In order to study quantitatively the acidity of very weak acids and at the same time the effect of a polar aprotic solvent on the basicity of hydroxide ion a Hammett H_ acidity function based on the ionization of 24 substituted anilines and diphenylamines has been established in the system dimethylsulfoxide-water-tetramethylammonium hydroxide. The basicity of hydroxide ion is increased dramatically as the solvent is changed from water to dimethylsulfoxide. The H_ of a 0.011 molar solution of tetramethylammonium hydroxide ranges from 12 in water to 26 in 99.6 mole % dimethylsul-foxide-water, an increase in basicity of fourteen powers of ten. The increase in basicity is due to the increased activity of the hydroxide ion brought about by the reduction in its solvation in the poor anion-solvating solvent, dimethyl sulfoxide and indicates the extensive solvation enjoyed by the hydroxide ion in water. The pKHA values of the indicator acids vary from 13.84 for 2,4-dinitrodiphenylamine to 25.63 for 3-chloroaniline. From a plot of log KHA versus Hammett substituent constants ( ϭ) for six monosubstituted diphenylamines a rho (ρ) value of 4.07 is found. The magnitude of substituent effects on the acidity of aniline appears to be quite similar. The acidities of all the substituted diphenylamines do not follow the above mentioned correlation with Hammett ϭconstants; the pKHA values of 4-amino-, 4-methoxy-, 4-methylsulfonyl-, and 4-nitrodiphenylamine are all less than expected from the Hammett ϭ constants for the substituents in these compounds. The 4-nitro substituent exerts a particularly large acid-strengthening effect on the acidities of aniline and diphenyl amine; the decreases in pKHA being approximately 8.4 and 6.8 pK units, respectively. The pKHA values of 17 compounds other than those indicators used to establish the H_ function have been determined with the aid of the H_ function. Most of these compounds are alkyl-substituted 4-nitroanilines. Alkyl groups ortho to the amino group of 4-nitroaniline cause a decrease in the pKHA (an increase in acidity). Similarly, N-methyl-, N-ethyl-, and N-isopropyl-4-mitro- aniline are all stronger acids than 4-nitroaniline itself. An explanation for the effects of alkyl substituents on the acidity of 4-nitroaniline in terms of the solvation of both the ionized and unionized amines is advanced. A Hammett Hₒ acidity function based on the protonation of 17 diphenylamines in 20 volume % ethanol-aqueous sulfuric acid has been established. The Hₒ value for the most acidic solution studied is -6.97 for 11.2 molar sulfuric acid. This acidity function differs from that based on the protonation of azobenzenes in the same solvent system; the latter acidity function diverges to more, negative Hₒ values as the sulfuric acid concentration increases. The pKBH+ values for the protonation of the diphenylamines vary from 1.36 for 4 methoxydiphenylamine to -6.21 for 4,4'-dinitrodiphenylamine. A plot, of log KBH+ versus Hammett ϭ constants for five mono-substituted diphenylamines yields a rho (ρ) value of.3.36. The pKBH+ values for 4-methoxy-, 4-methyl-, 4-methylsulfonyl-, and 4-nitro-diphenylamine are all less (morenegative) than expected from the Hammett substituent constants. Substituent effects on the basicities of aniline and diphenylamine are the same. This is evident from the fact, that a plot of the pKBH+ values of 11 diphenylamines versus the pKBH+ values of the corresponding anilines yields a good straight line with slope 1.01. The basicities of several nitro-substituted diphenylamines appear to vary regularly and do not reflect the presence of a strong interaction between the nitro group and sulfuric acid. A plot of the acidity versus the basicity (pKHA versus pKBH+) for nine diphenylamines yields, a straight line with slope 1.30. In a similar plot for 33 substituted anilines and diphenylamines two types of behaviour are observed. Those anilines and diphenylamines without an ortho or para hitro group fall about the line with slope 1.30 while those amines with at least one nitro group in the ortho or para position fall on a different, curved line with a slope of less than unity. / Science, Faculty of / Chemistry, Department of / Graduate

There are many advantages and some disadvantages associated with the fall application of nitrogen fertilizers. The advantages of applying fertilizer at this time appear very convincing. It is easier to get onto the land in the fall. During the fall, famers usually have more time to apply fertilizer than they do in the spring. In the fall the fertilizer companies offer better service. This is because the fall application of fertilizer lengthens out their season, thus making it possible for them to handle more fertilizer.

The objectives of this study were: 1) To evaluate short-term composting of hardwood bark with combinations of poultry litter and ammonium nitrate and 2) To determine the suitability of composted material for ornamental plant media. In a 3-month accelerated composting study, hardwood bark was amended with (20% & 40%) poultry litter, (1% & 2%) ammonium nitrate, or unamended. Composting was run in fifteen 35- gallon containers and samples were collected at day 0, 45, and 90 for pH, moisture content, carbon-to-nitrogen ratio, compost maturity, toxicity, and green house evaluations. The amendment containing 40% poultry litter showed significantly higher weight reduction than others at days 45 and 90. Also, this treatment showed significantly higher mass weight in transplanted zinnia and gardenia than other treatments and was comparable to commercial media. Overall, results indicated that the amendment of hardwood bark with poultry litter could produce comparable product to currently used commercial container media.

No description available.

No description available.

Une grande variété des eaux résiduelles industrielles et résidentielles contenant de l’ammonium sont rejetées dans la nature sans traitement approprié. Étant donné que cela peut constituer une menace à la fois pour l’environnement et pour la santé humaine, il est courant d’éliminer l’ammonium en le convertissant en azote gazeux qui est rejeté dans l’atmosphère. Bien que cela aide à se conformer aux règlementations environnementales, l’ammonium est un produit de grande valeur, étant l’un des principaux composants des engrais. Malgré cette grande disponibilité en tant que sous-produit, ce nutriment est généralement produit à partir de zéro par des techniques très consommatrices d’énergie qui génèrent des émissions de gaz à effet de serre telles que le procédé Haber-Bosch. Les systèmes de dégazage et absorption permettent de récupérer l’ammonium des eaux usées et de le revaloriser dans un produit utile. Son implémentation dans les grandes industries a été largement validée et rapportée dans la littérature. Des recherches continuent d’être effectuées pour étudier l’effet des différentes caractéristiques des eaux usées, telles que la teneur en chlorure et l’alcalinité, qui peuvent diminuer ou améliorer la récupération de l’ammonium. Plus important encore, son adaptation pour des implémentations à petite échelle n’a pas encore été explorée alors que la possibilité de traiter de petits volumes d’eaux usées et de récupérer des ressources et de l’eau sur site est très intéressante. Compte tenu de ce qui précède, l’objectif de ce projet est d’évaluer la faisabilité de la mise en œuvre de tels systèmes à petite échelle. Ce travail se concentre uniquement sur l’étape de dégazage. Pour cela, il est indispensable de caractériser les effluents de différentes sources et leurs effets sur l’efficacité de récupération de l’ammonium. Un système de dégazage et absorption a été reproduit à l’échelle du laboratoire. Les effets de la teneur en ammonium, de l’alcalinité, de la conductivité électrique et du pH ont été évalués dans des tests par lots utilisant des solutions synthétiques. À partir des résultats, une régression linéaire a été effectuée pour obtenir un modèle mathématique permettant de prédire l’élimination de l'ammoniac à partir des caractéristiques d’un effluent donné. Ce modèle a été utilisé comme noyau d'un modèle de conception qui évalue la faisabilité des systèmes d’extraction de l’ammoniac à partir des caractéristiques des eaux usées et d’un objectif d’élimination prédéfini. En tenant compte des facteurs économiques et à partir d’un problème d’optimisation itératif, le modèle produit la géométrie, le nombre d’unités de dégazage et l’alimentation en air qui minimisent à la fois les frais d'investissement et d’exploitation. Étant donné que la concentration d’ammoniac dans les eaux usées est connue et le pourcentage de récupération est fixé, la conception du procédé n’affecte pas le revenu obtenu de sa vente. Le modèle a été calibré sur la base de solutions synthétiques imitant la composition de l’urine, du lixiviat de compostage et des eaux usées d’aquaculture. Lorsqu’il a été validé par rapport à des effluents réels, il n’a pu prédire que l’efficacité d’élimination de l’urine. Un exemple d’étude de cas portant sur l’analyse technico-économique du fonctionnement d’un système de traitement d’urine à petite échelle a été réalisé. Bien que les frais d’exploitation soient approximativement le double (ou plus si l'épuration est envisagée) de ceux d’un procédé conventionnel d’élimination uniquement, il est intéressant d’un point de vue environnemental. Il est recommandé de poursuivre l’étude des effets des autres composants des eaux usées qui pourraient avoir un impact sur le procédé. Des recherches supplémentaires doivent être menées sur la réduction de frais d’exploitation afin de rendre ces options économiquement intéressantes. / A wide variety of ammonium-bearing industrial and domestic waste streams are discharged into nature without proper treatment. Since this can pose a threat to both the environment and human health, it is common practice to remove ammonium by converting it into nitrogen gas which is released to the atmosphere. Although this helps complying with environmental regulations, ammonium is a highly valuable product, being one of the main components in fertilizers. Despite this extensive availability as by-product, this nutrient is commonly produced from the ground up through highly energy consuming techniques that generate green house gas emissions such as the Haber-Bosch process. The stripping-scrubbing systems allow to recover ammonium from waste water and revalorize it as a useful product. Its application in large-scale industries has been widespread validated and reported in the literature. Research is still being done to study the effect of different characteristics of wastewater,such as chloride content and alkalinity that may decrease or enhance ammonium recovery. More importantly, its adaptation for small-scale applications has not yet been explored despite the fact that the possibility to treat small volumes of wastewater and the recovery of resources and water on-site arevery attractive. Considering the above, the objective of this project is to evaluate the feasibility of implementing such systems in small-scale industries. This work focuses on the stripping stage only.For this, it is essential to characterize the effluents from various sources and their effects on the ammonium recovery efficiency. A stripping-scrubbing system was reproduced at laboratory-scale. The effects of ammonium content, alkalinity, electrical conductivity, and pH were assessed in batch tests using synthetic solutions. From the results, a linear regression was performed to obtain a mathematical model to predict ammonia removal from the characteristics of a given effluent. This model was used as the core of a design model that evaluates the feasibility of ammonia stripping systems from the wastewater characteristics and a predefined removal target. Taking economic factors into accountby means of an iterative optimization problem, it outputs the geometry, number of stripping units, andair supply that minimized both investment and operating costs. Since the target is predefined and the wastewater composition known, the income from selling a fertilizing salt is independent of the design. The model was calibrated based on synthetic solutions mimicking the composition of urine, composting leachate, and aquaculture wastewater. When validated against real effluents, it only was able to predict the removal efficiency of urine. An example case study addressing the techno-economic analysis of the operation of a small-scale urine treatment system was conducted. Although the operating costs approximately double (or more if scrubbing is considered) that of a conventional removal-only process, it is interesting from an environmental perspective. It is recommended to continue studying the effects of other components of wastewater that could impact the process. Further research must bedone reducing operational costs in order to make these options economically interesting.

Surface application of broiler litter to grasslands can increase concentrations of ammonium (NH₄+-N) and dissolved reactive phosphorus (DRP) in surface runoff. It is not known, however, for how long after broiler litter applications that NH₄+-N and DRP concentrations remain elevated. Five 0.75-ha, fescue-bermudagrass paddlocks received four broiler litter applications in 1995 and 1996, and only inorganic fertilizer N in 1997 and 1998. Runoff from each paddock was measured, sampled, and analyzed for NH₄+-N and DRP. Flow-weighted NH₄+-N and DRP concentrations increased from background values of 0.5 and 0.4 mg L-1, respectively, to values as high as 50.7 mg NH₄+-N L⁻¹ and 18.8 mg DRP L-1 in a runoff event that occurred immediately after the third litter application. Concentrations remained high while broiler litter was being applied but decreased steadily after the last application, reaching values near 1 mg L⁻¹ (for NH₄+-N and DRP) by 19 months after the final application. Among the factors that affected the average concentration of NH₄+-N and DRP in cumulative runoff after a litter application were cumulative runoff, rates of total N and NH₄+-N applied, and cumulative total litter N, total litter P, and water-soluble litter P applied during the four years of the study. Soil test P also affected DRP concentrations, but its effect depended on when the paddocks last received broiler litter. There is a need for tools to identify situations in which the application of broiler litter may enrich surface runoff with P. One such tool is the simulation model Erosion Productivity Impact Calculator (EPIC). EPIC's ability to simulate runoff volume and losses of dissolved reactive P (DRP) was evaluated. Data from the five 0.75-ha, tall fescue-bermudagrass plots that were fertilized with broiler litter during two years, and received only inorganic fertilizer N for the two subsequent years, were compared with EPIC estimates. EPIC simulations of runoff volume in individual events did not show bias in three of the plots but underestimated runoff in one plot and overestimated runoff in another. On an annual basis, the runoff volumes simulated by EPIC were similar to the observed values. A modified version of EPIC yielded better estimates of event DRP losses than the original EPIC and generated estimates of annual DRP loss that were similar to observed values. These results suggest that the modified EPIC may be useful for identifying situations where there is a high risk of large annual P losses from grasslands fertilized with broiler litter. / Ph. D.

The sediment-water interface is an active biogeochemical zone within streams, where solutes come in contact with mineral surfaces, biota, and reducing conditions. Here, we sought to examine the influence of light, the sediment water interface, and algae on dissolved organic carbon (DOC), nitrogen, and phosphorus within Maple Creek, an agriculturally impacted stream located in Fremont, Nebraska. Simultaneous continuous injection experiments into replicate open- and closed-bottom chambers were used to control the hydrologic residence time. A bromide tracer was injected, and samples were taken for nutrient analysis in the surface and subsurface water at depths up to 8 cm. Dissolved oxygen (DO) and temperature were recorded in order to monitor biotic production. Experiments were conducted over 10 hours, encompassing both light and dark conditions. Results show a strong biotic influence at the sediment-water interface causing nutrient uptake and changes in carbon quality. Changes are especially pronounced during peak photosynthesis hours. The open-bottom mesocosms consistently showed removal of N and P from the surface water to the subsurface. An increase in DOC flux was observed in the open-bottom mesocosms and the organic matter pool exhibited evidence of microbial reduction. The closed-bottom mesocosm showed NH?⁺ increased likely due to photochemical oxidation. These results show the importance of promoting exchange through the subsurface and across the sediment-water interface due to the positive impact it has on nutrient retention. / Master of Science

Une grande variété des eaux résiduelles industrielles et résidentielles contenant de l'ammonium sont rejetées dans la nature sans traitement approprié. Étant donné que cela peut constituer une menace à la fois pour l'environnement et pour la santé humaine, il est courant d'éliminer l'ammonium en le convertissant en azote gazeux qui est rejeté dans l'atmosphère. Bien que cela aide à se conformer aux règlementations environnementales, l'ammonium est un produit de grande valeur, étant l'un des principaux composants des engrais. Malgré cette grande disponibilité en tant que sous-produit, ce nutriment est généralement produit à partir de zéro par des techniques très consommatrices d'énergie qui génèrent des émissions de gaz à effet de serre telles que le procédé Haber-Bosch. Les systèmes de dégazage et absorption permettent de récupérer l'ammonium des eaux usées et de le revaloriser dans un produit utile. Son implémentation dans les grandes industries a été largement validée et rapportée dans la littérature. Des recherches continuent d'être effectuées pour étudier l'effet des différentes caractéristiques des eaux usées, telles que la teneur en chlorure et l'alcalinité, qui peuvent diminuer ou améliorer la récupération de l'ammonium. Plus important encore, son adaptation pour des implémentations à petite échelle n'a pas encore été explorée alors que la possibilité de traiter de petits volumes d'eaux usées et de récupérer des ressources et de l'eau sur site est très intéressante. Compte tenu de ce qui précède, l'objectif de ce projet est d'évaluer la faisabilité de la mise en œuvre de tels systèmes à petite échelle. Ce travail se concentre uniquement sur l'étape de dégazage. Pour cela, il est indispensable de caractériser les effluents de différentes sources et leurs effets sur l'efficacité de récupération de l'ammonium. Un système de dégazage et absorption a été reproduit à l'échelle du laboratoire. Les effets de la teneur en ammonium, de l'alcalinité, de la conductivité électrique et du pH ont été évalués dans des tests par lots utilisant des solutions synthétiques. À partir des résultats, une régression linéaire a été effectuée pour obtenir un modèle mathématique permettant de prédire l'élimination de l'ammoniac à partir des caractéristiques d'un effluent donné. Ce modèle a été utilisé comme noyau d'un modèle de conception qui évalue la faisabilité des systèmes d'extraction de l'ammoniac à partir des caractéristiques des eaux usées et d'un objectif d'élimination prédéfini. En tenant compte des facteurs économiques et à partir d'un problème d'optimisation itératif, le modèle produit la géométrie, le nombre d'unités de dégazage et l'alimentation en air qui minimisent à la fois les frais d'investissement et d'exploitation. Étant donné que la concentration d'ammoniac dans les eaux usées est connue et le pourcentage de récupération est fixé, la conception du procédé n'affecte pas le revenu obtenu de sa vente. Le modèle a été calibré sur la base de solutions synthétiques imitant la composition de l'urine, du lixiviat de compostage et des eaux usées d'aquaculture. Lorsqu'il a été validé par rapport à des effluents réels, il n'a pu prédire que l'efficacité d'élimination de l'urine. Un exemple d'étude de cas portant sur l'analyse technico-économique du fonctionnement d'un système de traitement d'urine à petite échelle a été réalisé. Bien que les frais d'exploitation soient approximativement le double (ou plus si l'épuration est envisagée) de ceux d'un procédé conventionnel d'élimination uniquement, il est intéressant d'un point de vue environnemental. Il est recommandé de poursuivre l'étude des effets des autres composants des eaux usées qui pourraient avoir un impact sur le procédé. Des recherches supplémentaires doivent être menées sur la réduction de frais d'exploitation afin de rendre ces options économiquement intéressantes. / A wide variety of ammonium-bearing industrial and domestic waste streams are discharged into nature without proper treatment. Since this can pose a threat to both the environment and human health, it is common practice to remove ammonium by converting it into nitrogen gas which is released to the atmosphere. Although this helps complying with environmental regulations, ammonium is a highly valuable product, being one of the main components in fertilizers. Despite this extensive availability as by-product, this nutrient is commonly produced from the ground up through highly energy consuming techniques that generate green house gas emissions such as the Haber-Bosch process. The stripping-scrubbing systems allow to recover ammonium from waste water and revalorize it as a useful product. Its application in large-scale industries has been widespread validated and reported in the literature. Research is still being done to study the effect of different characteristics of wastewater, such as chloride content and alkalinity that may decrease or enhance ammonium recovery. More importantly, its adaptation for small-scale applications has not yet been explored despite the fact that the possibility to treat small volumes of wastewater and the recovery of resources and water on-site are very attractive. Considering the above, the objective of this project is to evaluate the feasibility of implementing such systems in small-scale industries. This work focuses on the stripping stage only. For this, it is essential to characterize the effluents from various sources and their effects on the ammonium recovery efficiency. A stripping-scrubbing system was reproduced at laboratory-scale. The effects of ammonium content, alkalinity, electrical conductivity, and pH were assessed in batch tests using synthetic solutions. From the results, a linear regression was performed to obtain a mathematical model to predict ammonia removal from the characteristics of a given effluent. This model was used as the core of a design model that evaluates the feasibility of ammonia stripping systems from the wastewater characteristics and a predefined removal target. Taking economic factors into account by means of an iterative optimization problem, it outputs the geometry, number of stripping units, and air supply that minimized both investment and operating costs. Since the target is predefined and the wastewater composition known, the income from selling a fertilizing salt is independent of the design. The model was calibrated based on synthetic solutions mimicking the composition of urine, composting leachate, and aquaculture wastewater. When validated against real effluents, it only was able to predict the removal efficiency of urine. An example case study addressing the techno-economic analysis of the operation of a small-scale urine treatment system was conducted. Although the operating costs approximately double (or more if scrubbing is considered) that of a conventional removal-only process, it is interesting from an environmental perspective. It is recommended to continue studying the effects of other components of wastewater that could impact the process. Further research must be done reducing operational costs in order to make these options economically interesting.

<p>New possibilities of nutrients removal by additions of magnesium compounds were studied in primary treatment and supernatant of side stream in wastewater treatment. The precipitation product from this method is magnesium ammonium phosphate (MAP) socalled struvite. High efficiencies on NH4-N and PO4-P removals have been demonstrated up to over 90 % respectively in side stream from dewatering of digested sludge. In order to find out the nutrient removal efficiency in raw wastewater and the feasibility of MAP recycling in wastewater treatment, the postulations of combining MAP and nitrification-denitrification process, and MAP and partial nitritation-anmmox process were carried out by experimental works in the laboratory at Land and Water Resources Department, KTH. It was found that 92-97 % of PO4-P and 57 % of NH4-N were removed from raw wastewater by Mg2+ addition at pH10 to pH10.5. The research work revealed that recycling of MAP by nitrification-denitrification and partial nitritation-anmmox processes may be a feasibly process combination. In MAP and nitrification -denitrification process, the released ammonium was mostly oxidized to nitrate in nitrification phase and ready for denitrification. Based on presented results on MAP and partial nitritation-anmmox process, it was found that the released ammonium was consumed by anammox bacteria.</p>