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Thesis (Ph. D.)--University of Wisconsin--Madison, 1953. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 68-69).

The Kaskaskia River is a large river system situated in central and southwestern Illinois serving as a tributary to the Mississippi River. Within the Lower Kaskaskia River Watershed (LKRW), an active urban-rural gradient currently exists in the Metro East area of St. Louis. Such areas of urbanization are particularly vulnerable to stream degradation. This study focuses on the effects of urbanization on water quality parameters within Silver and Richland Creeks, both of which are tributaries to the LKRW. Forty-three catchments within Silver and Richland Creeks were identified as study catchments. Stream water samples were collected within these catchments every two weeks in the dormant season and monthly in the growing season from January 2008 to August 2009. Stream storm samples were collected and stage was recorded within 4 intensively sampled catchments, which were representative of urban, village and agriculture watersheds. Stream samples were measured and analyzed for total suspended solids (TSS), turbidity, pH, specific conductance, total coliform, bacteria coliforms (as total coliform, fecal coliform (FC), and Escherichia coli (EC)), nutrients (orthophosphate, ammonium-N, nitrate-N, chloride, sulfate), and caffeine. GIS was utilized to identify percent urban land cover (LC) at the whole catchment scale and percent impervious surfaces (IS) at the riparian buffer scale. Whole catchment urban land cover (WCULC) was used to designate land cover categories of urban, village, and agriculture watersheds (>10.5%, >1% to 10.5%, and 0% to 1% WCULC, respectively). IS were identified at the riparian scale through manual digitization and classification of structures (i.e. buildings, houses) and roads (i.e. highways, streets) within 10, 30, and 50 m buffer widths. Correlations of water quality variables to percent whole catchment urban LC were comparable to that of riparian-scale IS (RIS). Whole storm Event Mean Concentrations (EMCs) for nitrate-N, orthophosphate, and sulfate were generally significantly lower in urban watersheds compared to village and agriculture watersheds. Stream water levels of EC, FC, and orthophosphate were relatively high. Levels of FC at both baseflow and stormflow and EC at stormflow far exceeded US EPA and IL EPA Review criteria, respectively. During baseflow, stream orthophosphate and nitrate concentrations within urban watersheds were significantly higher than in village and agricultural watersheds. The significant nutrient and bacteria levels in urban streams may be due to inputs via stormwater runoff, wastewater treatment effluent, and home septic systems. Although hydrometric data showed no significant differences among the intensively sampled catchments, the village watershed had much higher mean and larger maximum stream discharge compared to the urban and agriculture watersheds. Caffeine concentration in streams was not a useful indicator of anthropogenic impacts within the LKRW study area. Results from this study demonstrate that watershed managers can utilize WCULC since it is comparable to RIS. In addition, results further illustrate the need for urban best management practices to reduce water quality impacts, such as storm water management, improved wastewater treatment, and maintaining or developing vegetated riparian buffers.

Les orthophosphates de lanthanides dopés avec des Terres Rares (TR) (LnPO4) sont considérés comme des luminophores intéressants pour des applications optiques. Les luminophores sont des matériaux luminescents qui transforment certains types d'énergie (rayons X, ultraviolet, visible, infrarouge) principalement en lumière visible. Dans le cadre de cette thèse, les matrices YPO4 (orthophosphate d'yttrium), LuPO4 (orthophosphate de lutétium), GdPO4 (orthophosphate de gadolinium) et GdxY1-xPO4 (orthophosphate d'yttrium et gadolinium), dopées avec les ions Eu3+ (europium), Ce3+, Tb3+ (terbium), Er3+ (erbium), Tm3+ (thulium) et / ou Yb3+ (ytterbium) ont été synthétisés par procédé solvothermal. En jouant sur les conditions de synthèse, la phase cristalline, la taille et la morphologie des particules obtenues ont pu être contrôlées. Les échantillons ont été caractérisés par diffraction des rayons X (DRX), spectroscopie infrarouge de Transformée de Fourier, analyse thermogravimétrique (TG), spectroscopie Raman, microscopie électronique à balayage (MEB), microscopie électronique à transmission (MET), et spectroscopie de luminescence (spectres d’émission, d’excitation, rendements quantiques et déclins de fluorescence). En particulier, des nanofils et des nanoparticules de GdPO4:Eu3+, GdPO4:Tb3+ ont été élaborés, ainsi que des poudres de YPO4:Tb3+ avec des phases monoclinique, hexagonale ou quadratique. Il a été mis en évidence une influence significative de la structure cristalline et de la morphologie des luminophores sur leurs propriétés optiques. Des poudres avec une morphologie différente ont été utilisés comme charges pour la préparation de films composites polymère/luminophores. En jouant sur la formulation des orthophosphates et la nature des ions dopants, des luminophores fournissant une lumière proche du blanc idéal sous excitation UV ont pu être élaborés. L’ensemble de ce travail montre clairement les potentialités d’applications de ces matériaux dans des dispositifs basés sur une source d’excitation plasma ou sur la technologie des diodes électroluminescentes. / Rare earth (Re) doped lanthanide orthophosphates (LnPO4) are considered like promising phosphors for optical applications. Phosphors are luminescent materials which convert certain types of energy (X-ray, ultraviolet, visible, infrared) mainly into visible light. In this research Eu3+ (europium), Ce3+ (cerium), Tb3+ (terbium), Er3+ (erbium), Tm3+ (thulium) and/or Yb3+ (ytterbium) doped LuPO4 (lutetium orthophosphate), YPO4 (yttrium orthophosphate), GdPO4 (gadolinium orthophosphate) and/or GdxY1-xPO4 (yttrium-gadolinium orthophosphate) were synthesized by solvothermal process. By varying the synthesis conditions, the crystalline phase, particle size and morphology were controlled by the synthesis conditions these parameters affect the photoluminescent properties. The samples were characterized by means of X-ray Diffraction (XRD), Fourier transform Infrared (FT-IR), Thermogravimetric Analysis (TGA), Raman Spectroscopy, Scanning Electronic Microscopy (SEM), Transmission Electronic Microscopy (TEM) and photoluminescence spectroscopy (emission and excitation spectra, quantum yields and fluorescence decay times). In particular, nanowires and nanoparticles nanowires and nanoparticles of GdPO4:Eu3+, GdPO4:Tb3+ have been developed, as well as powders of YPO4:Tb3+ powders with monoclinic, hexagonal or tetragonal phases. It has been demonstrated a significant influence of the crystalline structure and morphology phosphors on their optical properties. Powders with different morphology were used as fillers for preparing luminescent composite polymer/phosphors films. By adjusting the orthophosphates formulation and dopant nature of ions, phosphors providing near perfect white light under UV excitation could be obtained. All of this work clearly shows the potential applications of these materials in devices based on a plasma excitation source or light emitting diode technology.

Chloride levels are increasing in some water supplies around the country due to use of road salts and seawater intrusion, which can increase the chloride-to-sulfate mass ratio (CSMR) and trigger serious water lead contamination from galvanic lead solder: copper pipe corrosion. Previous attempts to control this problem through simple water chemistry modifications were unsuccessful, but in this work a combination of zinc orthophosphate and moderate alkalinity mitigated lead release in testing at two utilities. Either zinc alone or phosphate alone were irrelatively ineffective, but the combination of zinc orthophosphate reduced lead leaching by 54-99% (compared to the control without inhibitors) if alkalinity was above about 55 mg/L as CaCO3. These results may help mitigate future lead in water contamination events. / MS

The objective of this study was to evaluate galvanic corrosion potential under various pH conditions, buffering capacities, and corrosion inhibitors including zinc orthophosphate (ZOP) and orthophosphate (OP). Bench-scale dump-and-fill experiments evaluated metals release from a lead and copper couple under stagnant conditions. Key findings from this study were that increasing DIC from 3 to 7 or 17 mg CaCO3/L significantly reduced lead release with or without corrosion inhibitor; however, the lowest lead concentrations were observed in water conditions with corrosion inhibitor addition. However, addition of 20 mg PO4/L as OP exacerbated lead release in some cases; though dissolved lead release was always below 28 µg/L, particulate lead was as much as 4 times greater compared to no corrosion inhibitor. Overall, this study demonstrated the potential of high dose ZOP and OP for lead corrosion control in drinking water, however, overdosing OP can lead to exacerbated particulate concentrations.

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.

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.

Th.--Sci. phys.--Toulouse--I.N.P., 1977. N°: 23.

Th. doct.-ing.--Physicochim. des matér.--Toulouse--I.N.P., 1978. N°: 20.