Frequent drainage and aeration problems occur in blueberry plantings on acid peats (pH 3.0 to pH 4.2) of British Columbia during a part of the growing season. The effect of waterlogging, pH, and form of N were studied under greenhouse conditions. Using one year old plants of Bluecrop blueberry, a split plot design was employed with two water tables for main plots and a factorial combination of 4 pH levels and 3 levels each of ammonium and nitrate N (20, 40, and 60 lbs. N/acre). An unfertilized check treatment was also included as a treatment. Growth records and leaf analysis showed that poor aeration under waterlogged conditions exhibited characters symptomatic of poor nutrition. Sparse leaf growth, smaller leaves with severe yellowing and premature leaf abscission were observed in the high water table treatments. Leaf analysis revealed highly significant differences in foliar N, P, K, Ca, Mg, and Fe levels. There was also a greater growth response to ammonium N and nitrate N. Higher levels of nitrate N (40, and 60 lbs. N/acre) caused severe leaf scorch. Although higher levels of ammonium N (40, and 60 lbs. N/acre) gave better growth response, growth was prolonged and fall leaf drop and wood maturation were delayed. Plants receiving 60 lbs. N/acre as ammonium N showed symptoms of dieback in the following spring. Although pH had very little effect on leaf nutrient composition, growth appeared to be better at a pH level of around 4.2. / Land and Food Systems, Faculty of / Graduate

Laser-based sensors can be used as non-invasive monitoring tools to measure parts per billion (ppb) levels of trace gases. Ammonia sensors are useful for applications in environmental pollutant monitoring, atmospheric and combustion kinetic studies, and medical diagnostics. This sensor was specifically designed to measure ammonia in exhaled breath to be used as a medical diagnostic and monitoring tool, however, it can also be extended for use in other applications. Although ammonia is a naturally occurring species in exhaled breath, abnormally elevated levels can be an indication of adverse medical conditions. Laser-based breath diagnostics have many benefits since they are cost effective, non-invasive, painless, real time monitors. They have the potential to improve the quality of medical care by replacing currently used blood tests and providing immediate feedback to physicians. This sensor utilizes a Quantum Cascade Laser and Wavelength Modulation Spectroscopy with second harmonic normalized by first harmonic detection in a 76 m multi-pass absorption cell to measure ppb levels of ammonia with improved sensitivity over previous sensors. Initial measurements to determine the ammonia absorption line parameters were performed using direct absorption spectroscopy. This is the first experimental study of the ammonia absorption line transitions near 1103.46 cm-1 with absorption spectroscopy. The linestrengths were measured with uncertainties less than 10%. The collisional broadening coefficients for each of the ammonia lines with nitrogen, oxygen, water vapor, and carbon dioxide were also measured, many of which had uncertainties less than 5%. The sensor was characterized to show a detectability limit of 10 ppb with an uncertainty of less than 5% at typical breath ammonia levels. Initial breath test results showed that some of the patients with chronic kidney disease had elevated ammonia levels while others had ammonia levels in the same range as expected for healthy patients. For all of the patients the breath ammonia level decreased during dialysis but the percent decrease varied considerably for each patient. The sensor has demonstrated improved sensitivity and has been applied to measure ppb levels of ammonia in exhaled breath. Further tests have been designed to improve the sensor and continue to investigate the medical applications.

Loss of ammonia from broiler litter degrades air quality, decreases litter fertilizer value, and can have negative health consequences for birds and their caretakers. Rates of NH3 emission from broiler houses are complicated by interrelated management and environmental factors such as air temperature, humidity, house style, ventilation rate,bird age, litter conditions, litter characteristics, and cleanout schedule. Wide variations inemission rates necessitate further investigation of litter characteristics and abatement techniques. The research was designed to clarify the impact of moisture effects that are critical to emissions for poultry litter, in conjunction with bedding type and temperature. Experiments were conducted on litter samples in the laboratory using anacid trap method for determining NH3 losses. Statistical models were developed for predicting release from each bedding material and within the range of litter moistureand temperatures found in commercial broiler houses. This allowed development of relationships that describe the effects of bedding, moisture, time, and temperature on litter generation that have not been published previously. First, type of bedding material was investigated within a limited scope of moisture contents. The results indicated that increasing moisture increases generation from litter. Literature supports the phenomenon that greater litter moisture content up to apoint elicits greater release. At the original moisture content, sand and vermiculite litters generated the most, whereas wood shavings, commercial, and rice hull. Second, an extended range of litter moisture contents (20 – 55%) was investigated while including temperature (18.3 – 40.6 °C) effects. Experiments were conducted using built-up commercial broiler litter from multiple flocks. Response surfaces were parabolic cylinders, indicating maximum production was between 37.4 and 51.5% litter moisture depending on temperature. Comparing the temperature extremes, the maximum up to 7 times greater at 40.6 vs. 18.3 °C. This research defines intermediate critical moisture levels in broiler litter where NH3 is maximized, providing target areasfor researchers and the poultry industry to develop management scenarios to reduce from litter.

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Ammonia and hydrogen are two alternative fuels that can help decarbonization as they can be produced using renewable energy. Ammonia has transportation, handling, and storage advantages over hydrogen even though its combustion characteristics are worse. One intermediate strategy to use ammonia or hydrogen as a fuel is to co-fire it with hydrocarbons. However, co-firing with hydrocarbons may emit harmful pollutants such as NOx and soot. This study investigates the effects of ammonia and hydrogen addition on soot formation in laminar coflow nitrogen-diluted-ethylene normal diffusion flames using experimental techniques. Ammonia and hydrogen were added separately to the fuel flow. Flame conditions from 0 to 50 vol% of the added species (ammonia or hydrogen) were tested. Laser diagnostics for measuring the distributions of polycyclic aromatic hydrocarbons (PAHs) and soot volume fraction (SVF), and intrusive measurements (using a thermocouple and probe sampling) were performed. Based on the results, ammonia addition suppressed soot formation while hydrogen addition enhanced it. In conditions with ammonia addition, the temperature measurements with a Type S thermocouple and adiabatic flame temperature simulations using CHEMKIN PRO showed similar temperature profiles and negligible adiabatic flame temperature differences respectively. The qualitative PAH measurements using planar laser induced fluorescence (PLIF) showed that the concentration of PAHs of four or larger rings reduced with ammonia addition. Soot volume fraction (SVF) measurements using planar laser induced incandescence (PLII) showed that the peak SVF decreased exponentially with ammonia addition. Particle size distributions showed that the incipient particles were formed, however growth to mature primary particles was limited with 25% or higher ammonia addition in the flame. Based on similar temperature profiles and decreasing trends in the distribution of PAHs and SVF, soot suppression with ammonia addition was linked to chemical effects. PLIF measurements with hydrogen addition could be affected by the temperature difference between the flames, therefore further investigation is needed. PLII measurements, however, showed that the soot volume fraction increased linearly with hydrogen addition.

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Contamination of natural waters due to nitrogenous wastes has become a crucial environmental problem due to deterioration of water quality and eutrophication in aquatic eco-systems. Thus, the reduction of nitrogen accumulation in the natural environment is vital to maintain a healthy eco-system. Bipolar membrane electrodialysis (BMED) is a promising technology for selective ammonia separation from high-strength wastewater, such as liquid digestates of food waste or wastewater sludge. This technology was recently studied for reducing membrane scaling problems associated with conventional electrodialysis (ED) systems due to the water splitting mechanism in the BPM interface. A bench-scale BMED stack was built using 5 pairs of cation exchange membranes (CEMs) and bipolar membranes (BPMs). Using the BMED stack, a simulated food liquid digestate solution was examined to separate ammonia with different voltage applications and inter-membrane distances. The highest ammonia recovery was obtained at a cell pair voltage of 5.83 V (81% separation). Experiments on investigation of optimal inter-membrane distance of BMED operation suggested that the inter-membrane distance could be increased up to 2.46 mm without a significant decrease in nitrogen recovery. The residual Ca2+ and Mg2+ in the CIP (clean-in-place) solution which explains the degree of the scaling problem in the BMED was observed consistently below 2% of the initial mass introduced to the system, indicating that BMED design and regular CIP were effective in scaling control. The ammonia loss through CEMs to the feed cell by back diffusion was minimized due to high pH in the base cell since uncharged free ammonia was dominant over ammonium cation in the base cell. The energy required for BMED operation was comparatively low; 1.93-6.93 kWh/kg-N within 90 mins. Therefore, BMED can be considered as a sustainable candidate for selective ammonia recovery at high energy efficiency with successful scaling control. / Thesis / Master of Civil Engineering (MCE)

Ammonia has shown great potential as a carbon-free fuel, in particular for marine transportation and energy production. Its low laminar flame speed, and the tradeoff between ammonia slip and NOx emission, pose challenges for industrial applications, and a more in-depth understanding of the combustion of ammonia is therefore needed. Raman spectroscopy is a powerful diagnostic often employed to investigate turbulence chemistry interactions and resolve the thermo-chemical structure of hydrogen and hydrocarbon-air flames. However, this technique has been used extensively in hydrocarbons (HCs) and hydrogen flames, but no quantitative Raman spectroscopy is available for ammonia flames, despite the current interest in ammonia combustion. First, this work extends Raman spectroscopy to the instantaneous and spatially resolved measurement of major species concentrations and temperatures in ammonia flames. The lack of detailed ammonia spectra at high temperatures, the strong flame luminosity, and fluorescence interference are the major obstacles to the implementation of Raman spectroscopy to ammonia flames. This thesis introduces a novel approach to estimating the temperature dependence of the Raman signal and fluorescence interference contributions from a series of counterflow diffusion flames. Species concentrations and temperature profiles from measurements are shown, and their accuracy and precision are discussed. Next, this work obtains the first quantitative Raman measurements of temperature, mass fractions, and mixture fractions in two turbulent ammonia/hydrogen/nitrogen diffusion jet flames simulating 14% (CAJF14) and 28% (CAJF28) partial ammonia cracking ratio with Reynolds numbers of 11,200. The scalar structure in turbulent flames is examined using conditional mean and RMS radial profiles, scatterplots in mixture fraction space, as well as statistics conditioned on mixture fraction and physical spaces. Finally, the probability of localized extinction and the differential diffusion (diff-diff) effects are analyzed in two turbulent flames. Lastly, an improved Raman/Rayleigh system is introduced for ammonia combustion at atmospheric pressure, which enables the 1D simultaneous laser-induced fluorescence (LIF) measurements of the amidogen (NH2) radical and interference-free Raman/Rayleigh measurements of major species and temperature in non-premixed and premixed NH3/H2-air flames.

The price fluctuation and depletion of crude oil have led to the fervent interest in finding alternatives that can satisfy our increasing need for energy. In the past decades, two primary approaches are seen as promising ways to remedy our dependence on crude oil: first, the use of natural gas, primarily methane, to produce high-value hydrocarbons, and second, the use of ammonia as a hydrogen carrier. In this dissertation, we used density functional theory (DFT) calculation and kinetic modeling to investigate methane activation and C-C coupling on WC as well as the ammonia decomposition over the CoNi alloy surface. From our methane conversion project, we investigated the reactivity of W-terminated WC(0001) and WC(112 ̅0) surface toward methane activation and conversion to produce C2 moieties using DFT. We first calculate the intermediates binding energies and activation and reaction energies of methane dissociation. We found that WC(112 ̅0) is better at dissociating the first C–H bond than WC(0001). Our results also indicate that the surface is likely populated by (CH)ads species. The mobility of (CH)ads species on both surfaces allows the possibility of C-C coupling, resulting in a precursor for higher hydrocarbon formation. Our results also demonstrate that the WC(0001) surface favors the production of the (C2H2)ads species, whereas the WC(112 ̅0) surface dissociates CHx completely, resulting in coke formation. Thus, methane dissociates readily on the WC surfaces whereas the formation of the C2 species is sensitive to the surface structure. The DFT study on ammonia decomposition has been performed in close collaboration with the experimental study. A highly active catalyst consisting of CoNi alloy nanoparticles well-dispersed on a MgO–CeO2–SrO mixed oxide support with potassium promotion exhibited a performance matching that of the Ru-based catalysts. Extensive characterization in combination with the DFT results revealed that the CoNi alloy surface and metal/oxide interfaces are the active sites for catalytic decomposition of ammonia. Moreover, the much improved catalytic activity stems mainly from the presence of interface where the recombinative desorption of nitrogen has been greatly enhanced. These have been demonstrated by examining the detailed elementary steps of ammonia decomposition on the Co, Ni, Co2Ni, CoNi2 (111) surfaces and at the CeO2/Co2Ni interface. We calculated the binding energies of intermediates and the activation energies of each elementary step in ammonia decomposition. We found that on the Co, Ni, Co2Ni, CoNi2 surfaces, N–N bond formation is the rate-determining step, with the CoNi alloy surfaces having a lower activation energy than the pure metal surfaces. Over the CeO2/Co2Ni interface, however, N–H bond dissociation becomes rate-determining. The high catalytic activity at the CeO2/Co2Ni interface originates from the localized charge polarization due to alloying and the presence of the oxide which drastically facilitates N2* formation. We then integrated the DFT-calculated adsorption and activation energies in the microkinetic modeling of ammonia decomposition on the Co, Co2Ni, CoNi2, and Ni surfaces, focusing on the alloying effect. Two cases were investigated: ammonia decomposition in the 1) absence and 2) presence of product re-adsorption. In both cases, we determined the turnover frequencies, the apparent activation energies, the steady-state coverages, the degree of rate control, and the reaction orders. Our results show that in both cases, the alloys have higher catalytic performance than the pure metals. We also found that as the temperature increases, ammonia decomposition switches from being limited by N–N (and N–NH) bond formation to N–H bond dissociation. This change of mechanism is predicted to occur at lower temperatures on the alloy surfaces. In the case of hydrogen re-absorption, the surface H* adatom retards the last N–H bond-breaking step, resulting in the high coverage of NH* species on the surfaces, making N–NH coupling an alternative pathway for N2 formation. Furthermore, our microkinetic results show that alloying Ni with Co reduces the effect of hydrogen inhibition at high hydrogen partial pressures. In summary, this dissertation provides information for the design of efficient catalysts toward methane conversion and ammonia decomposition.