Increased water- and fertilizer-use-efficiency in containerized crop production, via reduced water loss, enhances crop-available nutrients while reducing non-point source agrichemical contributions in accordance with regulatory standards. Previous studies detailed nutrient leaching patterns throughout crop production seasons, leaving little known about water and dissolved nutrient (solute) movement through soilless substrates during irrigation. The following experiments evaluated fundamental water and solute transport principles through pine-bark based substrates. 1) Ilex crenata Thunb. 'Bennett's Compactum' were grown in 2.7 L containers. Tensiometers detected wetting front (WF) movement throughout the substrate during irrigation. 2) Tracer solution (containing NO3-, PO43- and K+) and deionized water (DI) were applied to substrate-filled columns to characterize tracer breakthrough under saturated and unsaturated conditions. 3) Controlled-release fertilizer (CRF) was topdressed (surface-applied), incorporated (throughout substrate), dibbled (center of substrate) or not applied to fallow substrate, irrigated with DI and leachate analyzed to determine nutrient concentrations throughout irrigation. Tensiometers revealed that seasonal root growth affected substrate pre-irrigation moisture distribution. Wetting fronts channeled through the substrate before becoming thoroughly wetted. Tracer breakthrough occurred with less effluent volume under unsaturated conditions. Breakthrough of NO3- and PO43- was relatively conservative, though 37% of K+ was retained by the substrate. Leachate concentrations for topdressed and incorporated CRF peaked early (first 50mL effluent) before diminishing with continued leaching. Leachate concentrations for dibbled CRF initially increased (first 150mL leachate), plateaued and then diminished. These results show the relative rapidity which water and solutes move through pine-bark during irrigation and demonstrate methods for future research on within-irrigation solute transport. / Master of Science

Soil degradation is a common occurrence in Haiti that is mainly caused by the cultivation of marginal lands and deforestation, which both contribute to the excessive erosion rate seen in the country today. The Central Plateau of Haiti is a mountainous region in which a majority of the population is rural and practices subsistence agriculture on hillsides and steeply-sloping land. Essential plant nutrients, such as nitrogen (N) and phosphorus (P), are commonly a limiting factor in crop production, yet fertilizer is unavailable or is too expensive for smallholder farmers to purchase. This study was conducted to a) evaluate organic matter and nutrient stocks of various soils in the Central Plateau region, along with other chemical and physical characteristics and b) to evaluate the phosphorus-scavenging ability of commonly-grown crops to isolate those that may benefit subsequent smallholder yields. Soils from four locations in the Central Plateau were assessed for organic matter in labile and non-labile fractions as well as for cation exchange capacity (CEC), total organic carbon (C) and N, pH, texture, and other characteristics. Results indicated that most of the soil (92%) was contained within aggregates, and organic matter was mainly present in stable, slowly-decomposing fractions. Seven species were evaluated in a controlled-environment pot experiment for bulk and rhizosphere soil P and pH, plant dry weight, and above- and below-ground P tissue content as indicators of the species' ability to solubilize P from the soil. Velvet bean (Mucuna pruriens (L.) DC) produced the most biomass and was able to take up the most P, though lablab (Lablab purpureous (L.) Sweet), took up comparable amounts of P. / Master of Science / LTRA-6 (A CAPS program for the Central Plateau of Haiti)

Lanthanide-based nanoparticles are of interest for optical displays, catalysis, telecommunication, bio-imaging, magnetic resonance imaging, multimodal imaging, etc. These applications are possible partly because the preparation of lanthanide-based nanoparticles has made tremendous progress. Now, nanoparticles are routinely being made with a good control over size, crystal phase and even shape. Despite the achievements, little attention is given to the fundamental physical chemistry aspects, such as crystal structure, architecture, cation exchange, etc. The results of the study on the crystal structures of LnF3 nanoparticles show that the middle GdF3 and EuF3 nanoparticles have two crystal phases, which has then been tuned by doping with La3+ ions. However, the required doping level is very different from the bulk. While the results for the bulk are well explained by thermodynamic calculations, kinetics is actually responsible for the results of the undoped and doped GdF3 and EuF3 nanoparticles. The attempt to make LnF3 core-shell nanoparticles led to the finding of cation exchange, a phenomenon that upon exposure of LnF3 nanoparticles to an aqueous solution containing Ln3+ ions, the Ln3+ ions in the nanoparticles are replaced by the Ln3+ ions in the solution. The consequence of the cation exchange is that LnF3 core-shell nanoparticles are unlikely to form in aqueous media using a core-shell synthesis procedure. It has also been verified that nanoparticles synthesized using an alloy procedure do not always have an alloy structure. This means that the core-shell and alloy structure of nanoparticles in the literature may not be true. The investigation of the architecture of nanoparticles synthesized in aqueous media is extended to those synthesized in organic media. The dopant ion distribution in NaGdF4 nanoparticles has been examined. It has been found that they don’t have the generally assumed statistical dopant distribution. Instead, they have a gradient structure with one type of Ln3+ ions more concentrated towards the center and the other type more concentrated towards the surface of the nanoparticles. With the understanding of these physical insights, lanthanide-based core-shell nanoparticles are prepared using the cation exchange. These core-shell nanoparticles containing a photoluminscent core and a paramagnetic shell are promising candidates for multimodal imaging. / Graduate

O emprego de sistemas em fluxo com multi-impulsão são destaques quanto ao volume de efluentes gerados e a possibilidade de mecanização, operando em condições dinâmicas. A utilização de microbombas solenoide é potencial em processos de adsorção/dessorção de analitos, pois desempenham o fluxo pulsado, e quando operadas em conjunto com o estabelecimento da condição de leito fluidizado, contribuem para o aumento da eficiência de adsorção/dessorção. O objetivo geral deste trabalho foi desenvolver e avaliar sistemas de extração sólido-líquido e análises química em fluxo, explorando fluxos pulsados e o estabelecimento da condição de leito fluidizado, visando melhorar a eficiência de interação da amostra e reagente. Para tanto, foram desenvolvidos sistemas em fluxo com multi-impulsão associados ao uso de colunas de leito fluidizado. 1) Sistema para determinação da capacidade de adsorção de fósforo; determinação do fósforo remanescente (P-rem) em solos; 2) Sistema para determinação da capacidade de troca catiônica (CTC) de solos, avaliando a adsorção e a dessorção de analitos. Foi demonstrado que o fósforo e o cálcio contidos em solução são eficientemente adsorvidos/dessorvidos pelo solo, reduzindo significativamente os efeitos de aumento de pressão com o estabelecimento do leito fluidizado (fluidização pulsada) nas colunas contendo 50 mg de amostras de solo. A substituição do fluxo pulsado (microbomba solenoide) pelo fluxo contínuo (bomba peristáltica) limitou a interação sólido-líquido, pois estabeleceu caminhos preferenciais, desfavorecendo as condições de mistura. A utilização das microbombas solenoide em conjunto com a fluidização das amostras de solo, apresentou vantagens quanto à diminuição da quantidade de massa de solo requerida (entre 100 e 200 vezes), redução do consumo de reagentes e resíduos gerados (40 vezes), demonstrando o potencial do sistema em fluxo proposto por ser uma alternativa ambientalmente adequada. Os sistemas propostos são versáteis e facilmente adaptados para outros estudos de extração / Multi-pumping flow systems are highlights on the volume of effluents generated and mechanization, operating in dynamic conditions. Solenoid micro-pumps are potential in the analyte adsorption/desorption processes, because they play the pulsed flow and when operated in conjunction with the establishment of the fluidized bed condition, contribute to the increase of the adsorption/desorption efficiency. The objective of this work was to develop and evaluate solid-liquid extraction and flow analysis systems, exploring pulsed flows and establishing the fluidized bed condition in order to improve the solid-liquid interaction efficiency. It was developed multi-pumping flow systems associated with the establishment of the fluidized bed columns. 1) System for determination of phosphorus adsorption capacity; determination of the remaining phosphorus (P-rem) in soils; 2) System to determine the cation exchange capacity (CEC) of soils, evaluating the adsorption and desorption of analyte. It has been shown that the phosphorus and calcium contained in solution are efficiently adsorbed/desorbed by the soil, significantly reducing the effects of pressure increase with the establishment of the fluidized bed (pulsed fluidization) in the columns containing 50 mg of soil samples. The substitution of the pulsed flow (solenoid micro-pump) by the continuous flow (peristaltic pump) limited the solid-liquid interaction, since it established preferential pathways, undermining the mixing conditions. The use of the solenoid micro-pumps in conjunction with the fluidization of the soil samples presented advantages in terms of decreasing the amount of soil mass required (between 100 and 200-fold time), reducing the consumption of reagents, solutions and waste production (40-fold time), demonstrating the potential of this system to be an environmentally friendly alternative. The proposed systems are versatile and easily adapted to other extraction studies

Ethyl lactate (EL) plays a major role as green solvent and also a replacement for most petrochemical solvents. The esterification process of lactic acid and ethanol to produce EL is an equilibrium-limiting reaction and the selective removal of one of the reaction products can be improved using a membrane reactor and when coupled with a heterogeneous catalyst offers an opportunity for process intensification. This thesis investigates the batch process esterification reaction involving lactic acid (LA) and ethanol (EL) in the presence of a water selective membrane using different cation-exchange resin catalysts. The product was analysed using gas chromatograph coupled with mass spectrometry detector (GC-MS). The analytical methods used for the characterisation of the cation-exchange resins and membrane include Fourier transform infrared coupled with attenuated total reflectance (FTIR-ATR), scanning electron microscopy attached to energy dispersive analyser (SEM/EDAX), Liquid nitrogen physisorption and nuclear magnetic resonance (NMR) respectively. A novel method was developed for carrying out esterification reaction in a gaseous phase system using a flat sheet polymeric membrane. Prior to the esterification reaction, different carrier gases were tested with ceramic membrane to determine the suitable carrier gases for the analysis of esterification product. The four carrier gases used for the permeation test were argon (Ar), helium (He), carbon dioxide (CO2) and nitrogen (N2). A 15nm pore size commercially available tubular ceramic support, consisting of 77%Al2O3 and 23%TiO2 with the porosity of 45% was used for the carrier gas investigation. The support was modified with silica based on the sol-gel dip-coating techniques. The dip-coated membrane exhibited a higher molar flux with He (0.046mol m-2s-1) and Ar (0.037mol m-2s-1) with a much lower flux for N2 (0.037mol m-2s-1) and CO2 (0.035 mol m-2s-1) at 0.30 bar. Helium gas with the highest permeation rate were identified as the suitable carrier gas for the analysis of esterification product with GC-MS. The esterification reaction in the presence of four cation-exchange resins to produce ethyl lactate was carried out between 60-160 oC in a batch and membrane processes to determine the effectiveness resin catalysts for LA esterification. The effect of external mass transfer diffusion limitation between the liquid components and the resin catalysts was avoided by increasing the agitation time of the esterification reaction. The percentage conversion rate of the lactic acid feed from the batch process esterification was found to be in the range of 98.6 to 99.8%. The reaction kinetics of the esterification reaction was described based on two simplified mechanisms of Langmuir Hinshelwood model to describe the adsorption components on the surface of the catalysts. The lactic acid feed gave a conversion rate of up to 100 % confirming the effectiveness of the acetate membrane impregnated resin catalysts in the selective removal of water for the separation of ethyl lactate. The significance of producing ethyl lactate through batch process intensified by a water-selective membrane processes can be recommended for industrial LA production.

O emprego de sistemas em fluxo com multi-impulsão são destaques quanto ao volume de efluentes gerados e a possibilidade de mecanização, operando em condições dinâmicas. A utilização de microbombas solenoide é potencial em processos de adsorção/dessorção de analitos, pois desempenham o fluxo pulsado, e quando operadas em conjunto com o estabelecimento da condição de leito fluidizado, contribuem para o aumento da eficiência de adsorção/dessorção. O objetivo geral deste trabalho foi desenvolver e avaliar sistemas de extração sólido-líquido e análises química em fluxo, explorando fluxos pulsados e o estabelecimento da condição de leito fluidizado, visando melhorar a eficiência de interação da amostra e reagente. Para tanto, foram desenvolvidos sistemas em fluxo com multi-impulsão associados ao uso de colunas de leito fluidizado. 1) Sistema para determinação da capacidade de adsorção de fósforo; determinação do fósforo remanescente (P-rem) em solos; 2) Sistema para determinação da capacidade de troca catiônica (CTC) de solos, avaliando a adsorção e a dessorção de analitos. Foi demonstrado que o fósforo e o cálcio contidos em solução são eficientemente adsorvidos/dessorvidos pelo solo, reduzindo significativamente os efeitos de aumento de pressão com o estabelecimento do leito fluidizado (fluidização pulsada) nas colunas contendo 50 mg de amostras de solo. A substituição do fluxo pulsado (microbomba solenoide) pelo fluxo contínuo (bomba peristáltica) limitou a interação sólido-líquido, pois estabeleceu caminhos preferenciais, desfavorecendo as condições de mistura. A utilização das microbombas solenoide em conjunto com a fluidização das amostras de solo, apresentou vantagens quanto à diminuição da quantidade de massa de solo requerida (entre 100 e 200 vezes), redução do consumo de reagentes e resíduos gerados (40 vezes), demonstrando o potencial do sistema em fluxo proposto por ser uma alternativa ambientalmente adequada. Os sistemas propostos são versáteis e facilmente adaptados para outros estudos de extração / Multi-pumping flow systems are highlights on the volume of effluents generated and mechanization, operating in dynamic conditions. Solenoid micro-pumps are potential in the analyte adsorption/desorption processes, because they play the pulsed flow and when operated in conjunction with the establishment of the fluidized bed condition, contribute to the increase of the adsorption/desorption efficiency. The objective of this work was to develop and evaluate solid-liquid extraction and flow analysis systems, exploring pulsed flows and establishing the fluidized bed condition in order to improve the solid-liquid interaction efficiency. It was developed multi-pumping flow systems associated with the establishment of the fluidized bed columns. 1) System for determination of phosphorus adsorption capacity; determination of the remaining phosphorus (P-rem) in soils; 2) System to determine the cation exchange capacity (CEC) of soils, evaluating the adsorption and desorption of analyte. It has been shown that the phosphorus and calcium contained in solution are efficiently adsorbed/desorbed by the soil, significantly reducing the effects of pressure increase with the establishment of the fluidized bed (pulsed fluidization) in the columns containing 50 mg of soil samples. The substitution of the pulsed flow (solenoid micro-pump) by the continuous flow (peristaltic pump) limited the solid-liquid interaction, since it established preferential pathways, undermining the mixing conditions. The use of the solenoid micro-pumps in conjunction with the fluidization of the soil samples presented advantages in terms of decreasing the amount of soil mass required (between 100 and 200-fold time), reducing the consumption of reagents, solutions and waste production (40-fold time), demonstrating the potential of this system to be an environmentally friendly alternative. The proposed systems are versatile and easily adapted to other extraction studies

No description available.

We developed a three-step colloidal synthesis of near-infrared active Cu-In-Se (CISe)/ZnS core/shell nanocrystals (NCs) via a sequential partial cation exchange. In the first step binary highly copper deficient Cu2‒xSe NCs were synthesized, followed by a partial cation exchange of copper to indium ions yielding CISe NCs. In order to enhance the stability and the photoluminescence (PL) properties of the NCs, a subsequent ZnS shell was grown, resulting in CISe/ZnS core/shell NCs. These core/shell hetero-NCs exhibited a dramatic increase in size and a restructuring to trigonal pyramidal particles. The reaction parameters, e.g. the Cu:Se-ratio, the temperature and the time were carefully tuned enabling a distinct control over the size and the composition of the NCs. By varying only the size of the CISe/ZnS NCs (from 9 to 18 nm) the PL spectra could be tuned covering a wide range with maxima from 990 nm to 1210 nm. Thus, in these experiments we demonstrate a clear dependence of the optical properties of these materials on their size and extend the PL range of CISe-based nanoparticles further to the infrared part of the spectrum. Furthermore, the relatively large size of these NCs allows their detailed structural analysis via electron microscopy techniques, which is particularly challenging in the case of small particles and especially important to relate the size, composition and crystal structure to their optoelectronic properties.

No description available.

No description available.