In printed electronics there are many polyelectrolytes to choose from. While polyelectrolytes such as polystyrene sulfonic acid can fulfill many ofthe desired functionalities of a semiconductor, there is a need for other polyelectrolytes with other functionalities, such as functionality at low airhumidity and better cross-linking possibilities, while still functioning as a good semiconductor.Within this thesis, there is a description of general polyelectrolytes, as well as various usages.The synthesis and characterization of new polyelectrolytes that have been developed, based upon diallyldimethyl ammonium chloride (DADMAC)and a derivative of polystyrene sulfonic acid (PSSH) is described.The study and experimental testing of the polymers as polyelectrolytes under different conditions is described.

The goal of this project was to study the deliquescence kinetics of aerosol particles of atmospheric significance. In the course of this work a novel experimental method was developed, which utilizes the measurement of the water vapor loss in laminar aerosol flow to determine vapor uptake on the aerosol surface. The newly designed flow tube apparatus uses a system of Nafion based dryers and humidifiers, which greatly simplifies the optimization and control of the relative humidity in the aerosol flow. The design, which also utilizes a movable inlet, enables easy variation of the aerosol residence time in the deliquescence reactor, while keeping other experimental conditions constant. In this study, a numerical retrieval procedure was used to characterize aerosols in situ from their IR extinction spectra. The procedure allows that the aerosol size, number distribution, phase and composition be determined, provided the optical constants of all the components (materials) comprising the aerosol are known. For the purpose of studying the deliquescence kinetics of ammonium sulfate aerosol and monitoring their evolution from solid to liquid (state), we have acquired a set of optical constants for a range of (NH4)2SO4 compositions. A set of experiments in a somewhat modified flow tube set up was performed to produce AMS aerosols of known composition, including solid, saturated (water) solution (40 % wt.) and a series of diluted solutions with composition ranging between 40 and 10 % wt. in 5 % increments. The IR spectra of these model aerosols were used to derive the optical constants, using an inversion method proposed by Clapp. The derived refractive indices, which cover the spectral range from 590 to 5990 cm-1 with 2 cm-1 resolution, were compared with those already available in the literature. Using various examples to compare the quality of fittings to experimental spectra, we demonstrated that our optical constants present an improvement relative to those previously reported by B. Toon’s (for crystalline AMS) and S. Martin’s (for AMS solution). The suitability of applying this procedure to ammonium sulfate aerosols and its sensitivity to spectral range was also investigated and discussed. As a preparatory step for the deliquescence kinetics study, our new flow tube apparatus and the tools for the characterization of aerosol were verified in a standard deliquescence experiment performed on (NH4)2SO4 aerosols. The deliquescence process of an equilibrated aerosol flow was monitored as a function of increasing humidity and the deliquescence relative humidity (DRH) determined to be 79.6 ± 0.85 % which is, within experimental uncertainty, in an excellent agreement with the results reported by other research groups. In the kinetic experiment, a flow of solid (NH4)2SO4 aerosols is pre-humidified to a humidity close to, but enough below DRH that there is no detectable amount of liquid aerosols in the system. Such an equilibrated aerosol flow was introduced to the deliquescence reactor where it is further humidified in a controllable manner, by varying the position of the movable inlet. The amount of water transferred to the aerosol through the Nafion membrane was closely monitored, as well as the resulting increase in the water content in the aerosol flow (both gaseous and liquid). This was achieved by measuring the RHs and flow rates of the aerosol and humidification flow, and the characterization of aerosol composition and concentration using their IR spectra. The experimental conditions and aerosol residence times in the reactor where chosen such that no other diluted solution except for saturated (NH4)2SO4 droplets were produced in the process. The number distribution of deliquesced aerosols and the corresponding change in the water content in the aerosol flow were used by a newly developed kinetic model to determine the kinetics of the deliquescence process. Assuming fully developed laminar flow conditions, the water vapor concentration in the flow and its depletion in the presence of aerosol was modeled, to retrieve the value of the water vapor uptake. In the case of micron-sized ammonium sulfate aerosols, which were used in this study, the uptake coefficient,, was determined to be 0.0072 ± 6.54x10-3. The uncertainty associated with this value, as well as the suggested improvements to the experimental procedure and the kinetic model in order to reduce the uncertainty were discussed.

Decades of agricultural use of fertilizer and manure has resulted in nitrogen being the most common groundwater contaminant. Of the known processes for nitrogen attenuation, both denitrification and anammox produce a complete transformation of nitrogen species to dinitrogen gas (N2); however, denitrification is typically also associated with the release of N2O and CO2, both greenhouse gases. Anaerobic ammonium oxidation (Anammox), which has been recently discovered to be more prevalent in groundwater environments than previously thought, simultaneously removes NH4+ and nitrate (NO3-), does not require dissolved organic carbon (DOC), and does not produce greenhouse gas by-products. This study evaluates the natural occurrence of anammox in a manure lagoon plume, as well as the feasibility of enhancing anammox activity by mixing NH4+ rich groundwaters and NO3- rich groundwaters together. Fifteen experiments were undertaken with NH4+-N concentrations ranging between 5-100 mg/L, and a NO3--N ranging from 5-88 mg/L. These experiments suggest a nitrogen removal rate (based on NH4 + removal in anaerobic conditions) from anammox generally in the range of 0.1-0.2 mg/L/day. Based on an absence of dissolved oxygen (DO), and concomitant loss of NO3--N with associated 15N-NO3- enrichment (2.1-8.7‰ ) in 11 experiments, it is considered unlikely that nitrification was the cause of the NH4+ loss observed in these experiments. Concurrent 15NNH4+ enrichment of 4.1-11.5‰ was observed in these 11 experiments. Real-time quantitative polymerase chain reaction (qPCR) DNA analyses were used to show the presence of anammox bacteria and to demonstrate temporal population increases during the experiments (up to 16.3% anammox in total bacteria population) in the three experiments analyzed. Although anammoxrelated N removal rates were modest in these trials, such rates could be significant with respect to the multi-year residence times associated with most groundwater flow systems.

Increased development in Canadas northern environments has increased the need for accurate methods to detect adverse impacts on tundra ecosystems. Ammonium nitrate is a common water pollutant associated with many industrial and municipal activities, including diamond mining, and is of special concern due to the toxicity of ammonia in aquatic systems. One solution to reduce exposure of sensitive aquatic systems to nitrogenous compounds is to atomize (atmospherically disperse in fine particles) contaminated water over the arctic tundra which will reduce N loading to surface water. However, the toxicity of ammonium nitrate to arctic soils is poorly understood. In this study I investigate the potential toxicity of ammonium nitrate solutions to arctic soil functions such as carbon mineralization, nitrification and plant growth, to determine concentrations that can be applied without causing significant inhibition to these processes. <p>Arctic ecosystems are based on a soil type termed a cryosol that has an underlying permafrost layer. Often these soils are subject to cryoturbation, a process which heaves and mixes the soil, bringing the mineral horizons to the surface. I hypothesized that phytotoxicity test results in arctic soils would be highly variable compared to other terrestrial ecosystems due to the cryoturbation process and subsequent range of soil characteristics. The variability associated with phytotoxicity tests was evaluated using Environment Canadas standardized plant toxicity test in three cryoturbated soils from Canadas arctic exposed to a reference toxicant, boric acid. The phytotoxicity of boric acid to northern wheatgrass (<i>Elymus lanceolatus </i>) in cryosols was much greater than commonly reported in other soils, with less than 150 ug boric acid g-1 soil needed to inhibit root and shoot growth by 20%. There was also large variability in the phytotoxicity test results, with coefficients of variation for 10 samples ranging from 160 to 79%. Due to this variability in cryoturbated arctic soils, more than 30 samples should be collected from each control and potentially impacted area to accurately assess contaminant effects, and ensure that false negatives of toxicant impacts in arctic soils are minimized. <p>To characterize the toxicity of ammonium nitrate I exposed a variety of arctic soils and a temperate soil to different concentrations of ammonium nitrate solution over a 90 day time period. Dose responses of carbon mineralization, nitrification and phytotoxicity test parameters were estimated for ammonium nitrate applications. In addition to direct toxicity, the effect of ammonium nitrate on ecosystem resistance was investigated by dosing nitrogen impacted soils with boric acid. Ammonium nitrate solutions had no effect on carbon mineralization activity, and affected nitrification rates in only one soil, a polar desert soil from Cornwallis Island. In contrast, ammonium nitrate applications (43 mmol N L-1 soil water) significantly impaired seedling emergence, root length and shoot length of northern wheatgrass. Concentrations of ammonium nitrate in soil water that inhibited plant parameters by 20% varied between 43 to 280 mmol N L-1 soil water, which corresponds with 2,100 to 15,801 mg L-1 in the application water. Arctic soils were more resistant to ammonium nitrate toxicity than the temperate soil under these study conditions. However, it is not clear if this represents a general trend for all polar soils, and because nitrogen is an essential macro-nutrient, nitrogenous toxicity should likely be considered a special case for soil toxicity. As soil concentrations could be maintained under inhibitory levels with continual application of low concentrations of ammonium nitrate over the growing season, atomization of wastewater contaminated with ammonium nitrate is a promising technology for mitigation of nitrogen pollution in polar environments. <p>Increased development in Canadas northern environments has increased the need for accurate methods to detect adverse impacts on tundra ecosystems. Ammonium nitrate is a common water pollutant associated with many industrial and municipal activities, including diamond mining, and is of special concern due to the toxicity of ammonia in aquatic systems. One solution to reduce exposure of sensitive aquatic systems to nitrogenous compounds is to atomize (atmospherically disperse in fine particles) contaminated water over the arctic tundra which will reduce N loading to surface water. However, the toxicity of ammonium nitrate to arctic soils is poorly understood. In this study I investigate the potential toxicity of ammonium nitrate solutions to arctic soil functions such as carbon mineralization, nitrification and plant growth, to determine concentrations that can be applied without causing significant inhibition to these processes. <p>Arctic ecosystems are based on a soil type termed a cryosol that has an underlying permafrost layer. Often these soils are subject to cryoturbation, a process which heaves and mixes the soil, bringing the mineral horizons to the surface. I hypothesized that phytotoxicity test results in arctic soils would be highly variable compared to other terrestrial ecosystems due to the cryoturbation process and subsequent range of soil characteristics. The variability associated with phytotoxicity tests was evaluated using Environment Canadas standardized plant toxicity test in three cryoturbated soils from Canadas arctic exposed to a reference toxicant, boric acid. The phytotoxicity of boric acid to northern wheatgrass (<i>Elymus lanceolatus </i>) in cryosols was much greater than commonly reported in other soils, with less than 150 ug boric acid g-1 soil needed to inhibit root and shoot growth by 20%. There was also large variability in the phytotoxicity test results, with coefficients of variation for 10 samples ranging from 160 to 79%. Due to this variability in cryoturbated arctic soils, more than 30 samples should be collected from each control and potentially impacted area to accurately assess contaminant effects, and ensure that false negatives of toxicant impacts in arctic soils are minimized. <p>To characterize the toxicity of ammonium nitrate I exposed a variety of arctic soils and a temperate soil to different concentrations of ammonium nitrate solution over a 90 day time period. Dose responses of carbon mineralization, nitrification and phytotoxicity test parameters were estimated for ammonium nitrate applications. In addition to direct toxicity, the effect of ammonium nitrate on ecosystem resistance was investigated by dosing nitrogen impacted soils with boric acid. Ammonium nitrate solutions had no effect on carbon mineralization activity, and affected nitrification rates in only one soil, a polar desert soil from Cornwallis Island. In contrast, ammonium nitrate applications (43 mmol N L-1 soil water) significantly impaired seedling emergence, root length and shoot length of northern wheatgrass. Concentrations of ammonium nitrate in soil water that inhibited plant parameters by 20% varied between 43 to 280 mmol N L-1 soil water, which corresponds with 2,100 to 15,801 mg L-1 in the application water. Arctic soils were more resistant to ammonium nitrate toxicity than the temperate soil under these study conditions. However, it is not clear if this represents a general trend for all polar soils, and because nitrogen is an essential macro-nutrient, nitrogenous toxicity should likely be considered a special case for soil toxicity. As soil concentrations could be maintained under inhibitory levels with continual application of low concentrations of ammonium nitrate over the growing season, atomization of wastewater contaminated with ammonium nitrate is a promising technology for mitigation of nitrogen pollution in polar environments.

A study was conducted on an annual cropped field near Lanigan, Saskatchewan over two years (2005-2006, 2006-2007) to evaluate the effects of three extensive winter feeding systems (bale grazing (BG), swath grazing (SG) and straw-chaff grazing (ST-CH)) and one intensive winter feeding system (drylot (DL)) on cow performance, soil nutrients, crop yield and system cost of production.<p> Differences in BW (P<0.05) were observed during the 2005-2006 study period with the greatest difference occurring with cows in the SG feeding system. Cows grazing swaths (SG) had a BW loss of 8.0 kg over the 78 d trial period, however these cows consumed 15% less DM and 13% less TDN than cows bale grazing, grazing crop residue or fed in drylot pens. Differences in BW change (P<0.05) were also observed during Yr 2 between the cows fed drylot and cows grazing barley straw-chaff, 32.9 and 6.5 kg, respectively. This difference in body weight change (BW∆) and lower TDN consumption may be attributed to inaccessibility of the straw-chaff feed in the field, due to inclement weather and would suggest a lengthy acclimation period for extensive field grazing systems.<p> The effects of extensive winter feeding system on soil nutrients and soil structure were determined the following spring after winter grazing. NO3-N levels at the low slope position in the 0-15 cm depth were 53% higher on the BG sites than the ST-CH sites. This may be attributed to the larger concentration of feed, thus feed nutrients, in the BG feeding system. Phosphorus levels on the BG wintering sites were 34% higher than levels in the SG or ST-CH sites. Crop biomass measured on the BG sites was consistent with soil nutrients captured, resulting in a 15% increase in biomass compared to ST-CH and SG sites. Soil nutrient and crop biomass distribution was consistent among winter grazing sites with the ST-CH sites having the most uniform distribution of nutrients and crop biomass, and the BG sites having the least.

Saskatchewan producers traditionally overwinter their cattle in pens in the yard. The practice of winter feeding of cattle directly in the field is increasing in popularity leading to concerns about increased nutrients being deposited in soil and potentially lost in runoff water and to ground water. In 2008/2009 an experiment was conducted to observe the effect of in-field winter feeding of cows on the nutrients in spring snowmelt run-off. Approximately 100 cattle were baled grazed on a Russian wild ryegrass pasture at a stocking rate of 2240 cow-days ha-1 for 88 d during the winter at the Western Beef Development Center at Lanigan, SK. The spring 2009 ponded water was sampled from four basins in the control (no cattle were present) and four basins in the winter feeding treatment from the end of March to mid-April. Ground water samples from two piezometers in the control and two in the winter feeding area were gathered from the start of runoff until the middle of summer. Soil samples (0-10 cm) were collected in the fall 2008 before winter feeding and again in the spring 2009 after winter feeding on both the control and treated areas to examine the influence of winter feeding on soil nutrients. Orthophosphate-P and ammonium-N concentrations were elevated to levels up to 19.9 mg PO4-P L-1 and 102.3 mg NH4-N L-1 respectively in run-off from the winter feed treatment basins compared to the controls (2.1 mg PO4-P L-1 and 1.72 mg NH4-N L-1). Nitrate-N concentrations in snowmelt run-off water were similar from the winter-fed areas (0.008 mg NO3-N L-1 to 0.739 mg NO3-N L-1) and the control (0.001 mg NO3-N L-1 to 1.046 mg NO3-N L-1). This is explained by lack of sufficient time and temperature for organic N, urea and ammonium in the urine and fecal matter to convert to nitrate. In the ground water there was a slight increase in nutrient ion concentration in the winter feed basins compared to the control. Soil sampled in the spring from the winter feeding site had higher soluble nitrate, ammonium and phosphorus compared to the control. The soluble and exchangeable forms of phosphorus in the soil were lower compared to the fall soil samples for the control and winter feeding site, possibly due to immobilization by plant and microbial uptake in the spring. Caution should be used when selecting sites for in-field winter feeding system so the run-off water does not reach sensitive water bodies.

ABSTRACT LEAD(II) AND AMMONIUM EXCHANGE on Na-FORM of G&Ouml / RDES CLINOPTILOLITE ASiroglu, Sedat M.S., Department of Chemical Engineering Supervisor Prof. Dr. Hayrettin Y&uuml / cel September 2006, 89 pages Natural zeolites, especially clinoptilolite, have the ability of removing certain cations from wastewater by utilizing ion exchange and adsorption. In this study, ion exchange behaviour of G&ouml / rdes clinoptilolite at particle size range (0.5-0.25 mm) for lead and ammonium removal was investigated to establish the conditions under which clinoptilolite may be used in an economical and effective manner. Experiments were divided into two parts. Batch and continuous (column) experiments were carried out. In the batch experiments, experimental isotherms of NH4+-Na+, Pb2+-Na+ binary systems and NH4+-Pb2+-Na+ ternary system were obtained as the graphs of equivalent fractions of exchanging cation in solution versus equivalent fractions of cation in zeolite. It was determined that clinoptilolite has affinity for Pb2+ and NH4+ ions. Finally, the selectivity sequence of G&ouml / rdes clinoptilolite in the presence of Pb2+ and NH4+ together was determined as Pb2+ &gt / NH4+ &gt / Na+. In the column studies, removal of lead, ammonium and simultaneous removal of lead-ammonium solutions were investigated. The loading flow rates were selected as 8, 15, and 30 mL/min. The ion exchange capacity of clinoptilolite for lead and ammonium removal showed good performance. Flow rates at 8, 15, 30 mL/min, breakthrough capacities were found as 0.398 meq/g (Pb2+) and 0.337 meq/g (NH4+), 0.299 meq/g (Pb2+) and 0.297 meq/g (NH4+), 0.197 meq/g (Pb2+) and 0.198 meq/g (NH4+) for lead-ammonium-sodium system and corresponding column efficiencies were 63.36%, 51.38%, 34.05%, respectively.

Zeolites are crystalline, hydrated aluminosilicate minerals that are characterized by their ability to exchange some of their constituent cations with cations in aqueous solutions, without a major change in their crystalline structure. Clinoptilolite is the most abundant ype of zeolite and it has received extensive attention due to its favorable selectivity for mmonium and certain heavy metal cations. The aim of this study is to investigate the binary and ternary (multicomponent) ion xchange behavior of sodium form of G&ouml / rdes type clinoptilolite for ammonium,cadmium and sodium ions. For this purpose, NH4 +-Na+,Cd2+-Na+ binary systems and NH4 +-Cd2+-Na+ multicomponent system were investigated both in batch and column systems at 0.1 and 0.01 constant total normality respectively and at 250C constant temperature. As a result of binary and ternary experiments, clinoptilolite&rsquo / s affinity for both ions but greater affinity to NH4+ ion than Cd2+ ion was observed and the selectivity sequence of G&ouml / rdes clinoptilolite was determined as NH4+&gt / Cd2+&gt / Na+ in binary and multicomponent batch and column operations. Additionally, total ion exchange capacities and maximum exchange levels of G&ouml / rdes clinoptilolite for both ions were determined in batch systems whereas breakthrough capacities and column efficiencies (for three different flow rates) were determined in column systems. Finally, it was concluded that the increase of the flow rate reduced the breakthrough capacities and column efficiencies of G&ouml / rdes clinoptilolite for ammonium and cadmium ions in multicomponent column systems involving more than one cation.

Reproduction de : Thèse de doctorat : Chimie et physico-chimie des polymères : Le Mans : 2008. / Titre provenant de l'écran-titre.

In this dissertation I explain the theoretical and experimental details of nuclear magnetic resonance force microscopy (NMRFM). I report the data that I have collected on ammonium hexafluorophosphate at room temperature using NMRFM. This experiment measured cantilever deflection as a function of applied magnetic field. I also report on the progress of a new dynamical room-temperature NMRFM microscope. I describe the new probe and its advantages over the previous generation probe and I show the current calibration measurements. / text