Thesis (Th. M.)--Dallas Theological Seminary, 2002. / Includes bibliographical references (leaves [61]-65).

Thesis (Th. M.)--Dallas Theological Seminary, 2002. / Includes bibliographical references (leaves [61]-65).

Thesis (Th. M.)--Dallas Theological Seminary, 2002. / Includes bibliographical references (leaves [61]-65).

Thesis (MSc.(Pharmacology)--Faculty of Health Sciences)-University of Pretoria, 2008.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Environmental problems have become increasingly acute and frequent in recent decades, mainly due to unrestrained population growth and increased industrial activity. The textile industry merits especial attention in this context, since large volumes of water are used in finishing processes, which results in substantial quantities of liquid effluent. The objective of this work was to determine the optimum conditions for adsorption/desorption of reactive dyes, employing humin in batch experiments and with fixed bed columns where the humin was immobilized on silicate. Immobilization was confirmed by Fourier transform infrared analysis. Adsorption isotherms were constructed, and the kinetic data fitted to literature models. Multiple adsorption/desorption cycles were investigated using the fixed bed column. Results of the batch experiments showed that adsorption of Reactive Red 120 (RR 120) and Reactive Orange 16 (RO 16) by humin was most effective at pH 1.0, while optimum adsorption of Reactive Blue 2 (RB 2) was obtained at pH 2.0. Adsorption equilibria were rapidly achieved for all initial dye concentrations tested. Temperature measurements indicated that all of the processes were exothermic and could be described using a pseudo-second order kinetic model. The Freundlich isotherm provided the best fit for RO 16, while the Langmuir isotherm best described the adsorption of RR 120 and RB 2. In column experiments, adsorption efficiencies of 96.2 %, 62.1 % and 44.6 % were obtained for RR 120, RO 16 and RB 2, respectively, while the corresponding desorption efficiencies for these dyes were 81.4 %, 51.3 % and 23.7 %, respectively. Reductions in retention efficiency of 16 % (RO 16), 21 % (RR 120) and 26 % (RB 2) were observed between the first and second cycles. Reductions between the second and third cycles were of 7 %, 1 % and 1 %, respectively, indicating that the column could be used in further cycles. Overall, the biosorbent showed excellent performance in removal of reactive dyes, with the additional advantage that it could be regenerated and reused. / Nas últimas décadas, os problemas ambientais têm se tornado cada vez mais críticos e frequentes, principalmente devido ao desmedido crescimento populacional e ao aumento da atividade industrial. A indústria têxtil merece atenção redobrada nesse contexto pela elevada quantidade de água utilizada nos processos de acabamento e geração de grandes volumes de efluentes líquidos. Esse trabalho teve como objetivo determinar as condições ótimas de adsorção / dessorção de corantes reativos utilizando experimentos em bateladas e colunas de leito fixo com humina imobilizada em silicato. A imobilização da humina foi verificada utilizando-se a técnica de espectroscopia de infravermelho com transformada de Fourrier. Isotermas de adsorção foram construídas e os dados cinéticos foram ajustados aos modelos encontrados na literatura. Resultados dos experimentos em batelada mostraram que a adsorção de Reactive Red 120 e Reactive Orange 16 por humina foi mais efetiva em pH 1,0 e pH 2 para o RB 2. E múltiplos ciclos de adsorção/dessorção foram testados nos experimentos em coluna de leito fixo com humina imobilizada em silicato. Os equilíbrios de adsorção foram alcançados rapidamente para todas as concentrações iniciais de corante utilizadas. Medições da temperatura indicaram que o processo foi exotérmico e descrito por um modelo cinético de pseudo-segunda ordem para todos os corantes. A isoterma de Freundlich se ajustou melhor para o RO 16, enquanto que a isoterma de Langmuir descreveu melhor a adsorção de RR 120 e do RB 2. Experimentos em coluna mostraram eficiências de adsorção de 96,2; 62,1 e 44,6% para o RR120, RO 16 e RB 2, respectivamente, bem como boa eficiência de dessorção de 81,4; 51,3 e 23,7% para os mesmos corantes, respectivamente. Uma diminuição da eficiência de retenção foi observada entre o primeiro e o segundo ciclo para o RO 16, RR 120 e RB 2 de aproximadamente 16, 21 e 26%, respectivamente. Entre o segundo e o terceiro ciclo de 7, 1 e 1% para os mesmos corantes. O que mostra a possibilidade de utilização da coluna em ciclos adicionais. O biossorvente apresenta um excelente desempenho na remoção de corantes reativos, com a vantagem que pode ser regenerado e reutilizado.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The use of chlorine and other compounds to treat water for human consumption has attracted the attention of the scientific community, due to reactions with natural organic matter (NOM) that could generate subproducts undesirable from the human health perspective. The trihalomethanes (THMs) are frequently found in water treatment systems, with chloroform (CHCl3), dichlorobromomethane (CHBrCl2), dibromochloromethane (CHBr2Cl) and bromoform (CHBr3) being the most common. Alternative adsorbents for removal of these compounds are sought, that are economically viable, easily disposed of and readily regenerated without losing their properties. The objective of the present work was to assess the performance of batch and fixed bed column systems, using humin in natura and immobilized on sodium silicate, respectively, for adsorption of the principal THMs found in water supply systems, as well as to determine the regeneration capacity of humin following thermal desorption. Kinetically, adsorption of THMs by humin followed a pseudo-second order reaction, with more than 50 % removal in the first 5 minutes for all compounds studied, and equilibrium described by the Freundlich model reached in 240 minutes. The THM adsorption results were significant at p < 0.05 for both batch (74.6 83.2 % removal) and column (99.7 % removal in optimized tests) experiments, and were significantly (p < 0.05) influenced by flow rate and bed height. The potential of humin for removal of the THMs was confirmed in thermal desorption tests, when increases in adsorption capacity (significant at p < 0.05) of 18.88 % (CHBr3), 18.09 % (CHBr2Cl), 24.16 % (CHBrCl2), 20.15 % (CHCl3) and 24.16 % (total trihalomethanes) were observed 17 between the first and fifth uses of the same adsorbent bed. The results demonstrate the potential of humin for removal of THMs. / A utilização de cloro e outros compostos nas Estações de Tratamento de Água para consumo humano têm atraído a atenção da comunidade científica devido as suas reações com a matéria orgânica natural (MON) as quais podem gerar subprodutos indesejáveis na perspectiva da saúde humana. Os trihalometanos são frequentemente encontrados nos sistemas de tratamento de água, sendo os mais comuns o clorofórmio (CHCl3), diclorobromometano (CHBrCl2), dibromoclorometano (CHBr2Cl) e bromofórmio (CHBr3). Adsorventes alternativos são pesquisados para remoção desses compostos, os quais sejam economicamente viáveis, de fácil disposição e que possam ser facilmente regenerados sem perda das suas propriedades. Assim, o objetivo do presente trabalho foi avaliar a performance da adsorção em batelada e em coluna de leito fixo usando humina in natura e imobilizada em sílica de sódio, respectivamente, na adsorção dos principais trihalometanos (THM) encontrados no sistema de abastecimento de água, bem como avaliar a capacidade de regeneração da mesma após a dessorção térmica. Cineticamente, a adsorção dos THM por humina pode ser descrita pelo modelo de pseudo segunda ordem, com capacidade de remoção de mais de 50% nos primeiros cinco minutos para todos os compostos em estudo. O modelo da isoterma de Freundlich foi o que melhor se ajustou com tempo de equilíbrio de 240 min. Os resultados da adsorção dos THM foram significativos p<0,05 para os ensaios em batelada (74,6-82,2% de remoção) e em coluna (99,7% de remoção para os testes otimizados), sendo influenciado significativamente pelo fluxo e altura do leito adsorvente. Os ensaios de dessorção térmica 15 comprovaram o potencial da humina na remoção dos THM, devido ao aumento significativo p<0,05 de 18,88, 18,09, 24,16, 20,15 e 24,16% para o CHBr3, CHBr2Cl, CHBrCl2, CHCl3 e trihalometanos totais respectivamente, na capacidade de adsorção da humina entre primeiro e o quinto ciclo de reuso do leito. O trabalho demonstra o potencial da humina na remoção de THM.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Environmental problems have become increasingly acute and frequent in recent decades, mainly due to unrestrained population growth and increased industrial activity. The textile industry merits especial attention in this context, since large volumes of water are used in finishing processes, which results in substantial quantities of liquid effluent. The objective of this work was to determine the optimum conditions for adsorption/desorption of reactive dyes, employing humin in batch experiments and with fixed bed columns where the humin was immobilized on silicate. Immobilization was confirmed by Fourier transform infrared analysis. Adsorption isotherms were constructed, and the kinetic data fitted to literature models. Multiple adsorption/desorption cycles were investigated using the fixed bed column. Results of the batch experiments showed that adsorption of Reactive Red 120 (RR 120) and Reactive Orange 16 (RO 16) by humin was most effective at pH 1.0, while optimum adsorption of Reactive Blue 2 (RB 2) was obtained at pH 2.0. Adsorption equilibria were rapidly achieved for all initial dye concentrations tested. Temperature measurements indicated that all of the processes were exothermic and could be described using a pseudo-second order kinetic model. The Freundlich isotherm provided the best fit for RO 16, while the Langmuir isotherm best described the adsorption of RR 120 and RB 2. In column experiments, adsorption efficiencies of 96.2 %, 62.1 % and 44.6 % were obtained for RR 120, RO 16 and RB 2, respectively, while the corresponding desorption efficiencies for these dyes were 81.4 %, 51.3 % and 23.7 %, respectively. Reductions in retention efficiency of 16 % (RO 16), 21 % (RR 120) and 26 % (RB 2) were observed between the first and second cycles. Reductions between the second and third cycles were of 7 %, 1 % and 1 %, respectively, indicating that the column could be used in further cycles. Overall, the biosorbent showed excellent performance in removal of reactive dyes, with the additional advantage that it could be regenerated and reused. : / Nas últimas décadas, os problemas ambientais têm se tornado cada vez mais críticos e frequentes, principalmente devido ao desmedido crescimento populacional e ao aumento da atividade industrial. A indústria têxtil merece atenção redobrada nesse contexto pela elevada quantidade de água utilizada nos processos de acabamento e geração de grandes volumes de efluentes líquidos. Esse trabalho teve como objetivo determinar as condições ótimas de adsorção / dessorção de corantes reativos utilizando experimentos em bateladas e colunas de leito fixo com humina imobilizada em silicato. A imobilização da humina foi verificada utilizando-se a técnica de espectroscopia de infravermelho com transformada de Fourrier. Isotermas de adsorção foram construídas e os dados cinéticos foram ajustados aos modelos encontrados na literatura. Resultados dos experimentos em batelada mostraram que a adsorção de Reactive Red 120 e Reactive Orange 16 por humina foi mais efetiva em pH 1,0 e pH 2 para o RB 2. E múltiplos ciclos de adsorção/dessorção foram testados nos experimentos em coluna de leito fixo com humina imobilizada em silicato. Os equilíbrios de adsorção foram alcançados rapidamente para todas as concentrações iniciais de corante utilizadas. Medições da temperatura indicaram que o processo foi exotérmico e descrito por um modelo cinético de pseudo-segunda ordem para todos os corantes. A isoterma de Freundlich se ajustou melhor para o RO 16, enquanto que a isoterma de Langmuir descreveu melhor a adsorção de RR 120 e do RB 2. Experimentos em coluna mostraram eficiências de adsorção de 96,2; 62,1 e 44,6% para o RR120, RO 16 e RB 2, respectivamente, bem como boa eficiência de dessorção de 81,4; 51,3 e 23,7% para os mesmos corantes, respectivamente. Uma diminuição da eficiência de retenção foi observada entre o primeiro e o segundo ciclo para o RO 16, RR 120 e RB 2 de aproximadamente 16, 21 e 26%, respectivamente. Entre o segundo e o terceiro ciclo de 7, 1 e 1% para os mesmos corantes. O que mostra a possibilidade de utilização da coluna em ciclos adicionais. O biossorvente apresenta um excelente desempenho na remoção de corantes reativos, com a vantagem que pode ser regenerado e reutilizado.

The objective of this study was to use pedological evidence in conjunction with Geographic Information Systems, and soil physical and chemical analyses as means to better understand the agricultural landscape surrounding the ancient Maya city of Uci. Specifically, the query of this thesis is to determine whether there is an association between settlement density and soil resources, and what relationship if any there is between the ancient sacbe of Uci and its surrounding agricultural potential. Stable carbon isotope analysis of the humin fraction of the soil organic matter was conducted on several profiles from karst depressions known as rejolladas near the site center, and from a select number of sufficiently deep profiles along and surrounding the ancient sacbe, and from beneath ancient structures. A strong C isotopic signature of ancient C4 crops was found in a limited number of profiles while a majority of the profiles showed no evidence, or little to inconclusive evidence due to a mixture of C3 and C4 plants in the natural landscape. A majority of the soils surrounding Uci are shallow to extremely shallow and many profiles sampled and studied did not allow for C isotopic analysis. Isotopic evidence along with other soil chemical and physical characteristics suggests that settlement density was linked to soil resources, specifically in the case of the rejolladas proximity to the Uci site center. However, it does not appear that the construction and location of the sacbe was linked to its surrounding soil resources or agricultural potential even though ancient maize crops may have been cultivated sporadically close to the sacbe and nearby structures. The soil resources of Uci are not conducive to the production of large maize crops and the ancient Maya of this area likely utilized maize along with alternative crops, arboriculture, wild game and trade to sustain its population.

This work has like objective develop a methodology for determination of triclosan (2,4,4' tricloro-2 -hidroxidifenol ether), in natural waters through the carbon paste electrode use chemically modified with humin, insoluble fraction of the peat obtained from turf of Saint Amaro of Brotas. The triclosan is commercially known like Irgasan DP 300®, is a bactericidal of ample spectrum, used broadly in products of personal hygiene, in the industry textile and pharmaceutical. Triclosan is introduced in the environment through the discarding of domestic, industrial sewer and for packings of hygienic cleaning products. It is considered low toxicity, however his metabolite are more lipofílic and more persistent in the aquatic environment, among them are: metyl-triclosan, chlorophenol, quinone and the dioxin. The inquiry of the physical-chemical characteristics and the capacity of absorption of triclosan by the paste of carbon and of the paste of carbon modified with humin were carried out using scanning electron microscopy coupled to energy dispersive system (SEM/EDS), electronic paramagnetic resonance (EPR) and by espectrofotometry. Results of SEM/EDS and EPR showed that there is a significant interaction of the triclosan with the paste of carbon modified with humin. The capacity of absorption of the paste of carbon modified with humin is bigger than to of the paste carbon, 4,76 ± 0.01 of paste. The study of the behavior electrodic of the triclosan in the electrode modified was developed employing itself to technical of cyclic voltammetry. The triclosan presented a peak of irreversible oxidation in 0,386 V (vs Ag/AgCl), under trial controlled by diffusion, with transference of an electron and a proton. Without no previous treatment of the sample, the approach developed by of screenprinted by square wave voltammetry, was what it got better resulted analytical, with limits of detection of 2,0 x 10-6 mol.L-1 and quantification 6,0 x 10-6 mol.L-1, with index of recuperation for 4,0 x 10-6 mol.L-1 of 100,4 %. The presence of triclosan was detected in waters of the river San Francisco in the concentration of 6,5 x 10-6 mol.L-1 by the approach voltammetry developed. The approach was validated comparing the results with the technical one of espectrofotometry, not having significant difference between the approaches for interval of confidence of 95 %. / Este trabalho tem como objetivo desenvolver uma metodologia para determinação de triclosan (2,4,4 tricloro-2 -hidroxidifenol éter), em águas naturais através do uso de eletrodo de pasta de carbono quimicamente modificado com humina, fração insolúvel da turfa obtida da turfeira de Santo Amaro das Brotas SE. O triclosan, é comercialmente conhecido como Irgasan DP 300®, é um bactericida de amplo espectro, usado amplamente em produtos de higiene pessoal, na indústria têxtil e farmacêutica. O triclosan é introduzido no meio ambiente através do descarte de esgoto doméstico, industrial e por embalagens de produtos de higienização. É considerado de baixa toxicidade, porém seus metabólitos são mais lipofílicos e mais persistentes no meio ambiente aquático, dentre eles estão: metiltriclosan, clorofenóis, quinonas e as dioxinas. A investigação das características físico-químicas e a capacidade de adsorção de triclosan pela pasta de carbono e da pasta de carbono modificada com humina foram realizadas usando microscopia eletrônica de varredura acoplada a sistema de energia dispersiva (MEV-EDS), ressonância eletrônica paramagnética nuclear (EPR) e por espectrofotometria. Resultados de MEV/EDS e EPR mostraram que há uma interação significativa do triclosan com a pasta de carbono modificada com humina. A capacidade de adsorção da pasta de carbono modificada com humina é de 4,76 ± 0,01 mg.g-1 de pasta. O estudo do comportamento eletródico do triclosan no eletrodo modificado foi desenvolvido empregando-se a técnica de voltametria cíclica. O triclosan apresentou um pico de oxidação irreversível em 0,386 V vs Ag/AgCl, sob processo controlado por difusão, com transferência de um elétron e um próton. Sem nenhum tratamento prévio da amostra, o método desenvolvido por voltametria de redissolução anódica por onda quadrada foi o que obteve melhores resultados analíticos, com limites de detecção de 2,0 x 10-6 mol.L-1 e de quantificação 6,0 x 10-6 mol.L-1, com recuperação para 4,0 x 10-6 mol.L-1 de 100,4 %. A presença de triclosan foi detectada em águas do rio São Francisco na concentração de 6,5 x 10-6 mol.L-1 pelo método voltamétrico desenvolvido. O método foi validado comparando os resultados com a técnica de espectrofotometria, não havendo diferença significativa entre os métodos para intervalo de confiança de 95 %.

The ancient Maya of the Classic period (1700-1050 B.P.) relied on maize agriculture to support their populations. The agricultural systems they employed to produce that maize varied in form and degree of intensity, with more productive forms of agriculture needed in the Late Classic period (1350-1050 B.P.) to sustain the peaking population. It is likely that the ancient systems of production agriculture contributed to environmental degradation that in turn contributed to the pressures that culminated in the collapse of the civilization. In this study, stable carbon isotope ratios contained in the soil organic matter were used to further investigate ancient maize cultivation in the Petexbatan region of Guatemala. Maize, a plant that uses the C4 photosynthetic pathway, leaves a different carbon (13C) isotopic signal in the soil than the C3 plants of the native forest vegetation. Soil profiles were collected from various landscape features around the Classic Maya site of Aguateca: bajos (or wetlands), control locations (areas not conducive to agriculture), defensible locations (areas within or near defensive walls), rehoyadas (natural karst depressions), and upland locations (level soils from across the rest of the landscape). The samples were tested for various chemical and physical properties, and the bulk soil organic matter and humin fractions were analyzed on a mass spectrometer to determine δ13C values. Graphs of the isotopic values were examined and the bulk and humin δ13C enrichment values for the landscape feature categories were compared statistically using ANOVA methods. We determined that the bulk and humin δ13C values of the Bajo and Rehoyada categories showed significantly greater enrichment than the Control, Defensible, and Upland locations. This enrichment was likely the result of sustained periods of maize cultivation, especially in the Rehoyadas. Surface soil bulk and humin δ13C enrichment values do not show that the Bajo or Rehoyada categories are influenced by modern C4 vegetation, nor do the enrichment values of the Control, Defensible or Upland soils. In other words, C3 vegetation dominates each of the landscape features today under natural conditions and probably would have done so anciently absent human interference. (Savanna soils are an exception, but none were identified in the study area.) When the thinner midslope (Backslope) Rehoyada profiles were compared to Control, Defensive, and Upland samples of similar depth, the Backslope Rehoyada profiles had significantly greater bulk δ13C enrichment values that may have resulted from maize cultivation. There was also a significant difference among the surface soil bulk and humin δ13C values of the Backslope Rehoyada, Control, Defensive, and Upland categories, though the reasons are less clear. Both the Bajos and Rehoyadas would have been valuable agricultural resources for maize production for the ancient Maya.