Thesis (M. Sc. Agriculture (Soil Science)) -- University of Limpopo, 2021 / Globally and in most parts of South Africa, there is a trend of increasing shrub encroachment in savanna rangelands. A number of studies have investigated the impact of shrub encroachment on soil organic carbon content (SOC) and soil organic carbon stocks (SOCs) in savannas. So far there is no clear consensus on whether shrub encroachment increases or decreases the level of SOC and SOCs, especially in semi arid savanna grasslands. Furthermore, knowledge on the effects of shrub encroachment on SOCs is largely restricted to the topsoil, as this is the part of the profile influenced by inputs and losses of soil organic matter. How shrub encroachment affects the vertical distribution of SOCs is rarely considered in the existing literature and the edaphic factors controlling SOCs with depth are poorly understood. The objectives of this study were (i) to quantify the vertical distribution of SOC and SOCs and (ii) to identify the edaphic factors controlling the vertical distribution of SOC and SOCs in a shrub-encroached savanna grassland sited on shallow plinthic soil. To achieve the objectives, a vegetation and soil survey of the savanna grassland was conducted whereby sampling areas were demarcated and characterized into open and shrub encroached grassland plots. In each encroachment level, three pits were randomly dug to the limiting layer on plots sited on the same soil type and similar topographic position. Soil samples were collected from the pits at depth intervals of 0-10, 10-20, 20-30, 30-40, 40-50, 50-60 and 60-70 cm. The collected soil samples were analyzed for chemical and physical properties in the laboratory. Correlation analysis was carried out to determine the relationship between SOC and SOCs, which were the variables of interest in this study and related controlling soil physicochemical properties. The results showed that SOC was significantly greater (P<0.05) in the shrub-encroached grassland compared to open grassland. Furthermore, the results revealed that SOC was on average 19 and 13% greater in the topsoil (0-20 cm) and subsoil (20-70 cm) of shrub encroached grassland compared to open grassland. The greater SOC in the topsoil of the shrub-encroached grassland was mainly attributed to higher SOC inputs from plant litter and detritus derived from trees and grasses, which are the dominant plant life forms in savannas. In the topsoil, SOC and SOCs were positively correlated with extractable phosphorus (P) (r = 0.60; P < 0.05), while in the subsoil they were positively correlated ix with extractable phosphorus (r = 0.54), soil porosity (r = 0.52), extractable copper (r = 0.46), extractable zinc (r = 0.41), exchangeable calcium (r = 0.37) and negatively correlated with mean weight diameter (r = -0.43). Overall, SOC and SOCs under both shrub-encroached and open grasslands vertically decreased with soil depth. The results obtained highlighted that the factors controlling the level of SOC and SOCs differs in the topsoil and subsoil of the studied shrub encroached grassland. These findings suggest that in the shallow plinthic soil investigated in this study, SOC in the topsoil is controlled by the macronutrient P, while in the subsoil it is physically protected by soil aggregates and chemically stabilized via complexation interactions with exchangeable cations and heavy metals. In-depth understanding of the physico-chemical factors controlling SOC storage is critical to foster management practices that will improve the cycling of SOC in shrub-encroached savanna grasslands.

Cette thèse présente le devenir atmosphérique de trois alcools saturés CH3(CH2)4OH, CH3CH2CH2CH(OH)CH3 et (C2H5)2CHOH, de trois esters CH3CH2CH2C(O)OC2H5, CH3CH2C(O)OC2H5 et CH3CH2C(O)OCH2CH2CH3 ainsi que d’un HFC insaturé (CF3)2C=CH2 avec OH et Cl. La constante de vitesse de la réaction avec OH de ces composés a été déterminée en fonction de la température (253 – 373 K), en utilisant la technique Photolyse Laser Pulsée couplée à la Fluorescence Induite par Laser (PLP-FIL). La constante de vitesse de la réaction de OH et de Cl avec les alcools, les esters et l’hexafluoroisobutène (HFIB) a été également déterminée à température ambiante en utilisant la chambre de simulation atmosphérique. Pour la réaction du radical OH avec le HFC et de l’atome Cl avec les esters et le HFC, il s’agit d’une première détermination des constantes de vitesse. Les constantes de vitesse obtenues sont comparées à la littérature, la réactivité des alcools et des esters a été discutée. Enfin, le calcul des durées de vie de ces composés ainsi que la recherche de leurs produits éventuels ont permis d’évaluer l’impact atmosphérique de ces composés sur l’environnement. / In this thesis we report the atmospheric fate of three saturated alcohols: CH3(CH2)4OH, CH3CH2CH2CH(OH)CH3 and (C2H5)2CHOH, three esters: CH3CH2CH2C(O)OC2H5, CH3CH2COOC2H5 and CH3CH2COOCH2CH2CH3 and an unsaturated HFC with OH radicals and Cl atoms. The rate coefficients of OH reactions with these compounds have been measured over the temperature range 253 – 373 K, using the Pulsed Laser Photolysis – Laser Induced Fluorescence technique (PLP-LIF). Moreover the rate coefficients of OH and Cl reactions with alcohols, esters and hexafluoroisobutene (HFIB) have been determined at room temperature, using smog chambers. For the reaction of OH radicals with HFIB and Cl atoms with esters and HFIB, the rate coefficients obtained in this study present the first determination. The results have been compared with the literature and the reactivity of the compounds has been discussed. Finally, the atmospheric lifetimes of these compounds have been determined and the OH oxidation products have been identified, which allows us to estimate the atmospheric impact of these compounds.

Indiana University-Purdue University Indianapolis (IUPUI) / Eagle Creek Reservoir (ECR), located in the Midwestern U.S., is a freshwater limnic system plagued by seasonal Harmful Algal Blooms (HABs) which generate water-fouling Geosmin (GSM) and 2-Methylisoborneol (MIB) Taste and Odor (T&O) compounds. Past investigations of T&O event dynamics have identified Actinomycetes as responsible for MIB production and several genera of cyanobacteria for GSM production. During 2018, a temporally and spatially expansive sampling regimen of the reservoir was carried out and a battery of biological, chemical, physical, and hyperspectral experiments performed. The resulting data was analyzed using time series, cross-correlation, lag time, and multivariate analyses as well as machine learning algorithms to pick apart and interrogate any relationships between HABs, T&O events, and environmental parameters. The results show that local weather and watershed conditions exert significant control over the state of the reservoir and the behavior of the algal community. GSM and MIB peaked during early May under well-mixed, cold, and nutrient-rich water column conditions, then declined under summer thermal stratification before making a small resurgence during late season mixing. Bloom die-off and decay was effectively ruled out as a mechanism controlling T&O concentrations, and no links were found between T&O concentrations and algal biomass. Strong evidence was found that GSM/MIB concentrations were a response by bloom microbes to changing nutrient conditions within the reservoir, and it was determined that nutrient fluxes from the watershed 30-40 days prior to peak T&O concentrations are likely instrumental in the development of the slow- ix growing microbes characteristic of the reservoir. Attempts were made to assess spatial and temporal variability but no significant spatial differences were identified; differences between sampling sites were far smaller than differences between different sampling dates. The findings here add to the growing body of literature showing T&O and HAB dynamics are more closely linked to the relative abundance and speciation of nutrients than other parameters. Additionally, these findings carry important implications for the management of ECR and other similar freshwater reservoirs while highlighting the importance of reducing watershed eutrophication.

<p>Additive manufacturing (AM) can be an advantageous substitute to various traditional manufacturing techniques. Due to the ability to rapidly create products, AM has been traditionally used to prototype more efficiently. As the industry has progressed, however, use cases have gone beyond prototyping into production of complex parts with unique geometries. Amongst the most popular of AM processes is fused deposition modeling (FDM). FDM fabricates products through an extrusion technique where plastic filament is heated to the glass transition temperature and extruded layer by layer onto a build platform to construct the desired part. The purpose of this research is to elaborate on the potential of this technology, while considering environmental impact as it becomes more widespread throughout industry, research, and academia.</p> <p>Although AM consumes resources more conservatively than traditional methodologies, it is not free from having environmental impacts. Several studies have shown that additive manufacturing can affect human and environmental health by emitting particles of a dynamic size range into the surrounding environment during a print. To begin this study, chapters investigate emission profiles and characterization of emissions from FDM 3D printers with the intention of developing a better understanding of the impact from such devices. Background work is done to confirm the occurrence of particle emission from FDM using acrylonitrile butadiene styrene (ABS) plastic filament. An aluminum bodied 3D printer is enclosed in a chamber and placed in a Class 1 cleanroom where measurements are conducted using high temporal resolution electrical low-pressure impactor (ELPI), scanning mobility particle sizer (SMPS), and optical particle sizer (OPS), which combined measure particles of a size range 6-500nm. Tests were done using the NIST standard test part and a honeycomb infill cube. Results from this study show that particle emissions are closely related to filament residence time in the extruder while less related to extruding speed. An initial spike of particle concentration is observed immediately after printing, which is likely a result of the long time required to heat the extruder and bed to the desired temperature. Upon conclusion of this study, it is theorized that particles may be formed through vapor condensation and coagulation after being released into the surrounding environment.</p> <p>With confirmation of FDM ultrafine particle emission at notable concentrations, an effort was consequently placed on diagnosing the primary cause of emission and energy consumption based on developed hypotheses. Experimental data suggests that particle emission is mainly the result of condensing and agglomerating semi-volatile organic compounds. The initial emission spike occurs when there is dripping of semi-liquid filament from the heated nozzle and/or residue left in the nozzle between prints; this supports the previously stated hypothesis regarding residence time. However, the study shows that while printing speed and material flow influence particle emission rate, the effects from these factors are relatively insignificant. Power profile analysis indicates that print bed heating and component temperature maintaining are the leading contributors to energy consumption for FDM printers, making time the primary variable driving energy input.</p> <p>To better understand the severity of FDM emissions, further investigation is necessary to diligence the makeup of the process output flows. By collecting exhaust discharge from a Makerbot Replicator 2x printing ABS filament and diffusing it through a type 1 water solution, we are able to investigate the chemical makeup of these compounds. Additional exploration is done by performing a filament wash to investigate emissions that may already be present before extrusion. Using solid phase micro-extraction, contaminants are studied using gas chromatography mass spectrometry (GCMS) thermal desorption. Characterization of the collected emission offers more comprehensive knowledge of the environmental and human health impacts of this AM process.</p> <p>Classification of the environmental performance of various manufacturing technologies can be achieved by analyzing their input and output material, as well as energy flows. The unit process life cycle inventory (UPLCI) is a proficient approach to developing reusable models capable of calculating these flows. The UPLCI models can be connected to estimate the total material and energy consumption of, and emissions from, product manufacturing based on a process plan. The final chapter focuses on using the knowledge gained from this work in developing UPLCI model methodology for FDM, and applying it further to the second most widely used AM process: stereolithography (SLA). The model created for the FDM study considers material input/output flows from ABS plastic filament. Energy input/output flows come from the running printer, step motors, heated build plate, and heated extruder. SLA also fabricates parts layer by layer, but by the use of a photosensitive liquid resin which solidifies when cured under the exposure of ultraviolet light. Model material input/output flows are sourced from the photosensitive liquid resin, while energy input/output flows are generated from (i) the projector used as the ultraviolet light source and (ii) the step motors. As shown in this work, energy flow is mostly time dependent; material flows, on the other hand, rely more on the nature of the fabrication process. While a focus on FDM is asserted throughout this study, the developed UPLCI models show how conclusions drawn from this work can be applied to different forms of AM processes in future work.</p>

Acute indoor concentrations of benzene and ethanol were evaluated in the California Polytechnic State University San Luis Obispo’s pilot winery workroom. Air samples were collected during four different wine-making activities: fermentation, fermentation with Brix content testing, post-alcoholic fermentation pressing, and storage/finishing. Average workroom benzene concentrations ranged from 0.05 to 0.12 mg/m3. Ethanol concentrations in the winery workroom varied with the activity, ranging from 0.9 to 12 mg/m3. Pressing and fermentation with Brix content testing both led to higher indoor ethanol concentrations than fermentation without Brix content testing and storage/finishing. Tracer gas decay air exchange tests were conducted to determine the air exchange rate of the winery workroom. A single-space mass-balance model was used to estimate the air exchange rate for the entire workroom. The calculated air exchange rates were correlated with wind speeds and wind direction to create a linear model estimating air exchange rates based on wind speed. These air exchange rates and the indoor concentrations of ethanol were used with the single-space mass-balance model to calculate an ethanol emission rate for each activity. Total estimated ethanol emissions for the four activities were 3.1 lbs. ethanol per 1000 gallons of wine produced.

Black carbon (BC) and polycyclic aromatic hydrocarbons (PAHs) are two atmospheric pollutants produced by motor vehicles using carbonaceous fuels. As a part of the Mexico City Project, measurements of BC, PPAHs and many other gas- and particle-phase emissions were measured in Mexico City using a mobile laboratory during the Mexico City Metropolitan Area field campaign in April 2003 (MCMA-2003). The main goal of this research is to estimate emissions of BC and particulate PAHs (PPAHs) for Mexico City's vehicle fleet. The emissions of gas-phase pollutants such as carbon monoxide (CO), total nitrogen oxides (NOy) and volatile organic compounds (VOC) are also estimated. The mobile lab has previously been used to chase vehicles and measure their emissions, but analysis has traditionally focused on determining emission factors of individual vehicles associated with specific chasing events. The laboratory continuously samples ambient air from an inlet at the front of the van, and it is always "seeing" exhaust plumes from the vehicles around it while driving through traffic. We have developed an algorithm that automatically identifies the exhaust plume measurement points, which are then used as the basis for calculation of emission factors. In the nearly 90 hours of on-road sampling during the field campaign, we have identified ~30,000 exhaust measurement points. The large sample size enables us to estimate fleet-average emission factors and thus the emission inventory. Motor vehicles are estimated to emit annually 1,960 tons of BC, 56.2 tons of PPAHs, 1,320,000 tons of CO, 125,000 tons of NOy and 2440 tons of VOCs. The spatial and temporal patterns of BC and PPAHs in different locations with in MCMA are also studied. / Master of Science

Western Palm Beach County, FL is characterized by thick deposits organic soils at shallow depths. Because of their high void ratio and compressibility, these soils undergo large primary consolidation followed by extended periods of secondary compression causing excessive premature structural distress. Although soil stabilization has been largely used with remarkable results in soft, expansive and non-organic soils, limited research and practice exist in the implementation with highly organic soils. The main motivation of this research was to investigate the effects of cement stabilization on the compressibility behavior of organic rich soils, and develop mix design criteria for optimum cement contents necessary to induce the desired engineering behavior. This optimized mix design may provide guidelines for Deep Mixing Methods in organic soils. / by Juan Ramirez. / Thesis (M.S.C.S.)--Florida Atlantic University, 2009. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2009. Mode of access: World Wide Web.

A geração de resíduos sólidos é inerente ao desenvolvimento humano. O concreto armado é um dos materiais mais utilizados pelo homem e tem o cimento Portland como seu principal constituinte, o qual é produzido pela moagem de clínquer e gesso. O clínquer pode ser definido como um mineral artificial, obtido a partir das reações físico-químicas de calcário, argila e corretivos a altas temperaturas, em forno rotativo industrial, mediante a queima de combustíveis fósseis. No início da década de 70 foram realizadas as primeiras experiências de substituição de combustíveis fósseis por resíduos industriais nos Estados Unidos e países europeus, através da técnica denominada co-processamento, resultando na manufatura de um produto ao mesmo tempo em que os resíduos eram eliminados. O co-processamento se baseia na recuperação da energia disponível nos resíduos, substituindo parte daquela fornecida pelos combustíveis tradicionais ou na substituição de matérias-primas por resíduos com características químicas semelhantes àquelas normalmente empregadas na produção do clínquer. No estado de São Paulo as primeiras iniciativas para a utilização de resíduos industriais em fornos de clínquer ocorreram no início da década de 90. A partir de 1997 os órgãos ambientais de alguns estados brasileiros normatizaram procedimentos de licenciamento da atividade que foi, posteriormente, uniformizada por norma em âmbito federal. No ano de 1995 a Companhia de Cimento Ribeirão Grande/SP, Brasil, iniciou os procedimentos visando a substituição parcial dos combustíveis utilizados nos fornos rotativos por uma mistura de resíduos industriais. No período de 1995 a 2002 foram realizadas campanhas de amostragens em chaminés para avaliação das emissões atmosféricas dos dois fornos de produção de clínquer. A análise dos resultados obtidos associada às demais informações disponíveis de monitoramento das características das matérias-primas e combustíveis utilizados, bem como dos produtos finais, clínquer e cimento, não evidenciou alterações significativas nos níveis de emissões atmosféricas, sobretudo de material particulado e óxidos de enxofre, que pudessem ser associadas à utilização dos resíduos. Foram confirmadas as baixas emissões de inorgânicos e evidenciado o papel representado pelos resíduos no aporte dessas substâncias no sistema-forno, concluindo-se que esse aporte pode ser tão ou mais importante pela via da alimentação da farinha, cujos teores estão associados às características das jazidas minerais utilizadas. Foi também confirmada a alta eficiência do sistema-forno na destruição e remoção dos compostos orgânicos perigosos alimentados durante os testes de queima. / The production of industrial residues in inherent to the human development. The cement concrete is one of the most used material, manly the type portland cement, which is constituted by grinding clinker and gypsum together. Clinker can be defined as an artificial mineral obtained by applying physico-chemical reactions, at very high temperatures, to an appropriated mixture of limestone, clay, and some other materials in a rotating industrial kiln wich burns fossil fuels. In the early 1970 decade occurred the first experiences substituting fossil fuels by organic residues in USA and Europe through a technique named co-processing that results the production of certain manufacture while eliminates residues. Co-processing is based in the recovery of thermal energy and/or the mass of some constituents from some residues, with the same chemical characteristics of normal sources of energy, then economizing fuels and mass constituents and making better use of residues, otherwise useless and environmentally polluters. In the state of São Paulo this practice began in early 1990 decade and by 1997 it was started the standardization of the rules for its use in some units of the federation. Later this activity was regulated by nationally approved standard rules. In 1995 the industry Companhia de Cimento Ribeirão Grande (CCRG), a cement plant located in the city of Ribeirão Grande, São Paulo state, Brazil, started procedures searching the partial substitution of the normal fuels by a mixture of industrial residues in its two rotating kilns. The gaseous emissions from the chimneys of these two clinker kilns were studied from 1995 to 2002 about the use of residues as part of the fuel. Analyses of the final results associated with other informations concerning to the quality of raw minerals, fuels and products did not show significant alterations in atmospheric emissions, mainly for particulate material and sulfur oxides, related with the use of residues. The emissions of inorganic continued to be low and not significantly altered by the presence of residues. It was possible to conclude that the alterations in inorganic emissions depend more from the quality of the raw minerals feed in the kilns, which is more difficult to control, than from the presence of residues being burn with the fuel. It was shown a high efficiency in the destruction of dangerous organic compounds feed in the cement kilns, under test conditions.

Thesis (Ph. D.)--Joint Program in Oceanography/Applied Ocean Science and Engineering (Massachusetts Institute of Technology, Dept. of Biology; and the Woods Hole Oceanographic Institution), 2013. / Cataloged from PDF version of thesis. / Includes bibliographical references. / The sinking flux of particles is an important removal mechanism of carbon from the surface ocean as part of the biological pump and can play a role in cycling of other chemical species. This work dealt with improving methods of measuring particle export and measuring export on different scales to assess its spatial variability. First, the assumption of ²³⁸U linearity with salinity, used in the ²³⁸U-²³⁴Th method, was reevaluated using a large sample set over a wide salinity range. Next, neutrally buoyant and surface-tethered sediment traps were compared during a three-year time series in the subtropical Atlantic. This study suggested that previously observed imbalances between carbon stocks and fluxes in this region are not due to undersampling by traps. To assess regional variability of particle export, surface and water-column measurements of ²³⁴Th were combined for the first time to measure fluxes on ~20 km scales. Attempts to relate surface properties to particle export were complicated by the temporal decoupling of production and export. Finally, particle export from ²³⁴Th was measured on transects of the Atlantic Ocean to evaluate basin-scale export variability. High-resolution sampling through the water-column allowed for the identification of unique ²³⁴Th features in the intermediate water column. / by Stephanie Anne Owens. / Ph.D.

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