland cells. Effectiveness was lost in scale up due to the extensive accumulation of accreted ammonia and organic carbon over the past 35 years of operation. Both constituents are stirred up during operation of the large scale aeration system, which consumes much of the available oxygen reducing the potential for influent ammonia conversion. As a result of deferred maintenance throughout the lifetime of the AWTF treatment wetlands, the capacity to improve water quality will continue to degrade if maintenance and harvest of accumulated biomass continues to be avoided. Consequently, inhibited performance coupled with future increases to water quality standards could result in a preventable economic burden for the City of Arcata. Full-scale in-situ aeration to facilitate nitrification is a plausible solution for increases to ammonia 83 limits, dictated by the NCRWQCB. Nevertheless, an increase in treatment capacity in addition to algal and plant detritus harvesting will be necessary to generate appropriate ammonia removal efficiencies in a full scale system for AWTF. Recommendation The City of Arcata can utilize conventional treatment technologies like a bio-tower, trickling filter, or an aeration channel to reduce ammonia and nitrate concentrations. These are proven technologies that effectively reduce nitrogen levels, although they would require substantial infrastructure development and operational training. Space is limited at the AWTF and it would be advantageous to avoid additional infrastructure development. Conventional technologies exist to sufficiently reduce nutrient loads, although there is still potential to utilize an in-situ aeration design when considering alternative treatment methods. The aquaphyte experiment has proven that artificial aeration in wetland cells has the potential to be an effective method to facilitate nitrification, but further research is required to determine necessary operational and design parameters of a full-scale system. Installing an aeration system into a full-scale newly established wetland cell (2-3 years old) would help quantify how much the internal load affects the treatability of influent loading. Additionally, it could be beneficial to construct a new wetland treatment cell, perhaps where previous hatchery ponds existed, with the particular objective of reducing ammonia concentrations. This step in research and scale would help AWTF further understand the feasibility of in-situ aeration. AWTF 84 is an aging system and its capacity to improve water quality will continue to become inhibited as it stores nutrients and organic carbon. A new treatment wetland would be beneficial to the city, as it will be required to temporarily shut down existing treatment wetlands to eventually manage the deferred maintenance of biomass and peat removal. Consequently, in order for in-situ aeration systems to become a viable option to sustainably treat nitrogen loading, AWTF should adhere to a strict peat and plantharvesting operational schedule. This will prolong the effectiveness of treatment wetlands to improve water quality, although the nutrient dense biomass will also require mitigation. Capacity for composting or bio-digestion of the wetland plant biomass and nutrient laden peat should be incorporated within any new wetland design. Alternatively, Bioconversion through black soldier fly (Hermetia illuscens) production may be a viable option for the city of Arcata to reduce the biomass that has accumulated over the past 35 years of operation. Pilot scale black soldier fly systems have proven to reduce dairy waste, swine manure, chicken manure, municipal organic waste dry matter weight by 58%, 56%, 50%, and 68%, respectively (Sheppard, 2006 and Myers, 2008 and Diener, 2011). This process converts highly concentrated nutrient laden waste into high value pupae biomass that is approximately 35% lipid and 45% proteins that can create potential revenue for the City of Arcata (Diener, 2009). It is recommended that the City of Arcata take steps in mitigating the accumulation of biomass and peat. In addition, supplementary research with a full-scale in-situ aeration 85 system is necessary to accurately determine its feasibility at AWTF. Land area for further study is available in the previously used hatchery ponds. 86 REFERENCES Austin, D. , and Nivala, J. (2009). Energy requirements for nitrification and biological nitrogen removal in engineered wetlands. Ecological Engineering, 35(2), 184-192. 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Nutrient Removal in Wetlands During Intermittent Artificial Aeration. Environmental Engineering Science. Volume 25, Scotland, UK 91 APPENDIX A Operational parameters Date Notes time (min) sec/500mL Volume (gal) Flowrate (gpm) HRT (days) Rotameter (SCFH) 12/31/12 60 1.00 0.13 0.13 2.7 0 1/1/13 60 1.00 0.13 0.13 2.7 0 1/2/13 60 1.00 0.13 0.13 2.7 0 1/3/13 59 0.98 0.13 0.13 2.6 0 1/4/13 58 0.97 0.13 0.14 2.6 0 1/5/13 60 1.00 0.13 0.13 2.7 0 1/6/13 59 0.98 0.13 0.13 2.6 0 1/7/13 58 0.97 0.13 0.14 2.6 0 1/8/13 60 1.00 0.13 0.13 2.7 0 1/9/13 60 1.00 0.13 0.13 2.7 0 1/10/13 61 1.02 0.13 0.13 2.7 0 1/11/13 59 0.98 0.13 0.13 2.6 0 1/12/13 60 1.00 0.13 0.13 2.7 0 1/13/13 61 1.02 0.13 0.13 2.7 0 1/14/13 60 1.00 0.13 0.13 2.7 0 1/15/13 61 1.02 0.13 0.13 2.7 0 1/16/13 63 1.05 0.13 0.13 2.8 0 1/17/13 NA 0 1/18/13 NA 0 1/19/13 59 0.98 0.13 0.13 2.6 0 1/20/13 65 1.08 0.13 0.12 2.9 0 1/21/13 58 0.97 0.13 0.14 2.6 0 1/22/13 58 0.97 0.13 0.14 2.6 0 1/23/13 59 0.98 0.13 0.13 2.6 0 1/25/13 59 0.98 0.13 0.13 2.6 0 1/27/13 58 0.97 0.13 0.14 2.6 0 59 0.98 0.13 0.13 2.6 30 61 1.02 0.13 0.13 2.7 0 1/28/13 1/29/13 Air started air off electrical issue 92 Date Notes 1/30/13 air off Ball-valve system: parastalitic pump off-line needing repair, Flowrate taken as average of instantaneous and adjusted Flowrate taken as average of instantaneous and adjusted Flowrate taken as average of instantaneous and adjusted Flowrate taken as average of instantaneous and adjusted New air stone: ~60 SCFM above water Flowrate taken as average of instantaneous and adjusted Flowrate taken as average of instantaneous and adjusted 1/31/13 2/1/13 2/2/13 2/3/13 2/4/13 2/6/13 2/7/13 2/8/13 2/10/13 2/11/13 Flowrate taken as average of instantaneous and adjusted Flowrate taken as average of instantaneous and adjusted 2/13/13 2/15/13 Parastaltic back online, Flowrate taken time (min) sec/500mL Volume (gal) Flowrate (gpm) HRT (days) Rotameter (SCFH) 62 1.03 0.13 0.13 2.8 0 53 0.88 0.13 0.15 2.3 35 49 0.81 0.13 0.16 2.2 36 36 0.60 0.13 0.22 1.6 36 39 0.64 0.13 0.21 1.7 37 59 0.98 0.13 0.13 2.6 42 42 0.69 0.13 0.19 1.9 51 33 0.55 0.13 0.24 1.5 53 73 1.22 0.13 0.11 3.3 53 41 0.68 0.13 0.20 1.8 48 54 0.89 0.13 0.15 2.4 50 59 0.98 0.13 0.13 2.6 52 36 0.60 0.13 0.22 1.6 93 Date Notes as average of instantaneous and adjusted time (min) sec/500mL Volume (gal) Flowrate (gpm) HRT (days) Rotameter (SCFH) 2/17/13 56 0.93 0.13 0.14 2.5 51 2/18/13 56 0.93 0.13 0.14 2.5 52 2/19/13 68 1.13 0.13 0.12 3.0 2/21/13 65 1.08 0.13 0.12 2.9 52 63 1.05 0.13 0.13 2.8 52 65 1.08 0.13 0.12 2.9 52 60 1.00 0.13 0.13 2.7 52 2/25/13 59 0.98 0.13 0.13 2.6 53 3/1/13 59 0.98 0.13 0.13 2.6 52 3/3/13 59 0.98 0.13 0.13 2.6 52 3/4/13 59 0.98 0.13 0.13 2.6 52 59 0.98 0.13 0.13 2.6 52 2/22/13 2/24/13 2/24/13 Rinsed stabilization tank - minimal sediment Installed new float switch anchor 3/8/13 3/10/13 Ammonia probe on order 60 1.00 0.13 0.13 2.7 53 3/13/13 60 1.00 0.13 0.13 2.7 53 3/20/13 61 1.02 0.13 0.13 2.7 53 3/24/13 60 1.00 0.13 0.13 2.7 53 60 1.00 0.13 0.13 2.7 52 60 1.00 0.13 0.13 2.7 51 60 1.00 0.13 0.13 2.7 52 60 1.00 0.13 0.13 2.7 50 60 1.00 0.13 0.13 2.7 50 60 1.00 0.13 0.13 2.7 51 60 1.00 0.13 0.13 2.7 0 60 1.00 0.13 0.13 2.7 0 62 1.03 0.13 0.13 2.8 0 56 0.93 0.13 0.14 2.5 0 3/25/13 3/29/13 Slight drop in air: diffuser fouling? 3/31/13 4/5/13 4/6/13 4/7/13 Out: 68s/0.5L Out: 61s/0.5L, Air turned off at 4 pm 4/12/13 4/14/13 pump sounds funny 4/15/13 4/19/13 Pump malfunction - 94 Date 5/10/13 Notes switched to constant head system pump back online, air stone broke; installed new air stone time (min) sec/500mL Volume (gal) Flowrate (gpm) HRT (days) Rotameter (SCFH) 61 1.02 0.13 0.13 2.7 38 60 1.00 0.13 0.13 2.7 41 56 0.93 0.13 0.14 2.5 40 60 1.00 0.13 0.13 2.7 40 60 1.00 0.13 0.13 2.7 40 63 1.05 0.13 0.13 2.8 40 70 1.16 0.13 0.11 3.1 40 94 1.57 0.13 0.08 4.2 38 6/7/13 55 0.92 0.13 0.14 2.5 38 6/12/13 60 1.00 0.13 0.13 2.7 38 5/17/13 5/20/13 lots of new vegetation (bullrush, celery) 5/22/13 5/23/13 lots of red small organisms in pond 5/27/13 5/30/13 6/5/13 pump sounds funny replaced tubing, pump sounds less funny 6/13/13 windy 60 1.00 0.13 0.13 2.7 38 8/20/13 plant harvest 60 1.00 0.13 0.13 2.7 0 59 0.98 0.13 0.13 2.6 0 59 0.98 0.13 0.13 2.6 0 61 1.02 0.13 0.13 2.7 40 11/24/13 0.00 0.13 12/13/13 0.00 0.13 12/14/13 0.00 0.13 12/16/13 0.00 0.13 12/19/13 0.00 0.13 12/30/13 0.00 0.13 12/31/13 0.00 0.13 59 0.98 0.13 0.13 2.6 0 59 0.98 0.13 0.13 2.6 0 11/14/13 11/21/13 Turned on air after sample for nutrients 11/23/13 11/14/13 11/21/13 Turned on air after sample for 95 Date Notes nutrients time (min) sec/500mL 11/23/13 Aquaphyte water quality data 61 1.02 Volume (gal) 0.13 Flowrate (gpm) 0.13 HRT (days) Rotameter (SCFH) 2.7 40 96 Ammonia-N (mg/L) SP 1 Date (INF) 1/4/13 17.3 1/12/13 17.9 1/18/13 39.7 1/25/13 26.5 2/8/13 25.5 2/15/13 23.0 2/22/13 25.4 SP 2 SP 3a SP 3b SP 3 (Avg) SP 4 SP 5a SP 5b SP 5 (Avg) SP 6 SP 7a SP7 b SP 7 (Avg) SP 8 SP 9 (EFF) 16.7 16.4 14.3 15.4 14.3 13.7 9.1 11.4 10.7 11.8 7.1 9.5 8.5 9.3 18.4 18.2 16.6 17.4 16.4 16.0 9.7 12.8 13.9 12.4 6.9 9.7 8.6 9.0 25.3 39.8 24.0 31.9 25.6 14.3 9.6 11.9 11.7 13.6 7.8 10.7 7.4 11.9 25.7 24.3 24.5 24.4 24.3 22.8 13.6 18.2 16.9 16.4 12.9 9.5 15.9 25.4 19.3 15.9 17.6 15.5 14.7 13.4 14.1 15.5 16.1 14.4 16.2 16.7 22.7 22.8 18.2 20.5 17.6 17.5 15.0 16.2 16.9 16.3 9.4 12. 7 14. 6 15.4 15.0 14.3 25.9 19.6 2.0 10.8 1.4 0.8 0.3 0.5 0.5 0.7 0.1 0.4 0.4 0.4 Ammonia probe malfunction - no ammonia data 3/20/13 26.5 22.5 16.1 2.1 9.1 1.3 1.0 0.4 0.7 0.6 0.7 0.3 0.5 0.4 0.3 19.4 18.7 15.3 0.9 8.1 0.6 0.2 0.1 0.2 0.3 0.6 0.1 0.4 0.2 0.2 14.6 15.2 15.1 1.3 8.2 0.6 0.5 0.2 0.3 0.5 0.5 0.2 0.3 0.5 0.3 19.1 18.8 18.6 20.6 19.6 17.5 16.7 12.3 14.5 14.7 12.8 8.3 10.6 9.8 8.1 0.0 1.7 3.0 3.8 3.4 0.2 0.3 0.4 0.4 0.7 0.8 0.5 0.6 1.0 0.8 0.3 2.1 2.9 4.2 3.6 0.2 0.3 0.2 0.3 0.4 0.9 0.2 0.5 0.4 0.3 1.7 2.8 3.3 5.9 4.6 0.4 0.5 0.3 0.4 0.6 0.5 0.3 0.4 0.5 0.4 3/29/13 4/5/13 4/12/13 5/17/13 5/22/13 5/27/13 5/27/13 97 Nitrate-N (mg/L) SP 1 Date (INF 1/4/13 0.7 1/12/13 0.2 1/18/13 0.2 1/25/13 0.2 2/1/13 2/8/13 SP 2 SP 3 (Avg) SP7b SP 7 (Avg) SP 8 SP 9 (EFF) 3.0 6.9 4.9 5.2 4.6 2.8 3.3 6.4 4.9 4.1 4.1 5.4 4.5 4.8 8.4 6.6 7.4 3.6 4.6 2.7 1.8 1.8 4.8 3.3 2.9 1.3 5.3 3.0 4.2 3.1 4.2 3.3 3.7 4.8 4.1 9.1 9.7 9.3 9.5 7.8 5.7 6.7 6.2 5.1 4.7 3.1 5.4 5.2 6.3 5.7 5.5 5.1 5.5 5.3 5.0 5.5 21.6 13.5 21.5 22.4 20.9 21.6 21.1 19.7 19.5 19.6 17.9 17.6 4.2 17.9 11.0 18.5 19.4 19.0 19.2 19.2 18.1 16.3 17.2 16.8 17.0 1.7 9.6 25.8 17.7 26.2 26.0 25.7 25.8 23.2 21.1 16.4 18.7 16.7 16.8 2.9 2.3 4.4 18.2 11.3 18.3 18.0 16.0 17.0 15.9 13.7 12.3 13.0 11.2 11.0 4.3 2.4 1.9 16.6 9.2 17.1 16.6 14.5 15.6 14.4 13.1 9.7 11.4 10.1 8.7 2.8 2.0 0.9 0.6 0.7 0.6 0.5 0.7 0.6 0.3 0.4 0.7 0.6 0.3 0.8 5.9 2.7 1.3 1.4 1.4 5.9 5.4 3.2 4.3 3.5 2.4 1.1 1.7 0.6 0.8 5.1 1.4 1.0 0.7 0.8 3.6 3.3 2.0 2.7 1.7 1.0 0.5 0.8 0.3 0.2 2.0 0.4 0.2 0.3 0.3 2.9 2.6 1.0 1.8 1.5 0.8 0.4 0.6 0.3 0.3 SP 3a SP 3b 1.3 1.9 3.2 2.5 0.4 0.8 2.0 0.8 1.3 0.5 0.3 SP 4 SP 5 (Avg) SP 5a SP 5b SP 6 2.4 2.3 5.9 4.1 5.2 1.4 1.7 1.8 5.3 3.5 2.1 1.7 2.3 2.5 8.4 0.8 1.0 0.9 0.6 0.8 0.6 6.7 6.0 6.3 6.0 0.3 1.2 6.5 8.9 7.7 0.3 1.2 1.2 4.9 0.4 1.7 5.5 0.3 1.0 0.8 SP 7a 2/15/13 2/22/13 3/1/13 3/20/13 3/29/13 4/5/13 4/12/13 5/17/13 5/22/13 5/27/13 98 BOD (mg/L) Date 1/4/13 CBOD (mg/L) SP 1 (INF) SP 2 SP 4 SP 6 SP 8 SP 9 (EFF) SP 1 (INF) SP 2 SP 4 SP 6 SP 8 SP 9 (EFF) 18.5 13.2 13.7 10.4 8.6 7.6 18.3 17.2 18.1 14.1 8.6 4.4 16.8 12.6 12.8 9.5 13.4 7.5 7.3 5.9 19.1 17.8 18.2 22.2 18.1 14.2 8.2 8.0 15.4 23.8 24.7 22.7 13.2 11.6 11.2 11.0 23.2 32.4 27.2 18.2 16.3 16.7 13.3 11.0 27.2 16.8 15.3 23.0 23.1 BOD probe investigation - Lauren moved BOD equipment to campus 7.5 5.6 5.4 14.1 7.6 11.7 16.1 17.8 10.9 7.5 10.1 1/11/13 1/20/13 1/27/13 2/3/13 2/10/13 2/17/13 2/24/13 3/3/13 3/10/13 3/24/13 3/31/13 4/7/13 24.5 28.5 48.5 136.8 147.6 33.8 36.3 57.2 197.7 20.9 14.7 8.3 10.9 7.3 (a) 17.7 (a) 29.5 33.8 18.8 8.3 4.9 8.0 13.5 11.4 22.3 21.5 10.6 15.2 21.0 21.3 37.1 35.3 (a) 10.5 7.6 9.3 5.6 4.0 5.7 7.2 4.6 99 BOD (mg/L) Date 4/12/13 4/14/13 5/23/13 5/30/13 6/7/13 6/13/13 CBOD (mg/L) SP 1 (INF) SP 2 (a) (a) 108.0 108.8 84.8 42.8 SP 4 SP 6 47.6 40.8 SP 8 SP 9 (EFF) SP 1 (INF) SP 2 31.3 (a) 15.8 19.4 17.0 8.9 28.5 37.1 37.8 20.7 SP 4 14.0 SP 6 13.5 SP 8 SP 9 (EFF) (a) 7.9 9.7 12.6 100 TSS (mg/L) Date 1/20/13 SP 1 (INF) SP 2 SP 3a SP 3b (b) (b) (b) (b) 48 47 36 34 SP 3 (Avg) SP 4 SP 5a SP 5b (b) (b) (b) 40 68 37 SP 5 (Avg) SP 6 SP 7a SP7b (b) (b) (b) 39 22 22 SP 7 (Avg) SP 8 SP 9 (EFF) (b) (b) 23 20 1/27/13 35 52 22 2/3/13 40 44 44 26 2/10/13 54 54 44 34 188 52 57 25 2/17/13 53 67 39 28 34 34 20 24 22 35 19 24 21 22 15 59 96 84 62 73 71 43 31 37 63 34 34 34 28 16 55 92 43 39 41 28 39 33 31 31 31 43 2/24/13 3/3/13 3/10/13 67 3/24/13 67 3/31/13 80 4/7/13 140 19 8 48 8 4/14/13 46 24 8 5/23/13 102 53 45 19 67 95 45 56 51 72 38 47 43 38 26 47 61 100 43 70 57 58 37 49 43 35 18 204 76 140 96 53 50 51 55 30 32 31 29 18 45 39 42 63 43 39 41 52 31 32 32 29 18 75 4/12/13 5/30/13 162 33 21 6/7/13 81 14 6/13/13 99 14 101 Treatment Marsh 4 water quality data Date 5/22/13 5/30/13 6/6/13 6/7/13 6/13/13 6/17/13 6/26/13 Sample Location BOD (ppm) CBOD (ppm) NBOD (ppm) BOD (ppm) CBOD (ppm) NBOD (ppm) BOD (ppm) CBOD (ppm) NBOD (ppm) BOD (ppm) CBOD (ppm) NBOD (ppm) BOD (ppm) CBOD (ppm) NBOD (ppm) P2 -15 -5 109.20 5 ft 128.40 10 ft 20 ft 77.10 30 ft 40 ft 0.00 85.95 27.75 58.20 122.70 92.80 0.00 0.00 91.35 86.88 38.58 48.30 83.25 94.20 53.63 40.58 91.50 92.40 22.38 70.02 51.00 13.50 37.50 84.45 33.06 51.39 75.60 39.60 36.00 79.50 27.90 51.60 38.55 12.36 26.19 74.55 24.90 49.65 44.55 18.10 26.45 BOD (ppm) 64.05 59.25 59.25 58.80 CBOD (ppm) 23.60 40.62 24.72 23.10 NBOD (ppm) 40.45 18.63 34.53 35.70 BOD (ppm) 118.60 40.65 36.75 38.40 200 ft CBOD (ppm) NBOD (ppm) 7/3/13 BOD (ppm) 72.40 74.28 162.60 74.04 58.43 56.63 67.20 55.20 52.03 CBOD (ppm) 34.92 15.28 60.60 38.97 19.13 13.63 14.64 13.15 12.03 NBOD (ppm) 37.48 59.00 102.00 35.07 39.30 43.00 52.56 42.05 40.00 102 Date Sample Location P2 -15 -5 5 ft 10 ft 20 ft BOD (ppm) 53.64 70.68 71.00 41.60 108.80 36.43 36.08 CBOD (ppm) 28.04 17.95 17.31 14.80 18.56 8.80 7.38 NBOD (ppm) 25.60 52.73 53.69 26.80 90.24 27.63 28.70 75.72 69.12 34.60 33.30 35.63 37.80 7/17/13 BOD (ppm) 9/3/13 30 ft 40 ft 200 ft CBOD (ppm) NBOD (ppm) Ammonia (mg/l) Date 4/18/13 4/25/13 4/26/13 5/3/13 5/9/13 5/16/13 5/30/13 6/3/13 6/5/13 6/17/13 6/19/13 6/26/13 7/1/13 7/3/13 P2 0.2 5.4 2.0 1.7 0.1 0.0 0.4 1.4 0.2 -15 ft 8.2 3.9 5.9 0.4 11.1 8.1 -5 ft 18.9 18 13.6 14.8 4.8 7.7 3.1 0.0 11.4 3.6 0.4 7.2 9.6 Air 18.4 18 4.5 4.9 4.6 4.5 4.4 5.1 0.4 9.2 8.4 5 ft 18.8 18 19.8 16.0 15.7 7.9 5.2 4.7 5.2 4.2 7.5 0.4 9.6 10.1 10 ft 17.1 19 15 ft 20 ft 25 ft 30 ft 35 ft 40 ft 18 18 19 18 16.6 16.7 16.7 17.0 9.1 5.2 4.8 4.6 4.2 5.4 0.4 10.3 10.2 6.5 5.3 4.5 0.0 4.1 4.9 0.4 9.5 9.5 18 18.6 16.8 15.9 8.5 5.1 4.6 0.0 4.0 5.3 0.4 9.6 9.4 6.6 5.1 4.7 0.0 4.0 5.1 0.4 9.8 9.7 5.9 4.9 4.7 0.0 4.1 4.9 0.4 9.9 10.8 18 16.9 17.3 15.5 5.4 5.0 4.8 0.0 4.5 6.2 0.4 9.1 10.5 6.1 5.2 4.6 0.0 4.1 4.9 0.4 9.8 10.8 100 ft 0.0 0.4 9.6 11.6 TW-4 Eff 16.9 18.0 17.4 9.9 6.7 5.2 8.2 6.2 6.6 0.4 10.4 103 Ammonia (mg/l) Date 7/8/13 7/10/13 7/15/13 7/22/13 7/25/13 8/15/13 8/18/13 8/23/13 8/27/13 9/2/13 9/09/13 9/16/13 P2 0.6 0.9 0.1 0.1 -15 ft 8.7 6.8 9.3 13.2 -5 ft 8.7 6.5 9.2 13.0 Air 9.9 8.5 9.2 13.7 5 ft 10.1 6.8 9.2 13.9 10 ft 13.2 10.7 10.9 13.6 8.2 10.1 8.9 10.3 11.6 12.0 2.4 8.2 7.6 9.4 11.6 14.1 10.7 5.1 9.9 8.6 11.3 13.2 9.6 11.2 4.8 12.4 9.5 12.4 15.7 10.6 14.6 5.5 17.9 9.7 14.8 15.3 9.2 14.8 15 ft 10.8 16.7 9.9 14.7 8.8 11.0 9.6 12.9 10.4 14.2 20 ft 10.9 11.0 9.9 17.2 7.8 11.5 11.5 15.6 9.6 14.0 25 ft 11.3 30 ft 11.3 35 ft 11.2 40 ft 13.1 100 ft 12.6 9.9 15.8 9.9 13.0 8.9 12.8 9.2 12.9 9.2 13.1 TW-4 Eff 9.3 9.4 9.7 12.7 15.4 10.3 15.5 10.1 9.9 14.4 12.5 10.6 15.1 9.6 12.1 16.1 17.1 10.3 12.1 9.9 10.5 10.7 21.8 10.4 12.9 9.4 16.0 9.7 8.9 11.1 14.6 17.3 12.2 13.7 104 Nitrate (mg/L) Date 4/18/13 4/25/13 4/26/13 5/3/13 5/9/13 5/16/13 5/30/13 6/3/13 6/5/13 6/17/13 6/19/13 6/26/13 7/1/13 7/3/13 7/8/13 7/10/13 7/15/13 7/22/13 7/25/13 8/15/13 8/18/13 8/23/13 8/27/13 9/2/13 9.09/13 9/16/13 P2 -15 ft 0.8 Air 5 ft 10 ft 15 ft 20 ft 25 ft 30 ft 35 ft 40 ft 1.0 0.5 0.9 0.8 1.1 0.6 0.35 2.8 1.7 0.5 0.6 0.5 1.3 0.4 0.4 0.4 0.3 0.3 0.6 4.0 2.3 2.6 0.3 0.8 3.1 0.7 0.4 0.5 0.4 0.9 0.5 0.3 0.4 0.5 0.6 0.4 0.5 0.3 0.9 0.4 0.3 0.3 0.4 0.4 0.3 0.7 0.3 0.9 0.4 0.3 0.3 0.4 0.3 0.3 1.1 1.1 1.0 0.7 0.6 1.0 0.2 0.9 0.8 0.8 0.6 0.5 0.7 0.2 0.8 0.7 0.7 0.4 0.4 0.6 5.1 2.2 1.5 2.1 1.2 0.9 0.3 0.3 0.6 0.4 -5 ft 0.2 2.7 2.6 1.4 1.9 0.4 0.6 0.5 0.5 0.4 0.56 2.7 1.6 0.8 0.6 0.4 0.9 0.3 0.3 0.3 0.3 0.3 0.3 0.5 0.3 0.9 0.3 0.3 0.3 0.4 0.3 0.3 0.5 0.3 0.9 0.3 0.3 0.3 0.3 0.3 0.3 0.2 0.7 0.6 0.7 0.4 0.4 0.5 0.2 0.6 0.5 0.6 0.4 0.3 0.4 0.6 0.5 0.6 0.3 0.3 0.4 100 ft 2.6 2.5 1.4 0.5 0.4 0.0 0.5 0.4 1.8 0.5 0.4 0.3 0.49 2.5 1.8 2.2 0.5 0.4 0.6 0.3 0.9 0.3 0.3 0.3 0.3 0.3 0.3 0.6 0.3 0.9 0.3 0.3 0.3 0.5 0.3 0.9 0.3 0.3 0.3 0.5 0.3 0.9 0.3 0.4 0.2 0.5 0.3 0.9 0.3 0.4 0.3 0.3 0.2 0.3 0.2 0.3 0.2 0.3 0.2 0.2 0.2 0.6 0.5 0.5 0.3 0.3 0.4 0.6 0.4 0.5 0.3 0.3 0.4 0.5 0.4 0.4 0.3 0.2 0.3 0.5 0.4 0.4 0.3 0.2 0.3 0.5 0.3 0.5 0.3 0.2 0.3 0.5 TW 4 Eff 0.23 1.3 0.2 2.3 0.3 0.3 0.9 0.3 0.4 0.7 0.2 0.9 0.3 0.3 0.2 0.2 0.4 0.3 0.4 0.3 0.2 0.3 105 DO (mg/L) Date 4/18/13 4/25/13 4/26/13 5/3/13 5/9/13 5/16/13 5/30/13 6/17/13 6/19/13 6/26/13 7/1/13 7/3/13 7/8/13 7/10/13 7/15/13 7/22/13 7/25/13 8/15/13 8/18/13 8/23/13 8/27/13 9/2/13 9.09/13 9/16/13 -5 ft -15ft Air 5 ft 10 ft 15 ft 20 ft 25 ft 30 ft 35 ft 1.3 4.63 5.06 5.21 4.6 3.51 5.63 2.43 0.83 0.23 0.17 0.22 3.4 1.16 19.2 0.11 2.28 0.45 0.1 4.68 3.37 3.24 2.65 2.18 2 3.31 1.56 2.4 2.89 2.91 2.92 3.32 2.71 2.45 0.54 2.48 1.25 2.65 1.20 2.03 0.05 0.61 19.4 2.01 0.71 6.496 4.5 1.33 0.3 1.25 0.37 0.32 0.08 3.37 1.15 0.49 0.16 0.25 0.19 0.02 0.13 19.1 0.08 0.1 3.05 1.65 0.68 0.65 0.07 0.1 0.07 0.06 2.25 3.1 3.28 3.04 2.2 1.58 0.5 0.22 0.20 0.08 0.02 0.09 19.1 0.07 0.15 0.33 0.46 0.18 1.17 0.3 0.15 0.07 0.05 1.93 1.53 0.47 0.14 0.19 0.05 0.01 0.04 19.3 0.05 0.05 1.69 1.53 0.71 0.2 0.23 0.20 0.03 0.01 0.01 19.2 0.04 0.03 0.94 1.69 0.53 0.15 0.27 0.25 0.01 0.01 0.01 2.46 3.97 2.28 1.79 1.47 0.83 0.16 0.1 0.15 0.01 0.01 0.01 0.14 0.17 0.01 0.01 0.01 0.19 0.24 0.01 0.01 0.01 17.3 0.02 0.01 0.7 0.01 0.24 0.01 0.09 0.01 0.015 0.01 0.08 0.72 0.14 0.07 0.06 0.05 0.05 0.67 0.07 0.07 0.05 0.05 0.03 0.6 0 0 0 0.01 0.01 0.3 0 0.04 0 0 0.01 0.24 0 0.02 0 0 0.01 0.01 0.01 0 0 0 0 3.35 2.18 0 0.12 0.11 0.13 0.00 1.4 0.25 0.32 21.7 0.24 0.19 0.25 0.17 0.23 0.2 0.1 5.16 0.97 0.08 1.9 0.22 0.00 0.31 0.09 0.14 19 0.18 0.26 0.37 0.18 0.26 0.17 0.18 0.16 0.14 40 ft 100 ft TW 4 Eff 0.32 0.38 1.12 0.4 0.01 0 0 0.01 0.01 106 Normalized calculations tables Aquaphyte values Oxygen concentration 4.43 mg/l (average sp 3) 125.3 mg/ft 6.16 mg/l (average sp 4) 174.2 mg/ft Submerged surface area 3 mg/l (average sp 5) 50.9 mg/ft mg/l 116.8 mg/ft 8 feet 13.5 3 ft3 water 1.6 grams 55% porosity 272.88 ft 2 3 0.1494442 m 4.8093696 ft 3 56.74 Average between points 4.13 m volume of submerged media 3 1.8 2 26.97 3 2 ft /ft 3 Operational parameters Flow (gal/day) 190.5 (L/Day) 720.0 Flow (L/min) 3 0.5 ft /day 25.5 Velocity (ft/day) 15.1 contact time within reach of oxygen (Hrs) contact time within media (HRT) mass of oxygen available within oxygen reach (mg)/media surface 2 area ft 12.72 25% 5.77819 media surface area/ volume of oxygen reach 8.09 volume of media/volume of DO water 48% 107 Treatment Marsh 4 volume water within oxygen reach Length (ft) surface area on media (ft3/bag) 10 Width (ft) 18 Height (ft) 3 3 Water Volume (ft ) 7.84 2 strapping (ft ) 540 3 strapping volume (ft ) 2 3 3 strapping (ft /ft ) 180 540 3 6 bags of media (ft ) 2 plan view 47.04 3 biopac (ft /ft ) 2 surface area (ft ) 180 30 2 biopac (ft ) 1411.2 2 available surface area (ft ) media/reach volume 0.0926 70% 987.8 3 total media volume (ft ) 50.04 2 total media surface area (ft ) 1527.84 time through contact volume Oxygen concentration 2.2 mg/l 62.21 mg/ft volume of media storage container 3 wooden boxes (ft3) 14.6 chicken wire bags 72 water flow (gal/day) 22300 (L/Day) 84294 3 ft /day 2981.084 velocity (ft/day) 69.73 contact time within reach of oxygen volume (Hrs) 3.9 contact time within media (HRT) mass of oxygen available within oxygen reach (mg)/media surface area ft 6% 2 22.0 media surface area/ volume of oxygen reach 2.0 volume of media/volume of DO water 9%
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