The Kvarntorp area, some 200 km SW of Stockholm, Sweden, is a former mining site for alum shale. Kvarntorpshögen is a refuse dump from the hydrocarbon extraction during 1940-1965. The area is also dotted by abandoned quarries, which most are water filled today. The area is divided into two watersheds; the central and the eastern. Frommestabäcken is the main watercourse flowing out of the central watershed while Frogestabäcken is the corresponding watercourse in the eastern watershed. These two watercourses have been sampled annually since 1994 by consulting companies for the municipality of Kumla. The sampling sites at Ulftorpsbäcken (main inlet to the central watershed) and at the outlet from Serpentindammssystemet (the water treatment system in the central watershed) was added to the sampling program in 1997 and 1996 respectively. Other consulting companies have sampled the groundwater around Kvarntorpshögen (in 2004) and the water in the lake Norrtorpssjön (in 2004), which is an old water filled quarry. The lake Norrtorpssjön has also been sampled as part of a project performed by Örebro University. This thesis is a compilation and evaluation of all this data but the main part will be given focused on seasonal variations. Samples have been analysed with regard to the metals Na, K, Ca, Mg, Fe, Al, Li, B, As, Cu, Ni, Zn, Co, Cr, Cd, Pb, Mo, Sr and U. Other analysed parameters were tot-N, tot-P, bicarbonate (alkalinity), sulphate, chloride and the parameters pH, electrical conductivity and COD(Mn). Samples of bottom fauna have also been collected in Frommestabäcken. Concentration of most metals increased in the surface water while passing the Kvarntorp area. High metal concentrations were found for example in some of the groundwater samples. Such high concentrations were not observed in the samples from Frommestabäcken or Frogestabäcken, indicating for example dilution of metals or immobilisation through precipitation or adsorption. Seasonal effects on the dissolution and precipitation/adsorption of compounds were observed at all annually sampled watercourses. One of these effects was the spring- and autumn circulation of the lake Norrtorpssjön. The lake forms a thermocline during summer which causes higher concentrations of metals beneath the thermocline. During circulation these concentrations mixes throughout the depth profile which affects the amount of elements that is transported from the lake via Frogestabäcken. During winter the highest concentrations of metals are expected near the surface of the lake since the surface is colder than the rest of the water mass.

Airborne aerosols are crucial atmospheric constituents that are involved in global climate change and human life qualities. Understanding the nature and magnitude of aerosol-cloud-precipitation interactions is critical in model predictions for atmospheric radiation budget and the water cycle. The interactions depend on a variety of factors including aerosol physicochemical complexity, cloud types, meteorological and thermodynamic regimes and data processing techniques. This PhD work is an effort to quantify the relationships among aerosol, clouds, and precipitation on both global and regional scales by using satellite retrievals and aircraft measurements. The first study examines spatial distributions of conversion rate of cloud water to rainwater in warm maritime clouds over the globe by using NASA A-Train satellite data. This study compares the time scale of the onset of precipitation with different aerosol categories defined by values of aerosol optical depth, fine mode fraction, and Ångstrom Exponent. The results indicate that conversion time scales are actually quite sensitive to lower tropospheric static stability (LTSS) and cloud liquid water path (LWP), in addition to aerosol type. Analysis shows that tropical Pacific Ocean is dominated by the highest average conversion rate while subtropical warm cloud regions (far northeastern Pacific Ocean, far southeastern Pacific Ocean, Western Africa coastal area) exhibit the opposite result. Conversion times are mostly shorter for lower LTSS regimes. When LTSS condition is fixed, higher conversion rates coincide with higher LWP and lower aerosol index categories. After a general global view of physical property quantifications, the rest of the presented PhD studies is focused on regional airborne observations, especially bulk cloud water chemistry and aerosol aqueous-phase reactions during the summertime off the California coast. Local air mass origins are categorized into three distinct types (ocean, ships, and land) with their influences on cloud water composition examined and implications of wet deposition discussed. Chemical analysis of cloud water samples indicates a wide pH range between 2.92 and 7.58, with an average as 4.46. The highest pH values were observed north of San Francisco, coincident with the strongest land mass influence (e.g. Si, B, and Cs). Conversely, the lowest pH values were observed south of San Francisco where there is heavy ship traffic, resulting in the highest concentrations of sulfate, nitrate, V, Fe, Al, P, Cd, Ti, Sb, P, and Mn. The acidic cloud environment with influences from various air mass types can affect the California coastal aquatic ecosystem since it can promote the conversion of micronutrients to more soluble forms. Beyond characterization of how regional air mass sources affect cloud water composition, aircraft cloud water collection provides precious information on tracking cloud processing with specific species such as oxalic acid, which is the most abundant dicarboxylic acid in tropospheric aerosols. Particular attention is given to explore relationship between detected metals with oxalate aqueous-phase production mechanisms. A number of case flights show that oxalate concentrations drop by nearly an order of magnitude relative to samples in the same vicinity with similar environmental and cloud physical conditions. Such a unique feature was consistent with an inverse relationship between oxalate and Fe. In order to examine the hypothesis that oxalate decreasing is potentially related to existing of Fe, chemistry box model simulations were conducted. The prediction results show that the loss of oxalate due to the photolysis of iron oxalato complexes is likely a significant oxalate sink in the study region due to the ubiquity of oxalate precursors, clouds, and metal emissions from ships, the ocean, and continental sources.

Magister Scientiae - MSc / The research was driven by a need to increase the knowledge base concerning wetland ecological responses, as well as to identify and evaluate the factors driving the functioning of the Franschhoek Trust Wetland. An ecohydrological study was undertaken in which vegetation cover, depth to groundwater, water and soil chemistry were monitored at 14 sites along three transects for a 12 month period. The parameters used include temperature, pH, electrical conductivity (EC), sodium, potassium, magnesium, calcium, iron, chloride, bicarbonate, sulphate, total nitrogen, ammonia, nitrate, nitrite and phosphorus. T-tests and Principal Component Analysis (PCA) were used to analyze trends and to express the relationship between abiotic factors and vegetation. / South Africa

The fuel industry in many parts of the world is blending alcohols with motor fuel either to extend the fuel or to improve its octane rating or both. Unfortunately alcohols are hygroscopic and as a result, water becomes a component of the fuel. This can lead to phase separation and the formation of a water-rich layer which could have serious corrosion consequences. In an attempt to understand the phase-splitting in alcohol-petrol-water blends, phase equilibria in ternary systems (alcohol-hydrocarbon-water) have been determined by experiment. The phase equilibria in these ternary systems are also discussed in terms of modern theories of liquid mixtures and the UNIQUAC theory is applied to the "ethanol + benzene + water" ternary system. The alcohols are all the C₁, C₂, C₃ and C₄ alcohols, and the hydrocarbons include those typically found in petrol, e.g. cyclohexane, benzene and substituted benzenes.

The purpose of this study is to characterize the water chemistry of Lake Gregory in Crestline, California. The collection of water samples occurred a short time after the end of the summer recreational season in the late fall. Several chemical parameters were measured in an effort to determine the overall water quality during this time.

Orientador: Fabiano Tomazini da Conceição / Resumo: O processo de denudação continental é controlado por fatores exógenos como intemperismo químico e erosão dos solos. Nesse processo, os sistemas fluviais desempenham um papel fundamental ao transportar os materiais sólidos e dissolvidos de seu local origem até atingir os oceanos. Visando investigar o balanço de denudação no Planalto Alcalino de Poços de Caldas – MG, adotou-se o método de balanço de massa geoquímico aplicado em escala de bacia hidrográfica, cuja análise quantitativa foi baseada nos fluxos de entrada e saída de elementos/compostos químicos em duas pequenas bacias hidrográficas situadas na borda noroeste do planalto. A média da descarga fluvial de sólidos dissolvidos foi estimada em 32,5 t km-2 ano-1 sendo que cerca de 40 % desse fluxo foi atribuído à deposição atmosférica (14,0 t km-2 ano-1) enquanto o restante foi associado ao intemperismo químico das rochas (18,5 t km2 ano-1), enquanto a descarga sólida, estimada em 5,4 t km-2 ano-1, demostra um sistema fluvial de baixo fluxo de sedimento. A taxa de intemperismo químico de fonólitos, tinguaítos e nefelina sienito de Poços de Caldas (2,1 m Ma) foi inferior à taxa de remoção dos solos do planalto (4,0 m Ma), revelando uma tendência de exumação das rochas do maciço a uma velocidade de 1,9 m Ma. A taxa de denudação do Planalto de Poços de Caldas foi reduzida com o passar do tempo geológico e sob o clima atual o relevo de Poços de Caldas tende a se manter na paisagem com pouca alteração em sua forma em um lento pro... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The continental denudation process is controlled by exogenous factors such as chemical weathering and soil erosion. In this process, river systems play a key role in transporting solid and dissolved materials from their source site to the oceans. In order to investigate the denudation balance in the Poços de Caldas Alkaline Plateau - MG, the geochemical mass balance method applied in a watershed scale was adopted, whose quantitative analysis was based on the input and output flows of chemical elements / compounds in two small watersheds situated on the northwest edge of the plateau. The average fluvial discharge of dissolved solids was estimated at 32.5 t km-2 year-1 and about 40% of this flow was attributed to atmospheric deposition (14.0 t km-2 year-1) while the remainder was associated with the chemical weathering of the rocks (18.5 t km-2 year-1), while the solid discharge estimated at 5.4 t km-2 year-1 demonstrates a low sediment flow river system. The chemical weathering rate of phonolites, tinguaites and nepheline syenite from Poços de Caldas (2.1 m Ma) was lower than the removal rate from the plateau soils (4.0 m Ma), revealing a tendency for rock mass exhumation at a speed of 1.9 m Ma. The denudation rate of the Poços de Caldas Plateau has been reduced over time and under current weather the relief of Poços de Caldas tends to remain in the landscape with little change in its form in a slow process of exhumation of the rocks. / Doutor

This thesis resulted from analysis of the water in Lake Wichita so that sources of water content could be determined.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Macadamia activated carbon (MAC) was impregnated with different concentrations of nitric acid and heated under reflux to improve the structural characteristics of the adsorbent for both considerable reduction and enhanced removal of Cr(VI). The chemical oxidation of ACs increased the surface oxygenated functional groups. Adsorption of Cr(VI) was carried out by varying parameters such as contact time, pH, concentration, and adsorbent dosage. The optimum operating conditions for the adsorption of Cr(VI) were pH 1, contact time 240 min, adsorbent dosage 10.67 g/L and Cr(VI) concentration 100 mg/L. The results showed that the Macadamia–based AC could be used efficiently for the treatment of chromium-containing solutions as a low-cost alternative compared to commercial AC and other adsorbent reported. The results showed that treated MAC performed better than untreated MAC, signifying the effect of secondary treatment on the enhanced removal of pollutants. Comparable to the application of ACs is the development of imprinting technologies for selective metal ion remediation in environmental samples. The combination of ion imprinting effects and functionalized carbon adsorbents produce materials which effectively remove and selectively recognize the target analyte. Macadamia activated carbon (MAC) was chemically pre-treated with nitric acid to generate carboxyl groups on the surface. The carboxylated MAC was then reacted with triethylenetetramine, N,N’-diisopropylcarbodiimide and CrCl3.6H2O to produce MACN20-imprinted sorbents (MACN20-IIP). MACN20-non imprinted (MACN20-NIP) counterparts were prepared, but Cr3+ was excluded in the synthesis. Alteration of surface structural characteristics and characterization of prepared adsorbents as confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, elemental analysis, Brunauer–Emmett–Teller and scanning electron microscopy. MACN20-IIP and MACN20-NIP adsorbents were evaluated for their Cr3+ uptake from aqueous solution in batch format. Maximum conditions were achieved at pH 5, 50 mg/L Cr(III) initial concentration and 33.33 g/L of adsorbent dosage. Presence of co-ions slightly diminished the removal of Cr(III) by MAC-IIP adsorbents. Application of the MACN20-IIP and MACN20-NIP on spiked acid mine drainage artificial sample led to collapse in the removal efficiency of MACN20-NIP while MACN20-IIP still showed good removal efficiencies. These results demonstrated that surface imprinting led to better adsorption rates and capacity. The data was better described by the Freundlich multilayer adsorption and pseudo-second order kinetic rate model. The combination of both the carbon sorbent and the surface-mediated IIPs effectively improved total chromium remediation in aqueous systems.

M. Tech (Department of Chemistry, Faculty of Applied and Computer Sciences) Vaal University of Technology. / Agricultural waste such as Macadamia nutshells are currently receiving more attention for removal of hexavalent chromium (Cr(VI)). However, they have low adsorption capabilities when used in their raw form. In this study, the efficiency of using Macadamia nutshell powder modified with different concentrations of hydrogen peroxide, grafted with 1,5’-diphenylcarbizide (DPC) for the removal of hexavalent chromium from aqueous solution was explored. The effects of various parameters controlling adsorption of Cr(VI) onto Macadamia adsorbents such as initial concentration, contact time, adsorbent concentration and pH were investigated. The optimal operating parameters for Macadamia nutshells treated with hydrogen peroxide (MHP) adsorbents were determined to be 75 mg/L, 3 h, 0.1 g and pH 1. The optimal operating parameters for Macadamia nutshells treated with hydrogen peroxide and grafted with 1,5’-diphenylcarbizide (MHPD) were determined to be 150 mg/L, 1 h, 0.1 g and pH 3. Fourier transform infrared (FTIR) spectroscopy of the adsorbents revealed that treated MHP showed amino groups attached to the adsorbents. Thermogravimetric analysis (TGA) revealed that the grafted material lowered the thermal stability from 180◦C to 300◦C due to volatile nature of DPC. The surface of the MHPD materials was rough due to grafting. The results showed that the 1,5’-diphenylcarbazide treatment improved the removal efficiency of Cr(VI).

Polyelectrolytes of opposite charge in aqueous solution can undergo a liquid-liquid phase separation known as complex coacervation. Complex coacervation of ampholytic proteins with oppositely charged polyelectrolytes is of increasing interest as it results in a protein rich phase that has potential applications in food science, protein therapeutics, protein purification, and biocatalysis. However, many globular proteins do not phase separate when mixed with an oppositely charged polyelectrolyte, and those that do phase separate do so over narrow concentration, pH, and ionic strength ranges. Much of the work that has been done on complex coacervates looks at polymer-polymer systems. While there have been some initial studies showing that proteins can undergo complex coacervation, the major design factor studied to date has been overall protein charge. The tools of genetic engineering, which allow the precise tuning and placement of charge have not been used to more fully understand the design criteria for protein complex coacervation. In this dissertation, we developed a model protein library based on green fluorescent protein (GFP) to study the impact of protein net charge and charge distribution on protein phase separation with polyelectrolytes. We developed a short, ionic polypeptide sequence (6-18 amino acids) that can drive the liquid-liquid phase separation of globular proteins. We characterize the phase behavior of the protein library with a homopolymer and diblock copolymer of similar chemistry to elucidate how protein design impacts macro- and microphase separation. In these phase characterization studies, differences in the nature of phase separation as well as the salt stability of the protein coacervates with the different polymer species are identified. We finally used this model protein library to study the effects of the protein design and phase separation behavior for coacervate-based applications including intracellular protein delivery, purification, and protein stabilization.