The purpose of this research was to develop a single sludge multi-environment anoxic/aerobic biological treatment scheme that could achieve oxime degradation and nitrification in the same treatment process. Aerobic and anoxic batch experiments were initially performed to determine degrees of nitrification inhibition caused by three oximes, acetaldehyde oxime (AAO), aldicarb oxime (ADO), and methyl ethyl ketoxime (MEKO), and to investigate the fate of these oximes under anoxic, denitrifying conditions. Results from aerobic batch studies showed that MEKO was the only oxime which caused significant nitrification inhibition at concentrations expected in the industrial client's waste streams. Nitrification rates were reduced by 31% at MEKO concentrations as low as 2 mg/L and were almost completely inhibited above 9 mg/L. Results from anoxic batch studies demonstrated that MEKO was biologically degraded under nitrate limiting conditions, although the microorganism( s) responsible were not explicitly identified. Similar degradation trends were seen for AAO, but at significantly lower rates. ADO, however, appeared to be stable under all anoxic conditions examined. Results from batch studies were utilized to determine operational conditions for a single sludge multi-environment anoxic/anaerobic/aerobic sequencing batch reactor supplied with a synthetic organic wastewater containing up to 40 mgIL MEKO and 56 mgIL AAO. The system was able to achieve complete oxime degradation and nitrification when operated on a one day cycle with a twelve hour anoxic/anaerobic reaction phase and a nitrate:carbon ratio below 0.15 mg N0₃-N/mg TOC. / Master of Science

Anaerobic digestion (AD) has been shown to be an effective technique for energy recovery and stabilization of livestock wastes, municipal sludges and industrial wastewaters. However, further treatment is required to remove nitrogen from AD effluents to avoid detriments to surface and ground waters. The high free ammonia (FA) concentrations present in AD effluents can inhibit nitrification processes in conventional biological nitrogen removal (BNR) systems. The overall goal of this research was to develop a process for removal of nitrogen from AD swine waste (ADSW) effluent. The proposed solution was to incorporate particulate chabazite, which has a high cation exchange capacity, into a sequencing batch reactor (SBR) to adsorb ammonium and therefore ease nitrification inhibition. The process developed is called a chabazite-SBR. Three research questions were used to guide this research. First question (Chapter 3): How does chabazite pretreatment with groundwater (GW) affect the kinetics and cation exchange capacity during ammonium (NH4+) uptake? Kinetics and isotherm batch tests were performed with GW pretreated chabazite. In addition, sodium chloride (NaCl), and deionized water (DI) pretreated chabazite was included for comparison because these are typically used pretreatment methods. The Ion Exchange (IX) isotherm model was used to calculate the cation exchange capacity and the pseudo-first and film diffusion kinetics models were applied to quantify the effect of the pretreatment on the reaction rate. Results showed that the exchange capacity was slightly higher for GW pretreated chabazite compared with the other common pretreatment strategies; however, the enhancement was not significantly different. The kinetics of NH4+ uptake during the first four hours of contact was significantly improved by GW pretreatment when compared with other common pretreatment strategies. This was caused by an enhancement in film diffusion mechanisms. The findings of this first part of the research were important because it was shown that NaCl pretreatment is not needed to improve the kinetics and cation exchange capacity of chabazite. Second question (Chapter 4): How does addition of chabazite to ADSW centrate affect nitrification rates? Nitrification batch test with varying NH4+ concentrations were performed to identify the inhibitory NH4+ concentration. Additional nitrification batch tests treating real and synthetic waste with initial NH4+ concentration of 1,000 mg-N L-1 with added zeolite were performed. For the mixed liquor tested in this study, NH4+ concentrations must be maintained below 200 mg-N L-1 to relieve nitrification inhibition. Treatment of ADSW centrate requires a chabazite dose of 150 g L-1 to ease FA inhibition of nitrification. The rate of nitrification increased, by approximately a factor of 3, when chabazite was added to a batch reactor treating high NH4+ strength wastewater. However, Na+ release from the chabazite also plays a role in nitrification inhibition. The findings of this part of the research showed the potential for using chabazite for overcoming FA inhibition of nitrification during treatment of high NH4+ strength wastewater. Third question (Chapter 5): How effective is the chabazite-SBR in removing total nitrogen concentrations from ADSW centrate? A chabazite-SBR was operated for 40 weeks (cycles) to study the TN removal efficiency with varying carbon source. The efficiency of IX was also monitored over time. The chabazite-SBR process achieved stable TN removal from ADSW centrate during the 40 weeks of operation. Simultaneous nitrification-denitrification reduced chemical input requirements. Addition of an external organic carbon source at a rate of 3.2 g-COD g-N-1 resulted in maximum TN removal. An overall TN removal efficiency of 84% was achieved, with specific nitrification and denitrification rates of 0.43 and 1.49 mg-N g-VSS-1 hr-1, respectively. The IX stage of the chabazite-SBR was able to reduce FA concentrations to below the inhibitory level for nitrification inhibition over 40 chabazite-SBR cycles with no loss in IX efficiency over time and no fresh zeolite added to the reactor.

A pilot scale nitrogen (N) removal system was constructed and operated for approximately 365 days and was designed to remove inorganic total ammonia nitrogen (TAN) from solids-separated dairy manure. An anaerobic fermenter, upstream of the N removal reactor, produced volatile fatty acids (VFAs), to be used as an electron donor to fuel denitrification, and TAN at a COD:N ratio of 18:1. However, sufficient amounts of non-VFA COD was produced by the fermenter to fuel the denitrification reaction at an average NO3- removal rate of 5.3 ± 2 mg/L NO₃--N. Total ammonia N was removed from the fermenter effluent in an N removal reactor where a series of aerobic and anoxic zones facilitated aerobic TAN oxidation and anoxic NO₃- and NO₂- reduction. The minimum dissolved oxygen (DO) concentration allowing for complete TAN removal was found to be 0.8 mg/L. However, TAN removal rates were less than predicted using default nitrifying kinetic parameters in BioWin®, a biological modeling simulator, which indicated the presence of a nitrification inhibitor in fermented dairy manure. Furthermore, an N balance during the aerobic zone indicated that simultaneous nitrification-denitrification (SND) was occurring in the aerobic zone of the N removal reactor and was most apparent at DO concentrations below 1.3 mg/L. A series of nitrite generation rate (NGR) experiments confirmed the presence of an inhibitor in fermented dairy manure. A model sensitivity analysis determined that the most sensitive ammonia oxidizing bacteria (AOB) kinetic parameters were the maximum specific growth rate, , and the substrate half saturation coefficient, . Nitrifying inhibition terms of competitive, non-competitive, mixed competitive, and un-competitive were applied to the growth rate equation in BioWin® but an accurate representation of the observed TAN removal rates in the pilot scale system could not be found by adjusting the kinetic parameters alone. Reducing the default BioWin® hydrolysis rate by approximately 50% produced a more accurate calibration for all inhibition terms tested indicating that the hydrolyization of organic N in dairy manure is less than typical municipal waste water. / Master of Science